CN102023145B

CN102023145B - The method for evaluating adhesion property of film

Info

Publication number: CN102023145B
Application number: CN201010278031.5A
Authority: CN
Inventors: 川添雄太; 浅野哲
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2009-09-10
Filing date: 2010-09-08
Publication date: 2015-09-23
Anticipated expiration: 2030-09-08
Also published as: TWI479143B; JP2011080984A; KR20110027587A; KR101707424B1; CN102023145A; JP5577974B2; TW201129791A

Abstract

The present invention relates to the method for evaluating adhesion property of film.Method for evaluating adhesion property, it is evaluated the cohesive of film in laminated body, described laminated body be by do not conform to the material having the radiofluorescence by Ultraviolet radiation the 1st film and containing by Ultraviolet radiation the 2nd film of the material of radiofluorescence fit across hardening resin composition, and the solidification of this hardening resin composition is obtained, the method contains: across hardening resin composition by the 1st film and the laminating of the 2nd film, obtain the operation of laminated body; Through the stack layer body carry out illumination penetrate or laminate heated body by laminated body hardening resin composition solidification, obtain the operation of laminated body; Active energy beam is irradiated to the cured resin composition layer that have cured in laminated body, measures the operation of the fluorescence intensity of the fluorescence radiated by cured resin composition layer; Based on the measurement result of fluorescence intensity, evaluate the fusible operation of the 1st film and the 2nd film in laminated body.

Description

The method for evaluating adhesion property of film

Technical field

The present invention relates to the fusible method of evaluated for film.

Background technology

Be the fusible method for evaluating adhesion property of film in the laminated body of multiple film laminations of representative with polaroid as evaluation; a kind of method for evaluating adhesion property of film is disclosed in Japanese Unexamined Patent Publication 2008-299175 publication; its use cutter only cuts the diaphragm in polaroid, and to whether evaluating from this cut place stripping diaphragm.

Summary of the invention

But said method has cut the diaphragm in polaroid, and people require a kind of destruction without cutting the laminated body such as this diaphragm, to the method for evaluating adhesion property that intermembranous cohesive each in polaroid is evaluated.

In this condition, present inventor has performed further investigation, thus complete the present invention.

That is, the invention provides:

[1] method for evaluating adhesion property, it is the method for evaluating adhesion property evaluated the cohesive of film in laminated body, described laminated body is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the laminated body this hardening resin composition being solidified and obtains

The method contains following operation:

Across hardening resin composition by the 1st film and the laminating of the 2nd film, obtain the operation of laminated body;

Through the stack layer body carry out illumination penetrate or laminate heated body by laminated body hardening resin composition solidification, obtain the operation of laminated body;

Active energy beam (active エネ Le ギ mono-Line) is irradiated to the cured resin composition layer that have cured in laminated body, measures the operation of the fluorescence intensity of the fluorescence radiated by cured resin composition layer;

Based on the measurement result of fluorescence intensity, evaluate the fusible operation of the 1st film and the 2nd film in laminated body.

[2] method for evaluating adhesion property, it is the method for evaluating adhesion property evaluated the cohesive of film in laminated body, described laminated body is fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation, the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation and the 3rd film not containing the material of radiofluorescence by Ultraviolet radiation, and the laminated body this hardening resin composition being solidified and obtains

The method contains following operation:

Across the operation that the 1st film and the 2nd film are fitted by hardening resin composition;

The 2nd film, the opposition side of the side of having fitted the 1st film, across hardening resin composition laminating the 3rd film, obtain the operation of laminated body;

Active energy beam is irradiated to the cured resin composition layer that have cured in laminated body, measures the operation of the fluorescence intensity of the fluorescence radiated by cured resin composition layer;

Based on the measurement result of fluorescence intensity, evaluate the 1st film and the cohesive of the 2nd film and the fusible operation of the 2nd film and the 3rd film in laminated body.

[3] method for evaluating adhesion property Gen Ju [1], wherein, the 2nd film is polarizer.

[4] method for evaluating adhesion property Gen Ju [2], wherein, the 2nd film is polarizer.

[5] according to the method for evaluating adhesion property according to any one of [1] ~ [4], wherein, the 1st film is the diaphragm of protection the 2nd film.

[6] according to [2], [4] or the method for evaluating adhesion property described in [5], wherein, the 3rd film is the diaphragm of protection the 2nd film.

[7] according to the method for evaluating adhesion property according to any one of [1] ~ [6], wherein, the 1st film is the film containing at least a kind of resin be selected from acetyl cellulose resins, amorphous polyolefins resin, crystalline polyolefin resin and acrylic resin.

[8] according to the method for evaluating adhesion property according to any one of [1] ~ [7], wherein, the 2nd film is the film comprising polyvinyl alcohol resin.

[9] according to the method for evaluating adhesion property according to any one of [1] ~ [8], wherein, the 2nd film is the film of the resin comprising gas absorption quantity dichromatism pigment.

[10] according to method for evaluating adhesion property according to any one of [1] ~ [9], wherein, the 2nd film resin is carried out the film that uniaxial tension obtains.

[11] according to the method for evaluating adhesion property according to any one of [2] and [4] ~ [10], wherein, the 3rd film is the film containing at least a kind of resin be selected from acetyl cellulose resins, amorphous polyolefins resin, crystalline polyolefin resin and acrylic resin.

[12] according to the method for evaluating adhesion property according to any one of [1] ~ [11], wherein, hardening resin composition is containing monomer and/or oligomer and passes through irradiation active energy beam and the composition of the polymerization initiator of radiofluorescence.

[13] manufacture method of laminated body, it is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the manufacture method of the laminated body that this hardening resin composition is solidified

It is characterized in that, containing following operation:

(A) across hardening resin composition, the 1st film and the 2nd film are fitted, obtain the operation of laminated body;

(B) through the stack layer body carry out illumination penetrate or laminate heated body by laminated body hardening resin composition solidification, obtain the operation of laminated body;

(C) cured resin composition layer that have cured in laminated body is irradiated to the operation of active energy beam;

(D) active energy beam being subject to irradiating in above-mentioned operation (C) is measured, and the operation of the fluorescence intensity of the fluorescence radiated from cured resin composition layer;

(E) based on the fluorescence intensity measured in above-mentioned operation (D), evaluate the cohesive of the 1st film and the 2nd film in laminated body, and judge the operation of the quality quality of laminated body.

[14] manufacture method of laminated body, it is fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation, the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation and the 3rd film not containing the material of radiofluorescence by Ultraviolet radiation, and the manufacture method of the laminated body that this hardening resin composition is solidified

It is characterized in that, containing following operation:

The operation that 1st film and the 2nd film are fitted across hardening resin composition by (A '-1);

(A '-2) the 2nd film, the opposition side of the side of having fitted the 1st film, across hardening resin composition laminating the 3rd film, obtain the operation of laminated body;

(B ') through the stack layer body carry out illumination penetrate or laminate heated body by laminated body hardening resin composition solidification, obtain the operation of laminated body;

(C ') irradiates the operation of active energy beam to the cured resin composition layer that have cured in laminated body;

(D ') measures the active energy beam being subject to irradiating in above-mentioned operation (C '), and the operation of the fluorescence intensity of the fluorescence radiated from cured resin composition layer;

(E '), based on the fluorescence intensity measured in above-mentioned operation (D '), evaluates the 1st film and the cohesive of the 2nd film and the cohesive of the 2nd film and the 3rd film in laminated body, judges the operation of the good ring of laminated body quality.

According to the present invention, can when not destroying laminated body, easily evaluate the cohesive of film in laminated body, described laminated body is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the solidification of this hardening resin composition is obtained.

Accompanying drawing explanation

The schematic diagram of [Fig. 1] laminated body 1.

The schematic diagram of [Fig. 2] laminated body 5.

Symbol description

1,5 laminated body

2,8 the 2nd films

3,7,9 hardening resin compositions

4,10 the 1st films

6 the 3rd films

Embodiment

1st method for evaluating adhesion property of the present invention is the method for evaluating adhesion property evaluated the cohesive of film in laminated body, described laminated body is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the solidification of this hardening resin composition is obtained

It contains following operation:

2nd method for evaluating adhesion property of the present invention is the method for evaluating adhesion property evaluated the cohesive of film in laminated body, described laminated body is fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation, the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation and the 3rd film not containing the material of radiofluorescence by Ultraviolet radiation, and the solidification of this hardening resin composition is obtained

It contains following operation:

Be noted that in this manual, " laminated body " is the general name of any one of part or all laminated body that have cured of laminated body and the hardening resin composition do not solidified containing hardening resin composition.

