CN102023145A

CN102023145A - Method for evaluating adhesion property of film

Info

Publication number: CN102023145A
Application number: CN2010102780315A
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: 2011-04-20
Anticipated expiration: 2030-09-08
Also published as: TW201129791A; TWI479143B; KR20110027587A; JP2011080984A; KR101707424B1; CN102023145B; JP5577974B2

Abstract

The invention relates to a method for evaluating adhesion property of a film. The method for evaluating adhesion property of a film is used for evaluating the adhesion property of the film in a laminated body, wherein the laminated body formed by adhering a first film containing no materials capable of radiating fluorescent light under the ultraviolet irradiation to a second film containing no materials capable of radiating fluorescent light under the ultraviolet irradiation with a solidification resin combination therebetween and then solidifying the solidification resin combination. The method comprises the steps of: adhering the first film to the second film with the solidification resin combination therebetween so as to acquire the laminated body, solidifying the solidification resin combination in the laminated body by illuminating or heating the laminated body so as to acquire the laminated body, radiating the solidified solidification resin combination in the laminated body with active energy rays so as to measure the fluorescence intensity of the fluorescent light radiated from the solidification resin combination, and evaluating the adhesion property of the first and second films in the laminated body based on a measured result about the fluorescence intensity.

Description

The cohesive evaluation method of film

Technical field

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

Background technology

As estimating with the polaroid is the fusible cohesive evaluation method of film in the laminated body that forms of a plurality of film laminations of representative; a kind of cohesive evaluation method of film is disclosed in TOHKEMY 2008-299175 communique; its use cutter only cuts the diaphragm in the polaroid, and to whether peeling off diaphragm evaluation from this cut place.

Summary of the invention

But said method has downcut the diaphragm in the polaroid, and people require a kind of destruction without laminated body such as this diaphragms of cutting-out, come the cohesive evaluation method that each intermembranous cohesive in the polaroid is estimated.

Under this situation, the inventor furthers investigate, thereby has finished the present invention.

That is, the invention provides:

[1] cohesive evaluation method, it is the cohesive evaluation method that the cohesive of film in the laminated body is estimated, described laminated body is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and this hardening resin composition is solidified and the laminated body that obtains

This method contains following operation:

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

By laminated body being carried out rayed or laminate heated body the hardening resin composition in the laminated body is solidified, obtain the operation of laminated body;

To the cured resin composition layer irradiation active energy beam (active エネ Le ギ one Line) that has solidified in the laminated body, measure operation by the fluorescence intensity of the fluorescence of cured resin composition layer radiation;

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

[2] method for evaluating adhesion property; It is the method for evaluating adhesion property that the cohesive of film in the laminated body is estimated; The 2nd film of the material that described laminated body is the 1st film that will not contain the material of the radiofluorescence by the ultraviolet ray irradiation, do not contain the radiofluorescence by the ultraviolet ray irradiation and the 3rd film that do not contain the material of radiofluorescence by the ultraviolet ray irradiation are fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition; And this hardening resin composition is solidified and the laminated body that obtains

This method contains following operation:

Across the operation of hardening resin composition with the 1st film and the applying of the 2nd film;

At the opposition side of a side the 2nd film, that fitted the 1st film,, obtain the operation of laminated body across hardening resin composition the 3rd film of fitting;

To the cured resin composition layer irradiation active energy beam that has solidified in the laminated body, measure operation by the fluorescence intensity of the fluorescence of cured resin composition layer radiation;

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

[3] according to [1] described cohesive evaluation method, wherein, the 2nd film is a polarizer.

[4] according to [2] described cohesive evaluation method, wherein, the 2nd film is a polarizer.

[5] according to each described cohesive evaluation method in [1]～[4], wherein, the 1st film is the diaphragm of protection the 2nd film.

[6] according to [2], [4] or [5] described cohesive evaluation method, wherein, the 3rd film is the diaphragm of protection the 2nd film.

[7] according to each described cohesive evaluation method in [1]～[6], wherein, the 1st film is to contain the film that is selected from least a kind of resin in cellulose acetate resin, amorphous polyolefins resin, crystalline polyolefin resin and the acrylic resin.

[8] according to each described cohesive evaluation method in [1]～[7], wherein, the 2nd film is the film that comprises polyvinyl alcohol resin.

[9] according to each described cohesive evaluation method in [1]～[8], wherein, the 2nd film is to comprise the film that absorption has been orientated the resin of dichromatism pigment.

[10] according to each described cohesive evaluation method in [1]～[9], wherein, the 2nd film is that resin is carried out the film that uniaxial tension obtains.

[11] according to each described cohesive evaluation method in [2] and [4]～[10], wherein, the 3rd film is to contain the film that is selected from least a kind of resin in cellulose acetate resin, amorphous polyolefins resin, crystalline polyolefin resin and the acrylic resin.

[12] according to each described cohesive evaluation method in [1]～[11], wherein, hardening resin composition is to contain monomer and/or oligomer and the composition of the polymerization initiator of radiofluorescence by the irradiation active energy beam.

[13] manufacture method of laminated body, it is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and make the manufacture method of the laminated body that this hardening resin composition solidifies

It is characterized in that, contain following operation:

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

(B) by laminated body being carried out rayed or laminate heated body the hardening resin composition in the laminated body is solidified, obtain the operation of laminated body;

(C) to the operation of the cured resin composition layer irradiation active energy beam that solidified in the laminated body;

(D) measure the active energy beam be subjected to irradiation in the above-mentioned operation (C), and the operation of the fluorescence intensity of the fluorescence that radiates from cured resin composition layer;

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

[14] manufacture method of laminated body, the 2nd film of the material that it is the 1st film that will not contain the material of the radiofluorescence by the ultraviolet ray irradiation, do not contain the radiofluorescence by the ultraviolet ray irradiation and the 3rd film that do not contain the material of radiofluorescence by the ultraviolet ray irradiation are fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition, and make the manufacture method of the laminated body that this hardening resin composition solidifies

It is characterized in that, contain following operation:

(A '-1) is across the operation of hardening resin composition with the 1st film and the applying of the 2nd film;

(A '-2) at the opposition side of a side the 2nd film, that fitted the 1st film, across hardening resin composition the 3rd film of fitting, obtains the operation of laminated body;

(B ') solidifies the hardening resin composition in the laminated body by laminated body being carried out rayed or laminate heated body, obtains the operation of laminated body;

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

(D ') measures the active energy beam be subjected to irradiation in the above-mentioned operation (C '), and the operation of the fluorescence intensity of the fluorescence that radiates from cured resin composition layer;

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

According to the present invention, can be under the situation of not destroying laminated body, easily estimate the cohesive of film in the laminated body, described laminated body is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and this hardening resin composition is solidified obtain.

Description of drawings

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

The synoptic 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

The 1st cohesive evaluation method of the present invention is the cohesive evaluation method that the cohesive of film in the laminated body is estimated, described laminated body is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and this hardening resin composition curing is obtained

It contains following operation:

The 2nd method for evaluating adhesion property of the present invention is the method for evaluating adhesion property that the cohesive of film in the laminated body is estimated; The 2nd film of the material that described laminated body is the 1st film that will not contain the material of the radiofluorescence by the ultraviolet ray irradiation, do not contain the radiofluorescence by the ultraviolet ray irradiation and the 3rd film that do not contain the material of radiofluorescence by the ultraviolet ray irradiation are fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition; And this hardening resin composition curing is obtained

It contains following operation:

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

＜hardening resin composition 〉

Hardening resin composition is the resin combination that solidifies by rayed or heating, and it contains monomer and/or oligomer and by rayed or heating and the polymerization initiator of radiofluorescence.(monomer)

Acrylic monomer and epoxy that monomer can be enumerated polyester acrylate, urethane acrylate, PBAA ester, siloxane acrylate (シリコ Application ア Network リレ one ト), epoxy acrylate etc. are monomer.Monomer may also be referred to as and is single amount body, and it is the state of the raw material when coming synthetic resin by curing reaction.

Epoxy is that can to enumerate the hydrogenation epoxy be that monomer, ester ring type epoxy are that monomer and aliphatic epoxy are monomer to monomer.Epoxy is that the epoxy that monomer does not preferably contain aromatic rings is a monomer.

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

The ester ring type epoxy is that monomer can be enumerated the compound that contains structure shown in the formula (I).

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

Carbon number is that 1～4 alkyl can be enumerated methyl and ethyl.