< hardening resin composition >

Hardening resin composition is the resin combination penetrated by illumination or heated and solidify, and it contains monomer and/or oligomer, and is penetrated by illumination or heat and the polymerization initiator of radiofluorescence.(monomer)

Monomer can enumerate acrylic monomer and the epoxy monomer of polyester acrylate, urethane acrylate, PBAA ester, silicone acrylate (シリコ Application ア Network リレ mono-ト), epoxy acrylate etc.Monomer may also be referred to as singly measuring body, and it is the state of raw material when carrying out synthetic resin by curing reaction.

Epoxy monomer can enumerate hydrogenated epoxy system monomer, ester ring type epoxy monomer and aliphatic epoxy system monomer.The epoxy monomer of epoxy monomer preferably not containing aromatic rings.

Hydrogenated epoxy system monomer can by by aromatic epoxies system monomer in the presence of a catalyst, add pressure and carry out selective hydrogenation to obtain.Aromatic epoxies system monomer can enumerate the bis-phenol system monomer of the diglycidyl ether, the diglycidyl ether of Bisphenol F, the diglycidyl ether of bisphenol S etc. of bisphenol-A; Form the monomer of the formation phenolic resin varnish type epoxy resin of the monomer of phenol novolac epoxy resins (Off エノ mono-Le ノボラ Star Network エ Port キシ Trees fat), the monomer of formation cresol novolac epoxy (Network レゾ mono-Le ノボラ Star Network エ Port キシ Trees fat), the monomer of formation hydroxy benzaldehyde phenol novolac epoxy resins (ヒ De ロキシベ Application ズア Le デヒ De Off エノ mono-Le ノボラ Star Network エ Port キシ Trees fat) etc.; The multifunctional type epoxy monomer etc. of the glycidyl ether of tetrahydroxy benzene methylmethane, the glycidyl ether of tetrahydroxybenzophenone, epoxidation polyvinylphenol etc., the diglycidyl ether of preferred bisphenol-A.

Ester ring type epoxy monomer can enumerate the compound containing structure formula (I) Suo Shi.

(in formula, m represents the integer of 2 ~ 5, and the alkyl that the hydrogen atom contained in ring can be 1 ~ 4 by carbon number replaces, and also can remove formation key, with other group bonding by being formed 1 hydrogen atom contained in the methylene of ring).

Carbon number be 1 ~ 4 alkyl can enumerate methyl and ethyl.

As the structure shown in formula (I), preferred oxabicyclohexane structure (m=3), oxabicyclo heptane structure (m=4).

Compound containing structure formula (I) Suo Shi can enumerate following compound:

The 7-oxa-bicyclo[4.1.0 formic acid epoxycyclohexanecarboxylate that formula (II) represents

(in formula, R ¹and R ²represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other);

Two (the 7-oxa-bicyclo[4.1.0 formic ether) of the alkane glycol (ア Le カ Application ジォ mono-Le) that formula (III) represents;

(in formula, R ³and R ⁴represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other, n represents the integer of 2 ~ 20);

The epoxycyclohexyl-methyl ester of the alkane dicarboxylic acid that formula (IV) represents

(in formula, R ⁵and R ⁶represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other, p represents the integer of 2 ~ 20);

The epoxycyclohexyl-methyl ether of the polyglycol that formula (V) represents;

(in formula, R ⁷and R ⁸represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other, q represents the integer of 2 ~ 10);

The epoxycyclohexyl-methyl ether of the alkane glycol that formula (VI) represents;

(in formula, R ⁹and R ¹⁰represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other, r represents the integer of 2 ~ 20);

Diepoxy three spiro-compounds that formula (VII) represents

(in formula, R ¹¹and R ¹²represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other);

The diepoxy list spiro-compounds that formula (VIII) represents;

(in formula, R ¹³and R ¹⁴represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other);

The vinyl cyclohexene diepoxide that formula (IX) represents;

(in formula, R ¹⁵represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5);

The epoxycyclopentyl ether that formula (X) represents;

(in formula, R ¹⁶and R ¹⁷represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5 independently of each other);

The diepoxy tristane that formula (XI) represents.

(in formula, R ¹⁸represent that hydrogen atom or carbon number are the straight-chain alkyl of 1 ~ 5),

In these, preferably:

Ester (the R generated by 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol ¹and R ²the compound represented by formula (II) for hydrogen atom),

Ester (the R generated by 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl-7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol ¹4 are bonded in, R for methyl ²for methyl and the compound represented by formula (II) be bonded on 4),

Ester (the R generated by 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethylene glycol ³and R ⁴the compound represented by formula (III) for hydrogen atom, n are 2),

Ester (the R generated by (7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol and hexane diacid ⁵and R ⁶the compound represented by formula (IV) for hydrogen atom, p are 2),

Ester (the R generated by (4-methyl-7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol and hexane diacid ⁵4 are bonded in, R for methyl ⁶for methyl and the p be bonded on 4 be 2 the compound represented by formula (IV)) and

Ether (the R generated by (7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol and 1,2-ethylene glycol ⁹and R ¹⁰for hydrogen atom, r is the compound represented by formula (VI) of 2).

Aliphatic epoxy system monomer can enumerate many glycidyl ethers of aliphatic polyol and its alkylene oxide adduct.Specifically, can 1 be enumerated, the triglycidyl group ether of the diglycidyl ether of 4-butylene glycol, the diglycidyl ether of 1,6-hexanediol, glycerine, the triglycidyl group ether of trimethylolpropane, the diglycidyl ether of polyglycol, the diglycidyl ether of propylene glycol.

(oligomer)

Oligomer also referred to as being low polymer, the resin of its to be the degree of polymerization be lower state of the degree of polymerization of about 2 ~ 20.Oligomer can enumerate the oligomer of above-mentioned monomer, the epoxy oligomer preferably not containing aromatic rings.Epoxy oligomer not containing aromatic rings refers to come from structure and does not contain aromatic rings and the oligomer with the monomer of epoxy radicals.

The epoxide equivalent of monomer and oligomer is generally 30 ~ 3000g/ equivalent, is preferably 50 ~ 1500g/ equivalent.

Monomer and oligomer can individually use, also can by multiple used in combination.

(polymerization initiator)

As by the irradiation of active energy beam and the polymerization initiator of radiofluorescence, (1) roughly can be divided into be penetrated by illumination or heat and produce the radical polymerization initiator of free radical and (2) are penetrated by illumination or heat and produce cationic cationic polymerization initiators.Contain situation of acrylic monomer and/or oligomer etc. at such as hardening resin composition under, use radical polymerization initiator, contain the situation of epoxy monomer, vinyl ether system monomer and/or oligomer etc. at such as hardening resin composition under, use cationic polymerization initiators.The material being penetrated initiated polymerization by illumination is referred to as Photoepolymerizationinitiater initiater, is referred to as thermal polymerization by the material heating initiated polymerization.When using Photoepolymerizationinitiater initiater, can hardening resin composition be made at normal temperatures solidify, thus the thermotolerance considering the 1st film and the 2nd film or the distortion that causes by expanding need minimizing, and can well film to be bonded.

Active energy beam can enumerate visible ray, ultraviolet, X ray and electron beam.

(1) radical polymerization initiator

Radical polymerization initiator, according to the production process of free radical, is roughly divided into dehydrogenation type and molecule internal fissure type.Dehydrogenation type radical polymerization initiator can enumerate benzophenone and o-benzoyl yl benzoic acid methyl esters.Molecule internal fissure type radical polymerization initiator can enumerate benzoin ether, benzyldimethylketal (ベ Application ジ Le ジメチ Le ケタ mono-Le), Alpha-hydroxy alkyl phenones (α-ヒ De ロキシア Le キ Le Off エノ Application), alpha-aminoalkyl benzophenone (α-アミノア Le キ Le Off エノ Application), oxo benzoyl methyl benzoate (オキソベ Application ゾイ Le benzoic acid メチ Le), 4-benzoyl-4 '-methyldiphenyl sulphur, isopropyl thioxanthone, diethyl thioxanthone, 4-(diethylamino) ethyl benzoate, 2-hydroxy-2-methyl-1-phenyl-propan-one, benzyldimethylketal and 1, 2 Alpha-hydroxy alkyl phenones (1, 2 α mono-ヒ De ロキシア Le キ Le Off エノ Application).

(2) cationic polymerization initiators

Cationic polymerization initiators can enumerate diphenyl iodonium salt.And, in this manual, " Photoepolymerizationinitiater initiater " is not limited to the material remaining the ability causing photopolymerization reaction, also comprise the monomer or oligomer that to change because Photoepolymerizationinitiater initiater originally participates in photopolymerization reaction or around do not exist as photopolymerization reaction object, and cause the initiation for photopolymerization reaction not have contributive material.The cationic polymerization initiators participated in after polymerization initiation reaction splits into 2 or its above number molecules of interest, the fluorescent radiation of participation at least partially in the molecule after division usually.

Producing kation kind (カチオン Seed), lewis acidic Photoepolymerizationinitiater initiater as being penetrated by illumination, aromatic diazonium salt, aromatic series iodine can be enumerated salt, aromatic series sulfonium salt etc. salt, and iron-arene complex (iron-アレン Wrong body), but be not limited to these.Photoepolymerizationinitiater initiater is owing to producing catalytic action by light, even if therefore mix with monomer and/or oligomer, storage stability or operability are also excellent.

Aromatic diazonium salt can enumerate hexafluoro-antimonic acid diazobenzene, hexafluorophosphoric acid diazobenzene and hexafluoro boric acid diazobenzene.

Aromatic series iodine salt can enumerate diphenyl iodonium four (pentafluorophenyl group) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoro antimonate and two (4-nonyl phenyl) iodine hexafluorophosphate.

Aromatic series sulfonium salt can enumerate triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4, the two hexafluorophosphate of 4 '-bis-[diphenyl sulfonium base (ジ Off エニ Le ス Le ホニオ)] diphenyl sulfide, 4, the two hexafluoro antimonate of 4 '-bis-[two (beta-hydroxy ethoxy) phenyl sulfonium base (ス Le ホニオ)] diphenyl sulfide, 4, the two hexafluorophosphate of 4 '-bis-[two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulfide, 7-[two (to toluyl groups) sulfonium base]-ITX hexafluoro antimonate, 7-[two (to toluyl groups) sulfonium base]-ITX four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-diphenyl sulfonium base-diphenyl sulfide hexafluorophosphate, 4-(to tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium base-diphenyl sulfide hexafluoro antimonate and 4-(to tert-butyl-phenyl carbonyl)-4 '-two (to toluyl groups) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate.

Iron-arene complex can be enumerated dimethylbenzene-cyclopentadienyl group and close iron (II) hexafluoro antimonate, cumene-cyclopentadienyl group conjunction iron (II) hexafluorophosphate and dimethylbenzene-cyclopentadienyl group conjunction iron (II)-three (trifluoromethyl sulfonyl) methyl salt (キシレ Application-シ Network ロペ Application タジエニ Le iron (II)-トリス (トリ Off Le オロメチ Le ス Le ホニ Le) メタ Na イ De).

Photoepolymerizationinitiater initiater easily can obtain commercially available product, as commercially available product, with trade name name, can enumerate " カヤラ Star De PCI-220 ", " カヤラ Star De PCI-620 " (being made by Japanese chemical drug (strain) above), " UVI-6990 " (ユニオ Application カ mono-バイ De society system), " アデカオプトマ mono-SP-150 ", " アデカオプトマ mono-SP-170 " (being made by rising sun electrochemical industry (strain) above), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (being made by Japanese Cao Da (strain) above), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (being made by body どり chemistry (strain) above), " PI-2074 " (ロ mono-デイア society system), " CI-5120 " that preferred Japanese Cao Da (strain) is made.

When use Photoepolymerizationinitiater initiater time, can and use photosensitizer.By also with photosensitizer, the reactivity of monomer and/or oligomer can be increased, and improve physical strength, the bond strength of gained solidfied material.

Photosensitizer can enumerate carbonyls, organosulfur compound, persulfide (Over sulfide), redox based compound, azo and diazo-compounds, halogen compounds and photo-reduction pigment.

Specifically, benzoin methylether, benzoin iso-propylether, α can be enumerated, the benzoin derivatives such as alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone; The benzophenone derivates of benzophenone, 2,4-dichloro benzophenones, o-benzoyl yl benzoic acid methyl esters, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone etc.; The thioxanthone derivates of 2-chloro thioxanthone, ITX etc.; The anthraquinone derivative of 2-chloroanthraquinone, 2-methylanthraquinone etc.; The acridone derivatives of N-methylacridine ketone, N-butyl acridone etc.; α can also be enumerated in addition, α-diethoxy acetophenone, benzil, Fluorenone, xanthone, uranyl (ウラニ Le compound) and halogen compounds.These compounds can individually use, also can be used in combination.The content of photosensitizer is preferably 0.1 ~ 20 weight portion relative to hardening resin composition 100 weight portion.

Thermal polymerization produces kation kind or lewis acidic compound, specifically, can enumerate benzylsulfonium, チオ Off エニウム salt, チオラニウム salt, hexadecyldimethyl benzyl ammonium, pyridine salt, salt, carboxylate, sulphonic acid ester and amine acid imide.Thermal polymerization also easily can obtain commercially available product, as commercially available product, with trade name name, " アデカオプト Application CP77 " and " アデカオプト Application CP66 " (being made by rising sun electrochemical industry (strain) above), " CI-2639 " and " CI-2624 " (being made by Japanese Cao Da (strain) above), " サ Application エイ De SI-60L ", " サ Application エイ De SI-80L " and " サ Application エイ De SI-100L " (being made by three new chemical industry (strain) above) can be enumerated.

Polymerization initiator can individually use, or also can be used in combination by two or more.

The content of polymerization initiator, relative to hardening resin composition 100 weight portion, is generally 0.5 ~ 20 weight portion, is preferably 1 ~ 15 weight portion.

Hardening resin composition can promote the compound of polymerization further containing oxetane compound, polyol compound etc.Oxetane compound is the compound in molecule with 4 yuan of cyclic ethers, specifically, 3-ethyl-3-hydroxymethyl-oxetane, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanyl) methoxy] benzene, 3-ethyl-3-(phenoxymethyl) oxetanes, two [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3-(2-Ethylhexoxymethyl) oxetanes and phenol novolacs oxetanes (Off エ mono-ノ Le ボラ Star Network オキセタ Application) can be enumerated.Above-mentioned oxetane compound can use usually commercially available product, as commercially available product, with trade name name, " アロ Application オキセタ Application OXT-101 ", " アロ Application オキセタ Application OXT-121 ", " アロ Application オキセタ Application OXT-211 ", " アロ Application オキセタ Application OXT-221 " and " アロ Application オキセタ Application OXT-212 " (synthesizing (strain) by East Asia above to make) can be enumerated.Oxetane compound containing being proportionally generally 5 ~ 95 % by weight in hardening resin composition, being preferably 30 ~ 70 % by weight.Polyol compound does not preferably have the polyol compound of the acidic-group except phenolic hydroxyl group, specifically, the polyol compound of the functional group do not had beyond hydroxyl-removal, polyester polyol compound, polycaprolactone polyol compound, the polyol compound with phenolic hydroxyl group and polycarbonate polyol can be enumerated.The molecular weight of polyol compound is preferably 62 ~ 1000.The containing ratio of polyol compound is generally 0 ~ 50 % by weight in hardening resin composition, and preferably 0 ~ 30 % by weight.

Hardening resin composition and then also can containing other adjuvant, such as ion trap agent (イオ Application トラ Star プ drug) and antioxidant etc.Ion trap agent can enumerate the mineral compound of the ion trap agent of Powdered bismuth system, the ion trap agent of antimony system, the ion trap agent of magnesium system, the ion trap agent of aluminium system, the ion trap agent of calcium system, the ion trap agent of titanium system and their potpourri etc.Antioxidant can enumerate hindered phenol system antioxidant.

< the 1st film >

The material of 1st film not containing the radiofluorescence by Ultraviolet radiation.As the material of radiofluorescence by Ultraviolet radiation, polyethylene terephthalate, polycarbonate, polyethersulfone etc. can be enumerated.