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

The compound that contains structure shown in the formula (I) can be enumerated following compound:

The 7-oxa-bicyclo[4.1.0 formic acid epoxycyclohexyl methyl esters of formula (II) expression

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

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

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

The epoxycyclohexyl methyl ester of the alkane dicarboxylic acid of formula (IV) expression

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

The epoxycyclohexyl methyl ether of the polyglycol of formula (V) expression;

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

The epoxycyclohexyl methyl ether of the alkane glycol of formula (VI) expression;

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

Diepoxy three spiro-compounds of formula (VII) expression

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

The diepoxy list spiro-compounds of formula (VIII) expression;

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

The vinyl cyclohexene diepoxide of formula (IX) expression;

(in the formula, R ¹⁵Expression hydrogen atom or carbon number are 1～5 straight chain shape alkyl);

The epoxide ring amyl ether of formula (X) expression;

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

The diepoxy tristane of formula (XI) expression.

(in the formula, R ¹⁸Expression hydrogen atom or carbon number are 1～5 straight chain shape alkyl),

In these, preferred:

Ester (the R that generates by 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol ¹And R ²Compound for the expression of the usefulness formula (II) of hydrogen atom),

Ester (the R that generates by 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl-7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol ¹For methyl and be bonded in 4, R ²For methyl and be bonded in the compound of usefulness formula (II) expression on 4),

By 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1, the ester (R that 2-ethylene glycol generates ³And R ⁴For hydrogen atom, n is the compound of 2 usefulness formula (III) expression),

Ester (the R that generates by (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and hexane diacid ⁵And R ⁶For hydrogen atom, p is the compound of 2 usefulness formula (IV) expression),

Ester (the R that generates by (4-methyl-7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and hexane diacid ⁵For methyl and be bonded in 4, R ⁶For methyl and be bonded in the compound that p on 4 is 2 usefulness formula (IV) expression) and

By (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and 1, the ether (R that 2-ethylene glycol generates ⁹And R ¹⁰Be hydrogen atom, r is the compound of 2 usefulness formula (VI) expression).

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

(oligomer)

Oligomer is also referred to as and is low polymer, and it is that the degree of polymerization is the resin of the low state of about 2～20 the degree of polymerization.Oligomer can be enumerated the oligomer of above-mentioned monomer, and the epoxy that does not preferably contain aromatic rings is an oligomer.The epoxy that does not contain aromatic rings is that oligomer is meant and comes from the oligomer that does not contain aromatic rings in the structure and have 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 be distinguished use separately, also multiple mixing can be used.

(polymerization initiator)

As the polymerization initiator of radiofluorescence, roughly can be divided into (1) and produce cationic cationic polymerization initiators by rayed or heating by radical polymerization initiator and (2) that rayed or heating produce free radical by the irradiation of active energy beam.The situation etc. that contains acrylic monomer and/or oligomer at for example hardening resin composition down, use radical polymerization initiator, for example hardening resin composition contain epoxy be monomer, vinyl ether be the situation of monomer and/or oligomer etc. down, use cationic polymerization initiators.Material by the rayed initiated polymerization is referred to as Photoepolymerizationinitiater initiater, is referred to as thermal polymerization by the material that heats initiated polymerization.When using Photoepolymerizationinitiater initiater, hardening resin composition is solidified, thereby consider the thermotolerance of the 1st film and the 2nd film or the distortion that causes by expansion need reduce, and can be well that film is bonding.

Active energy beam can be enumerated visible light, ultraviolet ray, X ray and electron beam.

(1) radical polymerization initiator

Radical polymerization initiator roughly is divided into dehydrogenation type and molecule internal fissure type according to the production process of free radical.Dehydrogenation type radical polymerization initiator can be enumerated benzophenone and o-benzoyl yl benzoic acid methyl esters.Molecule internal fissure type radical polymerization initiator can be enumerated benzoin ether; benzyldimethylketal (ベ Application ジ Le ジメチ Le ケタ one 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-propane-ketone; benzyldimethylketal and 1; 2 Alpha-hydroxy alkyl phenones (1,2 α, one ヒ De ロキシア Le キ Le Off エノ Application).

(2) cationic polymerization initiators

Cationic polymerization initiators can be enumerated diphenyl iodonium

Salt.And, in this manual, " Photoepolymerizationinitiater initiater " is not limited to the residual material that the ability that causes photopolymerization reaction is arranged, also comprise owing to originally Photoepolymerizationinitiater initiater participates in photopolymerization reaction changing or not having monomer or oligomer on every side, and cause initiation for photopolymerization reaction not have the material of contributing as the photopolymerization reaction object.Cationic polymerization initiators after the participation polymerization initiation reaction splits into 2 or its above number molecules of interest usually, and at least a portion in the molecule after the division participates in fluorescent radiation.