1st film is preferably the diaphragm of protection the 2nd film.

1st film can enumerate acrylic resin film, polycarbonate resin adipose membrane, polysulfone resin film and the ester ring type polyimide resin film of the amorphous polyolefins resin molding, polymethyl methacrylate film etc. of the acetyl cellulose resins film, amorphism cyclo-olefin-polymer films etc. of tri acetyl cellulose film, diacetyl cellulose film etc., preferred acetyl cellulose resins film and amorphous polyolefins resin molding.

Amorphous polyolefins system resin normally has the resin of the structural unit coming from the cyclic olefin such as norborene, many rings norborneol alkene monomer, also can be the multipolymer of cyclic olefin and chain olefin.Specifically, thermoplasticity saturated norbornene system resin can be enumerated.As commercially available amorphous polyolefins system resin, " the ア mono-ト Application ", " ZEONEX " and " ZEONOR " of Japanese ゼオ Application (strain) of ジエイエスア mono-Le (strain), " APO " of Mitsui Chemicals (strain) and " アペ Le " can be enumerated.Utilize the known method such as solvent casting method, extrusion by melting by amorphous polyolefins resin film forming, obtain the 1st film.

1st film is preferably the low film of moisture permeability, specifically, preferably comprises the film of the moisture permeability transparent resin lower than tri acetyl cellulose.The moisture permeability of tri acetyl cellulose is 400g/m ²about/24hr.

The thickness of the 1st film is generally about 5 ~ 200 μm, is preferably 10 ~ 120 μm, is more preferably 10 ~ 85 μm.

< the 2nd film >

The material of 2nd film not containing the radiofluorescence by Ultraviolet radiation.

2nd film is preferably polarizer, preferably comprises the film of polyvinyl alcohol resin, preferably comprises the film of the resin of gas absorption quantity dichromatism pigment, also preferably resin is carried out uniaxial tension and the film obtained.

Polyvinyl alcohol resin can by carrying out saponification to obtain by polyvinyl acetate (PVA) system resin.Polyvinyl acetate (PVA) system resin can enumerate the polyvinyl acetate (PVA) of the homopolymer as vinyl acetate, vinyl acetate and can with the multipolymer of other vinyl acetate copolymerized monomer.

As can with other monomer of vinyl acetate copolymerized conjunction, unsaturated carboxylic acid, alkene, vinyl ether and unsaturated sulfonic acid can be enumerated.The saponification degree of polyvinyl alcohol resin is generally 85 ~ 100 % by mole, is preferably 98 ~ 100 % by mole.Polyvinyl alcohol resin also can so that modification, specifically, polyvinyl formal, the polyvinyl acetal with aldehyde modification can be enumerated.The weight-average molecular weight of polyvinyl alcohol resin is generally 1000 ~ 10000, is preferably 1500 ~ 10000.

For gas absorption quantity, the polyvinyl alcohol resin film of dichromatism pigment carries out the film that uniaxial tension obtains, and can obtain, that is, polyvinyl alcohol resin film is carried out the operation of uniaxial tension through following operation; By the operation of polyvinyl alcohol resin film with dichromatism pigment dyeing; The polyvinyl alcohol resin film boric acid aqueous solution of dyeing is carried out the operation processed; The operation of washing is carried out after utilizing boric acid aqueous solution process.

Uniaxial tension can carry out before dyeing, also can carry out with dyeing simultaneously, can also carry out after dyeing.When carrying out uniaxial tension after dyeing, can carry out before boric acid process, also can carry out in boric acid process.In addition, also uniaxial tension can be carried out in this multiple stage.Monoaxial stretching method can be set forth between the different roller of circular velocity (peripheral speed) along the method for uniaxial tension, to use hot-rolling along the method etc. of uniaxial tension.In addition, can enumerate carry out in an atmosphere stretching dry-stretch process, under the state with solvent swelling, carry out the wet type drawing process etc. that stretches.Stretching ratio is generally about 4 ~ 8 times.

Colouring method can enumerate the method in the aqueous solution be immersed in by polyvinyl alcohol resin film containing dichromatism pigment.Dichromatism pigment can enumerate iodine and dichroic dye.

When using iodine as dichromatism pigment, preferably polyvinyl alcohol resin film being immersed in the aqueous solution containing iodine and potassium iodide and dyeing.In aqueous solution, the content of iodine is relative to 100 weight parts waters, about being generally 0.01 ~ 0.5 weight portion, the content of potassium iodide relative to 100 weight parts waters, about being generally 0.5 ~ 10 weight portion.The temperature of aqueous solution is generally about 20 ~ 40 DEG C, and dip time is in aqueous generally about 30 ~ 300 seconds in addition.

When using dichroic dye as dichromatism pigment, preferably polyvinyl alcohol resin film being immersed in the aqueous solution containing dichroic dye and dyeing.In aqueous solution, the content of dichroic dye is relative to 100 weight parts waters, is generally 1 × 10 ^-3~ 1 × 10 ^-2about weight portion.Aqueous solution also can contain the inorganic salts of sodium sulphate etc. further.The temperature of aqueous solution is generally about 20 ~ 80 DEG C, and dip time is in aqueous generally about 30 ~ 300 seconds in addition.

Boric acid process is carried out preferably by being immersed in boric acid aqueous solution by the polyvinyl alcohol resin film of dyeing.The content of boric acid aqueous solution mesoboric acid, relative to 100 weight parts waters, about being generally 2 ~ 15 weight portions, is preferably about 5 ~ 12 weight portions.When using iodine as dichromatism pigment, boric acid aqueous solution is preferably containing potassium iodide.In boric acid aqueous solution, the content of potassium iodide is relative to 100 weight parts waters, about being generally 2 ~ 20 weight portions, is preferably 5 ~ 15 weight portions.Dip time in boric acid aqueous solution is generally about 100 ~ 1200 seconds, is preferably about 150 ~ 600 seconds, is more preferably about 200 ~ 400 seconds.The temperature of boric acid aqueous solution is generally more than 50 DEG C, is preferably 50 ~ 85 DEG C.

Washing process after boric acid process is carried out preferably by being immersed in water by borated polyvinyl alcohol resin film.After washing, implement dry process, obtain film.In washing process, the temperature of water is generally about 5 ~ 40 DEG C, and dip time is generally about 2 ~ 120 seconds.The drying process carried out afterwards can use air drier, far infra-red heater to carry out usually.Baking temperature is generally 40 ~ 100 DEG C.The processing time of dry process is generally about 120 ~ 600 seconds.

< the 3rd film >

The material of 3rd film not containing the radiofluorescence by Ultraviolet radiation.

3rd film, except the low resin molding of the moisture permeabilitys such as the amorphous polyolefins resin molding enumerated in the 1st film, can also use acetyl cellulose resins film, acrylic resin film and crystalline polyolefin resin molding.3rd film is also preferably the diaphragm of protection the 2nd film.

1st film and the 3rd film can one species each other mutually, also can be different.

< laminated body >

Fig. 1 represents the schematic diagram of an example of laminated body, described laminated body is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the solidification of this hardening resin composition is obtained.Laminated body 1 shown in Fig. 1 is the laminated body of the 1st film 4 and the 2nd film 2 being fitted across hardening resin composition 3.

Fig. 2 is the schematic diagram of an example of laminated body, described laminated body is fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation, the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation and the 3rd film not containing the material of radiofluorescence by Ultraviolet radiation, and the solidification of this hardening resin composition is obtained.Laminated body 5 shown in Fig. 2 the 1st film 10 and the 2nd film 8 is fitted and the laminated body of the 3rd film 6 of fitting in the opposition side of the side of laminating the 1st film 10 of the 2nd film across hardening resin composition 7 across hardening resin composition 9.

The manufacture method of laminated body of the present invention is below described.

For as laminated body 1, the 1st film and the 2nd film to be fitted the laminated body obtained across hardening resin composition, the manufacture method containing following operation can be utilized manufacture,

< operation (A) >

Operation (A) is such as implemented as follows, that is, the 2nd film is coated with hardening resin composition, and the coated film of gained hardening resin composition attaches the 1st film.

The coating process of hardening resin composition is not limited, the various apparatus for coating such as scraper, line rod, mold pressing coating machine, comma coating machine (カ Application マコ mono-タ mono-), gravure roll coating machine can be used to be coated with.In addition, the viscosity of being cured property of solvent resin combination can be used to regulate.