As produce kation kind (カチオン Seed), lewis acidic Photoepolymerizationinitiater initiater by rayed, can enumerate aromatic series diazo salt, aromatic series iodine

Salt, aromatic series sulfonium salt etc.

Salt, and iron-aromatic hydrocarbons complex compound (iron-アレン Wrong body), but be not limited to these.Photoepolymerizationinitiater initiater is owing to produce catalytic action by light, even therefore mix with monomer and/or oligomer, storage stability or operability are also excellent.

The aromatic series diazo salt can be enumerated hexafluoro-antimonic acid diazobenzene, hexafluorophosphoric acid diazobenzene and hexafluoro boric acid diazobenzene.

Aromatic series iodine

Salt can be enumerated diphenyl iodonium

Four (pentafluorophenyl group) borate, diphenyl iodonium

Hexafluorophosphate, diphenyl iodonium

Hexafluoro antimonate and two (4-nonyl phenyl) iodine Hexafluorophosphate.

The aromatic series sulfonium salt can be enumerated the triphenylsulfonium hexafluorophosphate; the triphenylsulfonium hexafluoro antimonate; triphenylsulfonium four (pentafluorophenyl group) borate; 4; the two hexafluorophosphates of 4 '-two [diphenyl sulfonium base (ジ Off エニ Le ス Le ホニオ)] diphenyl sulfide; 4; the two hexafluoro antimonates of 4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium base (ス Le ホニオ)] diphenyl sulfide; the two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulfide; 7-[two (to toluyl groups) sulfonium base]-2-isopropyl thioxanthone hexafluoro antimonate; 7-[two (to toluyl groups) sulfonium base]-2-isopropyl thioxanthone four (pentafluorophenyl group) borate; 4-phenylcarbonyl group-4 '-diphenyl sulfonium base-diphenyl sulfide hexafluorophosphate; 4-(to the tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium base-diphenyl sulfide hexafluoro antimonate and 4-(to the tert-butyl-phenyl carbonyl)-4 '-two (to toluyl groups) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate.

Iron-aromatic hydrocarbons complex compound can enumerate that dimethylbenzene-cyclopentadienyl group closes iron (II) hexafluoro antimonate, cumene-cyclopentadienyl group closes iron (II) hexafluorophosphate and dimethylbenzene-cyclopentadienyl group closes 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 can easily obtain commercially available product, as commercially available product, name with trade name, can enumerate " カヤラ Star De PCI-220 ", " カヤラ Star De PCI-620 " (above) by Japanese chemical drug (strain) system, " UVI-6990 " (ユニオ Application カ one バイ De society system), " アデカオプトマ one SP-150 ", " アデカオプトマ one SP-170 " (above) by rising sun electrochemical industry (strain) system, " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (above) by Japanese Cao Da (strain) system, " 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 " (above) by body どり chemistry (strain) system, " PI-2074 " (ロ one デイア society system), " CI-5120 " of preferred Japanese Cao Da (strain) system.

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

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

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

Thermal polymerization is to produce kation kind or lewis acidic compound by heating, specifically, can enumerate benzyl sulfonium salt, 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 can easily obtain commercially available product, as commercially available product, with the trade name name, can enumerate " アデカオプト Application CP77 " and " アデカオプト Application CP66 " (above), " CI-2639 " and " CI-2624 " (above), " サ Application エイ De SI-60L ", " サ Application エイ De SI-80L " and " サ Application エイ De SI-100L " (above) by three new chemical industry (strain) system by Japanese Cao Da (strain) system by rising sun electrochemical industry (strain) system.

Polymerization initiator can be distinguished use separately, perhaps also can mix more than 2 kinds and use.