As long as the solvent of solvent dissolving cured property resin combination, not restriction, the ester system organic solvent of the hydrocarbon system organic solvent, ethyl acetate etc. of preferred toluene etc.The thickness of the coated film that coating hardening resin composition obtains is generally 0.1 ~ 50 μm, is preferably 0.1 ~ 20 μm, more preferably 0.1 ~ 10 μm.

Before by the 1st film and the laminating of the 2nd film, also can implement the process of saponification process, corona treatment, Cement Composite Treated by Plasma, thickening coating process etc. to the face of laminating the 2nd film of the 1st film.In addition, the various processing layers of hard conating, anti-reflection layer, antiglare layer etc. also can be set on the face of the opposition side in the face of laminating the 2nd film of the 1st film.

< operation (B) >

Operation (B) is by irradiating light to the laminated body obtained in operation (A) or heating, and by the hardening resin composition solidification in laminated body, obtains the operation of laminated body.When hardening resin composition solidifies, the 1st film and the 2nd film interfix (set).

When penetrating the hardening resin composition solidification made in laminated body when utilizing illumination, not limiting light source used, is preferably that below 400nm has and sends out light source photodistributed at wavelength.Specifically, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp (ケミカ Le ラ Application プ), black lamp, microwave-excitation mercury vapor lamp (マイ Network ロウエ mono-Block excited Shui Silver lamp) and metal halide lamp can be enumerated.Photo-irradiation intensity is different according to the kind of the kind of hardening resin composition, particularly polymerization initiator, and the photo-irradiation intensity being preferably effective wavelength region for the activation of polymerization initiator is 0.1 ~ 100mW/cm ²polymerization initiator.Light irradiation time is different according to the kind of the kind of hardening resin composition, particularly polymerization initiator, preferably to its setting, to make with the accumulated light of the product representation of photo-irradiation intensity and light irradiation time as 10 ~ 5000mJ/cm ².

When the hardening resin composition solidification utilizing heat to make in laminated body, can heat by generally known method, do not limit for condition etc., the temperature usually more than thermal polymerization generation kation kind, lewis acidic temperature heats, usually 50 ~ 200 DEG C of enforcements.

< operation (C) >

Operation (C) is the operation that the cured resin composition layer that have cured in the laminated body obtained for above-mentioned operation (B) irradiates active energy beam.

The cured resin composition layer that have cured is radiofluorescence by the irradiation of active energy beam.Active energy beam is described above, can enumerate visible ray, ultraviolet, X ray and electron beam.

< operation (D) >

Operation (D) measures the active energy beam being subject to irradiating in above-mentioned operation (C), and the operation of the fluorescence intensity of the fluorescence radiated from cured resin composition layer.

Fluorescence intensity utilizes common determinator to measure.

< operation (E) >

Operation (E) is the fluorescence intensity based on measuring in above-mentioned operation (D), evaluates the cohesive of the 1st film and the 2nd film in laminated body, and judges the operation of the quality quality of laminated body.The intensity (fluorescence intensity) of the fluorescence of radiation changes according to the chemical state of polymerization initiator.Therefore, by measuring fluorescence intensity, the polymerization initiator can evaluating quantity is consumed, that is, the 1st film in laminated body and the 2nd film have carried out the so fusible state of the bonding of which kind of degree.In advance to the laminated body of the 1st film and the 2nd film being carried out fully laminating, measure the moment that polymerization initiator is consumed substantially, namely, the fluorescence intensity in the 1st film in laminated body and the 2nd film cohesive abundant moment, and it can be used as reference value, thus by comparing the fluorescence intensity of this reference value and mensuration, the cohesive of the 1st film and the 2nd film in laminated body can be evaluated, and judge the quality quality of laminated body.And, consider yield or temperature change etc., in hardening resin composition, many amounts containing needing in theory are multiplied by the polymerization initiator of the amount of the spacious and comfortable coefficient gained of regulation, and therefore polymerization initiator " is consumed " state referring to that the spike (free radical, acid etc.) only fully producing curing reaction is generated by polymerization initiator substantially.

This operation contains benchmark selectes step and evaluation procedure.Further, in following steps, the situation implementing operation (B) by irradiating light to the laminated body obtained in operation (A) is carried out describing.Laminated body by obtaining in heating process (A) is implemented to the situation of operation (B), as long as use the parameter obtained by heating-up temperature and heat time to replace accumulated light.(benchmark selectes step)

" benchmark selectes step " is to judging the step that the benchmark of cohesive quality is selected, such as can by following program selecting benchmark.

(I) on the 2nd film, hardening resin composition is coated with, to form certain thickness, the 1st film that this coated film is fitted, analogue formation sample.

(II) with arbitrary accumulated light, illumination is carried out for the model sample made in above-mentioned operation (I) to penetrate, make the model sample that the solid state of hardening resin composition is different, such as, from its uncured state to the model sample of any cure stage of completely crued state.Then, change accumulated light, and profit uses the same method to make the different model sample of cure stage.So make multiple model samples of different cure stage.

(III) for the multiple model samples made in above-mentioned operation (II), the intensity using fluorescence spectrum analyzer to measure the active energy beam irradiated and the fluorescence radiated is used as fluorescence spectrum, obtains the relation of accumulated light when solidifying and fluorescence intensity thus.

(IV) for the multiple model samples made, utilize known method for evaluating adhesion property to evaluate its cohesive, obtain accumulated light when solidifying and fusible relation, select accumulated light when showing abundant fusible solidification.Known method for evaluating adhesion property can enumerate the disbonded test etc. of cutter test, disbonded test etc.

(V) by the relation of the accumulated light during solidification obtained in above-mentioned operation (III) with fluorescence intensity, select the abundant fusible fluorescence intensity corresponding to accumulated light when solidifying of the performance selected in above-mentioned operation (IV) as benchmark (threshold value).

(evaluation procedure)

" evaluation procedure " is by comparing the fluorescence intensity selected benchmark (threshold value) selected in step in said reference and measure in above-mentioned operation (D), evaluating the fusible evaluation procedure of the 1st film and the 2nd film.

Specifically, if the fluorescence intensity ratio measured in operation (D) to select in step selected benchmark (threshold value) at benchmark high, then can be evaluated as cohesive good for this laminated body.In addition, if to select in step selected benchmark (threshold value) at benchmark low for the fluorescence intensity ratio measured in operation (D), then the cohesive of this laminated body can be evaluated as bad.Like this, can when can not be caused carrying out cohesive evaluation to laminated body when breakage by disbonded test etc.

Be noted that in production line etc., under roughly the same illuminate condition, use the hardening resin composition of one species.Therefore, different hardening resin composition is obtained in advance to the threshold value of fluorescence intensity, using the threshold value of this fluorescence intensity as benchmark, and to the fluorescence intensity measured in above-mentioned operation (D) with compare as the threshold value of the fluorescence intensity of this benchmark, carry out the presumption of the solid state of hardening resin composition in laminated body thus, and carrying out fusible evaluation, this is practical and effective.

In addition, owing to make use of and the comparing of the threshold value as benchmark, therefore can also easily evaluate relative to the threshold value as benchmark, the solid state of hardening resin composition relatively, that is, the cohesive of the 1st film and the 2nd film.In addition, by monitoring with or without the threshold value deviated from as benchmark, the exception of hardening resin composition etc. can be found in early days.Thus, a large amount of generations etc. of substandard products can be suppressed, the raising of production qualification rate can be realized.

For as laminated body 5, across hardening resin composition by the 1st film and the 2nd film laminating and across hardening resin composition the side of laminating the 1st film of the 2nd film opposition side laminating the 3rd film laminated body, the manufacture method containing following operation can be utilized manufacture

(A '-2) the 2nd film, the opposition side of the side of having fitted the 1st film, across hardening resin composition laminating the 3rd film and the 2nd film, obtain the operation of laminated body;

(E '), based on the fluorescence intensity measured in above-mentioned operation (D '), evaluates the 1st film and the cohesive of the 2nd film and the cohesive of the 2nd film and the 3rd film in laminated body, and judges the operation of the good ring of laminated body quality.