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

Hardening resin composition can further contain oxetane compound, polyol compound etc. and promote polymeric compounds.Oxetane compound is the compound that has 4 yuan of cyclic ethers in molecule, specifically, can enumerate 3-ethyl-3-methylol oxetanes, 1, two [(3-ethyl-3-oxetanyl) methoxy] benzene of 4-, 3-ethyl-3-(phenoxymethyl) oxetanes, two [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes and phenol novolaks oxetanes (Off エ one ノ Le ボラ Star Network オキセタ Application).Above-mentioned oxetane compound can use commercially available product usually, as commercially available product, with the trade name name, can enumerate " 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 " (above) by East Asia synthetic (strain) system.Containing of oxetane compound proportionally is generally 5～95 weight %, is preferably 30～70 weight % in hardening resin composition.Polyol compound does not preferably have the polyol compound of the acidic-group except that the phenol hydroxyl, specifically, can enumerate polyol compound, polyester polyols alcoholic compound, polycaprolactone polyol compound, polyol compound and polycarbonate polyol with phenol hydroxyl with hydroxyl-removal functional group in addition.The molecular weight of polyol compound is preferably 62～1000.The containing ratio of polyol compound is generally 0～50 weight % in hardening resin composition, preferred 0～30 weight %.

Hardening resin composition and then also can contain other adjuvant, for example ion trap agent (イオ Application トラ Star プ drug) and antioxidant etc.It is that ion trap agent, antimony are that ion trap agent, magnesium are that ion trap agent, aluminium are that ion trap agent, calcium are that ion trap agent, titanium are the mineral compound of ion trap agent and their potpourri etc. that the ion trap agent can be enumerated Powdered bismuth.It is antioxidant that antioxidant can be enumerated hindered phenol.

＜the 1 film 〉

The 1st film does not contain the material of radiofluorescence by the ultraviolet ray irradiation.As the material of radiofluorescence can be enumerated polyethylene terephthalate, polycarbonate, polyethersulfone etc. by the ultraviolet ray irradiation.

The 1st film is preferably protected the diaphragm of the 2nd film.

The 1st film can be enumerated 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 of the cellulose acetate resin molding, amorphism cyclo-olefin-polymer films of tri acetyl cellulose film, diacetyl cellulose film etc. etc. etc., preferred cellulose acetate resin molding and amorphous polyolefins resin molding.

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

The 1st film is the low film of moisture permeability preferably, 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 μ m, is preferably 10～120 μ m, more preferably 10～85 μ m.

＜the 2 film 〉

The 2nd film does not contain the material of radiofluorescence by the ultraviolet ray irradiation.

The 2nd film is polarizer preferably, preferably comprises the film of polyvinyl alcohol resin, preferably comprises the film of resin that absorption has been orientated the dichromatism pigment, also preferably resin is carried out uniaxial tension and the film that obtains.

Polyvinyl alcohol resin can be by being that resin carries out saponification and obtains with polyvinyl acetate (PVA).Polyvinyl acetate (PVA) be resin can enumerate polyvinyl acetate (PVA) as the homopolymer of vinyl acetate, vinyl acetate and can with the multipolymer of vinyl acetate copolymerized other monomer.

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

The polyvinyl alcohol resin film that has been orientated the dichromatism pigment for absorption carries out the resulting film of uniaxial tension, can obtain through following operation,, polyvinyl alcohol resin film is carried out the operation of uniaxial tension that is; With the operation of polyvinyl alcohol resin film with the dichromatism pigment dyeing; The operation handled with boric acid aqueous solution of polyvinyl alcohol resin film with dyeing; The operation of after utilizing boric acid aqueous solution to handle, washing.

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

Colouring method can be enumerated polyvinyl alcohol resin film is immersed in method in the aqueous solution that contains the dichromatism pigment.The dichromatism pigment can be enumerated iodine and dichroic dye.

When using iodine, preferably polyvinyl alcohol resin film is immersed in the aqueous solution that contains iodine and potassium iodide and dyes as the dichromatism pigment.The content of iodine is generally about 0.01～0.5 weight portion with respect to 100 weight parts waters in the aqueous solution, and the content of potassium iodide is generally about 0.5～10 weight portion with respect to 100 weight parts waters.The temperature of aqueous solution is generally about 20～40 ℃, and the dip time in aqueous solution was generally about 30～300 seconds in addition.

When using dichroic dye, preferably polyvinyl alcohol resin film is immersed in the aqueous solution that contains dichroic dye and dyes as the dichromatism pigment.The content of dichroic dye is generally 1 * 10 with respect to 100 weight parts waters in the aqueous solution ^-3～1 * 10 ^-2About weight portion.Aqueous solution also can further contain the inorganic salts of sodium sulphate etc.The temperature of aqueous solution is generally about 20～80 ℃, and the dip time in aqueous solution was generally about 30～300 seconds in addition.