Operation (A '-1) and operation (A '-2) is same with above-mentioned operation (A) implements.Operation (A '-2) is in the operation of opposition side laminating the 3rd film of the side of the 2nd film, the 1st film of having fitted.Further, operation (A '-2) can be carried out after operation (A '-1), also can carry out with operation (A '-1) simultaneously.

Operation (B ') is same with above-mentioned operation (B ') to be implemented.Operation (C ') is same with above-mentioned operation (C) to be implemented.Operation (D ') is same with above-mentioned operation (D) to be implemented.Operation (E ') is same with above-mentioned operation (E) to be implemented.

(evaluating apparatus)

Following explanation is carried out for the evaluating apparatus as the embodiment realizing evaluation method of the present invention.

Evaluating apparatus comprises fluorometric assay head, evaluation section.Fluorometric assay head is according to the irradiation instruction received from evaluation section, the mensuration active energy beam for measuring fluorescence is irradiated to laminated body, on the other hand, it accepts the fluorescence radiated from hardening resin composition, and the fluorescence intensity of mensuration is exported to evaluation section.

Evaluation section, according to penetrating from illumination or the irradiating state signal of heating arrangement, gives fluorometric assay head and irradiates instruction.

Illumination is penetrated or heating arrangement comprises illumination and penetrates or heating part and control part.Illumination is penetrated or heating part produces for the light that makes hardening resin composition solidify or heat according to the irradiation instruction from control part.Control part is penetrated or heating arrangement applying irradiation instruction to illumination according to from outside instructions such as users, with this irradiation command synchronization, irradiating state signal is outputted to evaluation section simultaneously.

Evaluation section comprises CPU (Central Processing Unit), display part, operating portion, storage part and irradiation warning portion.

CPU is according to the operation instruction from operating portion and penetrate from illumination or the irradiating state signal of heating arrangement, exports fluorometric assay ultraviolet irradiation indicate fluorometric assay head.CPU corresponds to and indicates the irradiation of the fluorometric assay active energy beam of fluorometric assay head, in order to impel the protection to the fluorometric assay active energy beam radiated from fluorometric assay head, lighting and irradiates warning portion or make it glimmer.CPU accepts the fluorescence intensity measured with head by fluorometric assay, evaluates, and this evaluation result etc. exported to display part the cohesive of the laminated body as object.Meanwhile, CPU will represent the outputs such as the signal (simulation, numeral) external device (not diagram) of the fluorescence intensity measured with head by fluorometric assay.And then CPU reads the various data pre-deposited from storage part, by the data etc. of measurement stored in storage part.

Display part contains the display of such as LCD (Liquid Crystal Display), CRT (Cathode Raytube) etc., the curve etc. of the fluorescence intensity change that its display accepts from CPU.

Operating portion comprises various switches etc., and it accepts the operation from user, and the operation instruction corresponding with this operation is exported to CPU.

Irradiate warning portion and comprise such as LED, lamp etc., it is for the user etc. of the position be in close to evaluating apparatus, and prompting fluorometric assay active energy beam is in irradiation.

Storage part comprises such as EEPROM (Electrically Erasable and ProgrammableRead only Memory) etc., and it is stored in determination data, the various data etc. corresponding with the kind of hardening resin composition.

Fluorometric assay head comprises light projector driving circuit, light-projecting component, half-reflecting mirror, light filter, photo detector, HPF (High Pass Filter), amplifying circuit, S/H (Sample and Hold) and analog-to-digital conversion portion (ADC).

Light projector driving circuit indicates according to the irradiation of the fluorometric assay active energy beam accepted from CPU, with the voltage of the cycle specified to light-projecting component applying pulse type.Light-projecting component comprises such as ultraviolet LED, and it is according to by the additional pulse voltage of light projector driving circuit, and produces fluorometric assay active energy beam and radiate.In embodiments of the present invention, light-projecting component is radiated at the fluorometric assay active energy beam that 365nm has main glow peak.

Half-reflecting mirror and light-projecting component are configured on same optical axis, it is through the fluorometric assay active energy beam radiated from light-projecting component, on the other hand, it makes to change from the travel path of the fluorescence radiated as the hardening resin composition the laminated body of determination object, and guides light filter into.Such as, the reflecting surface of half-reflecting mirror is formed by metal evaporation.

Light filter configures in order to the stray light eliminating the fluorometric assay active energy beam that irradiated by light-projecting component etc., and it makes the optical attenuation of ultraviolet region on the one hand, makes the light transmission of visibility region on the other hand.In embodiments of the present invention, the filtrator of light filter to be transmission peak wavelength the be multilayer dielectric film of the light of more than 410nm.

An example of photo detector comprises photodiode, and it according to the generation current through the intensity of the fluorescence of light filter incidence, and exports to HPF.

HPF by the fluorescence intensity signals that accepted by photo detector, flip-flop and low-frequency component removing, only make the signal of more than assigned frequency pass through, to extract the composition utilizing solidification ultraviolet to produce out.

Amplifying circuit amplifies the signal by HPF with the magnification (current/voltage conversion ratio) of regulation, and exports to S/H circuit.

Luminous opportunity of S/H circuit and light-projecting component synchronously samples to light reception intensity signal, keep the signal value gathered, until during sampling next time, be determined at each peak swing value of carrying out the signal in each cycle in the specified period of pulse type light projector thus, within each cycle, maintain the peak swing value of mensuration.

The voltage signal exported by S/H circuit (simulating signal) is converted to numerical value by analog-to-digital conversion portion, and exports to CPU.

Then, the optical system for fluorometric assay head is probably described.

Fluorometric assay head also has convergent lens.Form following structure, namely, light-projecting component, half-reflecting mirror, convergent lens and the hardening resin composition as object configure on the same line, and the fluorometric assay active energy beam irradiated from light-projecting component is converged to specific diameter range by convergent lens at hardening resin composition.The fluorescence radiated from hardening resin composition and fluorometric assay active energy beam are propagated in opposite direction in same path, and change travel path with half-reflecting mirror reflection.And then fluorescence is incident to photo detector by light filter.Further, roughly the same to the distance of hardening resin composition with from convergent lens to the distance of convergent lens from the shadow surface of light-projecting component.

(the cohesive evaluation of laminated body)

Such as, according to following process like that, carry out the cohesive evaluation of the selected of reference value and laminated body.And, the below process fusible example of laminated body of fitting for evaluating as laminated body 1, by the 1st film and the 2nd film across hardening resin composition, even if but for laminated body 5 such, across hardening resin composition by the 1st film and the 2nd film laminating, and across the laminated body of hardening resin composition at opposition side laminating the 3rd film of the side of laminating the 1st film of the 2nd film, also carry out the cohesive evaluation of the selected of reference value and laminated body according to the process same with it.

(reference value selected)

First, CPU is according to penetrate from illumination or whether the irradiating state signal of heating arrangement judges that illumination is penetrated or heated and start.Penetrate for illumination or heat situation about not starting, CPU is back to starting point (hereinafter referred to as step S1).

When illumination is penetrated or heat beginning, CPU applies to irradiate instruction (hereinafter referred to as step S2) to fluorometric assay with head.So fluorometric assay head irradiates fluorometric assay active energy beam to the hardening resin composition as object.CPU obtains fluorescence intensity from fluorometric assay head, and described fluorescence intensity is subject to the irradiation of fluorometric assay active energy beam and the intensity of the fluorescence that the polymerization initiator contained in this hardening resin composition is radiated.

Then, the fluorescence intensity that obtains stored in storage part, is judged the fluorescence intensity data that whether have accumulated more than stated number in storage part by CPU simultaneously.When not accumulating the fluorescence intensity data of more than stated number, CPU is back to step S2.

When have accumulated the fluorescence intensity data of more than stated number, CPU reads the fluorescence intensity data from the stated number of storage part, performs handling averagely (moving average), and calculates the fluorescence intensity in this moment.

And then CPU obtains the customizing messages of the evaluation results such as the fluorescence intensity calculated and the disbonded test inputted by user etc., and perform based on the customizing messages obtained selected (hereinafter referred to as step 3) of reference value.

Such as when fluorescence intensity is more than P ^atime, the evaluation result of disbonded test etc. is good, when fluorescence intensity is not more than P ^atime, if the evaluation result peeling off research is not good, then CPU selectes P ^aas reference value.

(the cohesive evaluation of laminated body)

CPU is according to penetrate from illumination or whether the irradiating state signal of heating arrangement judges that illumination is penetrated or heated and start.Penetrate for illumination or heat situation about not starting, CPU is back to starting point (hereinafter referred to as step S11).