Boric acid is handled preferably to be immersed in the boric acid aqueous solution by the polyvinyl alcohol resin film with dyeing and is carried out.The content of boric acid aqueous solution mesoboric acid is generally about 2～15 weight portions with respect to 100 weight parts waters, is preferably about 5～12 weight portions.When using iodine as the dichromatism pigment, boric acid aqueous solution preferably contains potassium iodide.The content of potassium iodide is generally about 2～20 weight portions with respect to 100 weight parts waters in the boric acid aqueous solution, is preferably 5～15 weight portions.Dip time in boric acid aqueous solution was generally about 100～1200 seconds, was preferably about 150～600 seconds, more preferably about 200～400 seconds.The temperature of boric acid aqueous solution is generally more than 50 ℃, is preferably 50～85 ℃.

Washing after boric acid is handled is handled and is preferably undertaken by borated polyvinyl alcohol resin film is immersed in the water.After washing, implement dried, obtain film.The temperature of water was generally about 5～40 ℃ during washing was handled, and dip time was generally about 2～120 seconds.The dried of carrying out can use air drier, far infra-red heater to carry out usually afterwards.Baking temperature is generally 40～100 ℃.The processing time of dried was generally about 120～600 seconds.

＜the 3 film 〉

The 3rd film does not contain the material of radiofluorescence by the ultraviolet ray irradiation.

The moisture permeability low resin moldings such as amorphous polyolefins resin molding of the 3rd film except enumerating in the 1st film can also use cellulose acetate resin molding, acrylic resin film and crystalline polyolefin resin molding.The 3rd film is also preferably protected the diaphragm of the 2nd film.

The 1st film and the 3rd film can same each other mutually kinds, also can be different.

＜laminated body 〉

Fig. 1 represents the synoptic diagram of an example of laminated body, described laminated body is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and this hardening resin composition is solidified obtain.Laminated body 1 shown in Figure 1 is the laminated body of the 1st film 4 and the 2nd film 2 being fitted and forming across hardening resin composition 3.

Fig. 2 is the synoptic diagram of an example of laminated body, the 2nd film of the material that described laminated body is the 1st film that will not contain the material of the radiofluorescence by the ultraviolet ray irradiation, do not contain the radiofluorescence by the ultraviolet ray irradiation and the 3rd film that do not contain the material of radiofluorescence by the ultraviolet ray irradiation are fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition, and this hardening resin composition are solidified obtain.Laminated body 5 shown in Figure 2 be across hardening resin composition 9 with the 1st film 10 and the 2nd film 8 is fitted and across hardening resin composition 7 in the opposition side of a side of applying the 1st film 10 of the 2nd film laminated body that the 3rd film 6 forms of fitting.

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

For as laminated body 1, across the laminated body that hardening resin composition is fitted the 1st film and the 2nd film to obtain, can utilize the manufacture method that contains following operation to make,

＜operation (A) 〉

The for example following enforcement of operation (A) promptly, is coated with hardening resin composition on the 2nd film, attach the 1st film on the coated film of gained hardening resin composition.

Coating process to hardening resin composition is unqualified, can use various apparatus for coating such as scraper, line rod, mold pressing coating machine, comma coating machine (カ Application マコ one タ one), gravure roll coating machine to be coated with.In addition, can use the viscosity of being cured property of solvent resin combination to regulate.

Solvent is so long as the solvent of dissolving cured property resin combination gets final product, and without limits, the ester of the hydrocarbon system organic solvent of preferred toluene etc., ethyl acetate etc. is an organic solvent.The thickness of the resulting coated film of coating hardening resin composition is generally 0.1～50 μ m, is preferably 0.1～20 μ m, more preferably 0.1～10 μ m.

Before the 1st film and the 2nd film are fitted, the also processing that can implement that saponification processing, corona treatment, Cement Composite Treated by Plasma, tackify coating are handled etc. to the face of applying the 2nd film of the 1st film.The various processing layers of hard conating, anti-reflection layer, antiglare layer etc. also can be set on the face of the opposition side of the face of applying the 2nd film of the 1st film in addition.