When illumination is penetrated or heat beginning, CPU applies to irradiate instruction (hereinafter referred to as step S12) to fluorometric assay with head.So fluorometric assay head irradiates fluorometric assay active energy beam to the hardening resin composition as object.CPU obtains fluorescence intensity from fluorometric assay head, and described fluorescence intensity is subject to the irradiation of mensuration active energy beam and the intensity of the fluorescence that the Photoepolymerizationinitiater initiater contained in this hardening resin composition is radiated.

Then, the fluorescence intensity that obtains stored in storage part, is judged the fluorescence intensity data that whether have accumulated more than stated number in storage part by CPU simultaneously.When not accumulating the fluorescence intensity data of more than stated number, CPU is back to step S12.

When have accumulated the fluorescence intensity data of more than stated number, CPU reads the fluorescence intensity data from the stated number of storage part, performs handling averagely (moving average), calculates the fluorescence intensity in this moment.

And then CPU, according to the fluorescence intensity calculated, performs fusible evaluation process (hereinafter referred to as step 13) of laminated body.Specifically, the subroutine that CPU calls containing following treatment scheme performs.

CPU obtain inputted by user etc. hardening resin composition, the 1st film and the kind of the 2nd film and the coated film of hardening resin composition the customizing messages (hereinafter referred to as step 14) of thickness etc., and according to the customizing messages obtained at step 14, read the reference value P as the specific fluorescence intensity of benchmark from storage part ^a(hereinafter referred to as step 15).Whether CPU exceedes the reference value P read in step 15 to the fluorescence intensity calculated ^acarry out judging (hereinafter referred to as step 16).Further, reference value also can be specified by user in advance.When the fluorescence intensity measured exceedes reference value P ^atime, the cohesive that CPU is considered as laminated body is good, and is back to process (step S11) originally.

On the other hand, when the fluorescence intensity measured does not exceed reference value P ^atime, CPU is considered as the poor adhesion of laminated body, and is back to process (step S11) originally.

Then, fusible evaluation result etc. to outputs such as display parts, and judges whether to meet and measures termination condition by CPU.Measure termination condition can suitably adopt following condition, that is, illumination penetrate or heat start after through official hour, such as obtain the condition judging to reach the such particular result of maximum degree of cure etc.When not meeting mensuration termination condition, CPU is back to step 12.On the other hand, when satisfied mensuration termination condition, CPU is back to starting point (step 11).

For laminated body, penetrate the difference of conditioned disjunction heating condition according to illumination, the cohesive of the 1st film and the 2nd film changes, and sometimes produces following problem.Such as when illumination is penetrated or heat insufficient, the laminated body obtained has the possibility of shortcomings such as the stripping of film, variable color occurring and/or fades.In addition, such as when illumination is penetrated or over-heating time, the laminated body obtained has the possibility producing wrinkle or the shortcoming such as curling on film.In order to this shortcoming of Timeliness coverage, and the cohesive of controlling diaphragm, need, under the state not destroying laminated body and in production line, to evaluate the cohesive of laminated body.

Therefore, in production line, introduce the evaluating apparatus with fluorometric assay head and evaluation section.Specifically, as described below.First, the 1st film exported is coated with hardening resin composition from the position of regulation.While this coating or in the further downstream side of production line, the 2nd film engages with the 1st film.The laminated body obtained like this from be positioned at production line further downstream side comprise illumination penetrate or heating part, control part illumination to penetrate or heating arrangement accepts for the light that makes hardening resin composition solidify or heat.

This illumination penetrate or heating arrangement downstream configuration evaluating apparatus.Evaluating apparatus along the direction orthogonal with throughput direction arrangement, and evaluates the cohesive of the laminated body of conveying.Evaluating apparatus evaluates the cohesive of the 1st film and the 2nd film in real time (online (in line)).And then, if which kind of shortcoming is this cohesive have, then carry out the process corresponding to the reason producing this shortcoming, such as, change the UV-lamp etc. forming light irradiation device.

Embodiment

Below describe the outline realizing the embodiment evaluated according to the cohesive of the laminated body of embodiment of the present invention.

In the method for evaluating adhesion property of the laminated body according to embodiment of the present invention, can in-service evaluation device and solidification ultraviolet lamp, the cohesive of the laminated body be configured on sample bench is evaluated.

Evaluating apparatus comprises fluorometric assay head and evaluation section.The fluorometric assay irradiation instruction of head according to the fluorometric assay active energy beam received from evaluation section, and irradiate the fluorometric assay active energy beam for measuring fluorescence to laminated body, on the other hand, it accepts the fluorescence radiated from the hardening resin composition laminated body, and the fluorescence intensity of mensuration is exported to evaluation section.

Evaluation section, according to the irradiating state signal from light irradiation device, applies the irradiation instruction of fluorometric assay active energy beam with head to fluorometric assay.Evaluation section evaluates the cohesive of laminated body according to the fluorescence intensity measured at fluorometric assay head.

Light irradiation device comprises light struck head portion and irradiates control part.Light struck head portion indicates according to from the solidification ultraviolet irradiation irradiating control part, irradiates solidification ultraviolet to laminated body.Irradiate control part according to from the outside instruction such as user, giving Ultraviolet radiation head solidification ultraviolet irradiation indicates, and while to indicate with this irradiation and synchronously to be exported to evaluation section by solidification ultraviolet irradiation status signal.

In brown spiral pipe (ス Network リユ mono-manages) (No.5), by the hydrogenated epoxy resin (diglycidyl ether of bisphenol-A, trade name: エピコ mono-ト YX8000, ジヤパ Application エ Port キシレジ Application (strain) makes, epoxide equivalent: 205g/ equivalent) 10.0g, light cationic polymerization initiators (aromatic series sulfonium salt, trade name: SP-500, (strain) ADEKA system) 4.0g mixes, modulation hardening resin composition X1.

In brown spiral pipe (No.5), by hydrogenated epoxy resin (trade name: エピコ mono-ト YX8000, ジヤパ Application エ Port キシレジ Application (strain) make) 7.0g, oxetane resin (3-ethyl-3-hydroxymethyl-oxetane (oxa-cyclobutanol (オキセタ Application ア Le コ mono-Le)), trade name: アロ Application オキセタ Application OXT 101, East Asia synthesis (strain) system) 3.0g, light cationic polymerization initiators (trade name: SP-500, (strain) ADEKA system) 4.0g mixes, modulation hardening resin composition X2.

In brown spiral pipe (No.5), by hydrogenated epoxy resin (trade name: エピコ mono-ト YX8000, ジヤパ Application エ Port キシレジ Application (strain) make) 10.0g, the light cationic polymerization initiators (compound of aromatic series sulfonium salt system, trade name: SP-152, (strain) ADEKA system) 4.0g mixes, modulation hardening resin composition X3.

Use cellulose ester membrane (trade name: 8UX-TAC, hereinafter referred to as A1) as the 1st film,

Use polyvinyl alcohol (PVA) dyestuff system's polarizer (hereinafter referred to as B1) as the 2nd film,

Use amorphous polyolefins resin molding (trade name: ZEONOR, Japan ゼオ Application (strain) system, hereinafter referred to as C1) or cellulose ester membrane (trade name: New-nTAC, コニカ (strain) makes, hereinafter referred to as C2) as the 3rd film.These A1, B1, C1 and C2 material not containing the radiofluorescence by Ultraviolet radiation.

The making > of < laminated body

Use shown in table 1, the 1st, the 2nd and the 3rd film and hardening resin composition, make laminated body S1 ~ S5 as follows.After 1st film is coated with hardening resin composition, laminating the 2nd film.And then, the 2nd film, laminating the 1st film face opposition side face on be coated with hardening resin composition after, laminating the 3rd film.

Be noted that the thickness of cured resin composition layer uses contact film thickness gauge ((strain) ニコ Application society system), calculate according to method shown below.

Measure the thickness of laminated body made, deducted the thickness of the 1st film, the 2nd film and the 3rd film that measure in advance by the thickness obtained respectively, by the value of gained divided by 2.Further, the thickness obtained, according to locating, shows as ± the deviation of about 20%, therefore changes and locates, carry out 3 place's mensuration, and the mean value of value when being measured at this 3 place is as the thickness of cured resin composition layer.Thickness is shown in table 1.

Table 1

< fluorescent strength determining >

By laminated body with make the 3rd film be in upside (irradiate mouth side) state, in ultraviolet lamp (trade name: CV-1100-G, Off ュ mono-ジヨ Application UV システ system ズジヤパ Application (strain) makes, use D valve, power 80%, height 4cm, speed 11m/ minute) in by regulation number of times.Laminated body is about 600mJ/cm2 (UVB) by accumulated light when 4 times in ultraviolet lamp.For each laminated body, change the mensuration that the power of ultraviolet lamp, speed and number of pass times carry out fluorescence intensity.

Use fluorescent strength determining device (trade name: OL201-1, (strain) センテツク society system), measured the fluorescence intensity (unit: V) of being radiated by hardening resin composition by fluorescent strength determining method.Fluorescent strength determining carries out as follows, namely, use LED365D-S (excitation wavelength is 365nm) as light source, OL201 (determined wavelength is 420 ~ 700nm) as detecting device, and set, make that the distance of lens and measured object is about 35mm, value for the projection quantity is 10%, sensitivity is 60%, sensitivity is 9.00.In addition, setting compensation value (オ Off セ Star ト), to make only to place device displayed value when corrosion resistant plate measures for zero.Now, device displayed value when measuring " ND-40 " as standard fluorescence luminescent substance is about 5.00V.Further, measuring is all that the state making the 3rd film be in upside (irradiating mouth side) is implemented.Measured value according to locating ± deviation of about 20%, therefore will change the mean value of the value of carrying out when 3 places measure that locates as fluorescence intensity.

< adhesion test 1>

The cohesive of the 1st film and the 2nd film is evaluated with cutter test method(s).Result is shown in table 2.

< adhesion test 2>

The cohesive of the 3rd film and the 2nd film is evaluated with cutter test method(s).Result is shown in table 2.

Cutter test method(s) carries out as follows, namely, first on the 1st film surface of laminated body, surface is formed until reach the ditch of about the 1cm of the 2nd film with cutter, then the angle of the blade of cutter and surface almost parallel (making the state that blade lies low) is made, put into cutter at the central portion of ditch, and point of a knife is passed through between the 1st film and the 2nd film, directly by cutter forwards (inboard) propelling.

Now, even if when also advancing without power, blade, cohesive is bad, be denoted as ×.When firmly a little, when blade enters about 5mm, cohesive is good, is denoted as △.Even if when quite exerting oneself, blade can not enter well and film self is at once cut-off time, cohesive is very good, is denoted as zero.This test after carrying out Ultraviolet radiation after about 1 hour, after about 3 hours, about 1 day (24 hours) implement afterwards.For the surface of the 3rd film of laminated body, carry out as described above, and evaluate equally.

< adhesion test 3>

Evaluate the cohesive of the 1st film and the 2nd film by disbonded test method, measure peel strength (unit: N).Result is shown in table 2.

Disbonded test uses オ mono-トグラ Off AGS-100D (trade name, society of (strain) Shimadzu Seisakusho Ltd. system) to carry out.2 films (the 1st film and the 2nd film) part of bonding is peeled off, and the bonded body of stripping place is fixed on one end, adherend is fixed on the other end, when carrying out tearing by being determined at expansion interval between the two, power used calculates peel strength.In order to calculate the peel strength of the 1st film and the 2nd film, make the sample that the 1st film and the 2nd membrane portions are peeled off.And cut into the size of about 2.5cm × 15cm.Now stripping portion and non-peel-away portion are in long axis direction.Be fixed on the upside of peel test device by the 1st film of stripping place of this sample, the sample after being peeled off by the 1st film is fixed on the downside of peel test device.

Be 1cm/ minute using peeling rate, force cell is that the mean value of 25N power used when peeling off about 5cm (about 5 minutes) is as peel strength.

Table 2

In table ,-represent undetermined.

From this result, if laminated body S 1 fluorescence intensity is more than 1.95V, then cohesive is good.If laminated body S2 fluorescence intensity is more than 2.14V, then cohesive is very good.If laminated body S3 fluorescence intensity is more than 2.38V, then cohesive is good.If laminated body S4 fluorescence intensity is more than 2.28V, then cohesive is good.If laminated body S5 fluorescence intensity is more than 4.81V, then cohesive is good.Therefore, for each laminated body, by suitably setting the benchmark (threshold value) of fluorescence intensity according to the above results, the cohesive of each laminated body can be evaluated.

Industrial applicability

According to method for evaluating adhesion property of the present invention, when not peeling off laminated body, its cohesive can be evaluated.

Claims

1. method for evaluating adhesion property, it is the method for evaluating adhesion property evaluated the cohesive of film in laminated body, described laminated body is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the laminated body this hardening resin composition being solidified and obtains

It contains following operation:

Based on the measurement result of fluorescence intensity, evaluate the fusible operation of the 1st film and the 2nd film in laminated body,

Above-mentioned evaluation be with the fluorescence intensity in cohesive abundant moment for reference value, undertaken by the measurement result comparing this reference value and above-mentioned fluorescence intensity,

Said reference value is the multiple model samples to being in different cure stage, obtain accumulated light and fluorescence intensity when solidifying and fusible relation, the fluorescence intensity that sufficient fusible accumulated light when solidifying of the performance selected by obtained relation is corresponding.

2. method for evaluating adhesion property, it is the method for evaluating adhesion property evaluated the cohesive of film in laminated body, described laminated body is fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation, the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation and the 3rd film not containing the material of radiofluorescence by Ultraviolet radiation, and the laminated body this hardening resin composition being solidified and obtains

It contains following operation:

Based on the measurement result of fluorescence intensity, evaluate the 1st film and the cohesive of the 2nd film and the fusible operation of the 2nd film and the 3rd film in laminated body,

3. method for evaluating adhesion property according to claim 1, wherein, the 2nd film is polarizer.

4. method for evaluating adhesion property according to claim 2, wherein, the 2nd film is polarizer.

5. method for evaluating adhesion property according to claim 1 and 2, wherein, the 1st film is the diaphragm of protection the 2nd film.

6. method for evaluating adhesion property according to claim 2, wherein, the 3rd film is the diaphragm of protection the 2nd film.

7. method for evaluating adhesion property according to claim 1 and 2, wherein, the 1st film is the film containing at least a kind of resin be selected from acetyl cellulose resins, amorphous polyolefins resin, crystalline polyolefin resin and acrylic resin.

8. method for evaluating adhesion property according to claim 1 and 2, wherein, the 2nd film is the film comprising polyvinyl alcohol resin.

9. method for evaluating adhesion property according to claim 1 and 2, wherein, the 2nd film is the film of the resin comprising gas absorption quantity dichromatism pigment.

10. method for evaluating adhesion property according to claim 1 and 2, wherein, the 2nd film resin is carried out the film that uniaxial tension obtains.

11. method for evaluating adhesion properties according to claim 2, wherein, the 3rd film is the film containing at least a kind of resin be selected from acetyl cellulose resins, amorphous polyolefins resin, crystalline polyolefin resin and acrylic resin.

12. method for evaluating adhesion properties according to claim 1 and 2, wherein, hardening resin composition is containing monomer and/or oligomer and passes through irradiation active energy beam and the composition of the polymerization initiator of radiofluorescence.

The manufacture method of 13. laminated body, it is fitted across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation and the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation, and the manufacture method of the laminated body that this hardening resin composition is solidified

It is characterized in that, containing following operation:

(E) based on the fluorescence intensity measured in above-mentioned operation (D), evaluate the cohesive of the 1st film and the 2nd film in laminated body, and judge the operation of the quality quality of laminated body,

The manufacture method of 14. laminated body, it is fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition at the 1st film not containing the material of radiofluorescence by Ultraviolet radiation, the 2nd film not containing the material of radiofluorescence by Ultraviolet radiation and the 3rd film not containing the material of radiofluorescence by Ultraviolet radiation, and the manufacture method of the laminated body that this hardening resin composition is solidified

It is characterized in that, containing following operation:

(E '), based on the fluorescence intensity measured in above-mentioned operation (D '), evaluates the 1st film and the cohesive of the 2nd film and the cohesive of the 2nd film and the 3rd film in laminated body, judges the operation of the good ring of laminated body quality,