＜operation (B) 〉

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

When utilizing rayed that hardening resin composition in the laminated body is solidified, unqualified to used light source, be the light source that has luminescence distribution below the 400nm preferably at wavelength.Specifically, can enumerate 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 one Block has been encouraged Shui Silver lamp) and metal halide lamp.Rayed intensity is according to the kind of the kind of hardening resin composition, particularly polymerization initiator and different, is that the rayed intensity in effective wavelength zone is 0.1～100mW/cm for the activation of polymerization initiator preferably ²Polymerization initiator.The rayed time is preferably set it according to the kind of the kind of hardening resin composition, particularly polymerization initiator and different, so that be 10～5000mJ/cm with the accumulation light quantity of rayed intensity and the product representation of rayed time ²

When utilizing heat that hardening resin composition in the laminated body is solidified, can heat with general known method, unqualified for condition etc., produce the kation kind at thermal polymerization usually, temperature more than the lewis acidic temperature heats, usually 50～200 ℃ of enforcements.

＜operation (C) 〉

Operation (C) is the operation of the cured resin composition layer irradiation active energy beam that solidified in the laminated body that obtains for above-mentioned operation (B).

The cured resin composition layer of having solidified is radiofluorescence by the irradiation of active energy beam.Active energy beam can be enumerated visible light, ultraviolet ray, X ray and electron beam as mentioned above.

＜operation (D) 〉

Operation (D) is to measure the active energy beam be subjected to irradiation in the above-mentioned operation (C), and the operation of the fluorescence intensity of the fluorescence that radiates from cured resin composition layer.

The common determinator of fluorescence intensity utilization is measured.

＜operation (E) 〉

Operation (E) is based on the fluorescence intensity of measuring in the above-mentioned operation (D), the cohesive of the 1st film and the 2nd film in the evaluation laminated body, and the operation of the quality quality of judgement laminated body.The intensity of fluorescence (fluorescence intensity) of radiation changes according to the chemical state of polymerization initiator.Therefore, by measuring fluorescence intensity, can estimate many a spot of polymerization initiators and be consumed, that is, the 1st film in the laminated body and the 2nd film have carried out bonding so fusible state of which kind of degree.Laminated body to the 1st film and the 2nd film are fully fitted and formed in advance, measure the moment that polymerization initiator is consumed basically, promptly, the 1st film in the laminated body and the 2nd film cohesive fluorescence intensity fully constantly, and with it as reference value, thus by the fluorescence intensity of this reference value relatively and mensuration, can estimate the cohesive of the 1st film and the 2nd film in the laminated body, and judge the quality quality of laminated body.And, consider yield or temperature change etc., in hardening resin composition, contain the polymerization initiator of amount that the amount that needs in theory multiply by the spacious and comfortable coefficient gained of regulation, so polymerization initiator " is consumed " state that is meant that the spike (free radical, acid etc.) that only fully produces curing reaction is generated by polymerization initiator basically more.

This operation contains selected step of benchmark and evaluation procedure.And, in following steps, for narrating by the situation of the laminated body irradiates light that obtains in the operation (A) being implemented operation (B).For the situation of implementing operation (B) by the laminated body that obtains in the heating process (A), as long as use by the parameter substitution accumulation light quantity that obtains heating-up temperature and heat time heating time.(benchmark is selected step)

" benchmark is selected step " is the step that the benchmark of judging the cohesive quality is selected, for example can be by following program selecting benchmark.

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

(II) carry out rayed for the model sample of making in the above-mentioned operation (I) to accumulate light quantity arbitrarily, make the different model sample of solid state of hardening resin composition, for example the model sample of any cure stage from its uncured state to completely crued state.Then, change the accumulation light quantity, and sharp using the same method made the different model sample of cure stage.So make a plurality of model samples of different cure stage.

(III) for a plurality of model samples of making in the above-mentioned operation (II), use fluorescence spectrum analyzer to measure the active energy beam that is shone and the intensity of fluorescence that radiates is used as fluorescence spectrum, the accumulation light quantity when obtaining to solidify thus and the relation of fluorescence intensity.

(IV) for a plurality of model samples of making, utilize known cohesive evaluation method to estimate its cohesive, accumulation light quantity and fusible relation when obtaining to solidify, the accumulation light quantity when selecting the abundant fusible curing of performance.Known cohesive evaluation method can be enumerated the disbonded test of cutter test, disbonded test etc. etc.

The accumulation light quantity and the relation of fluorescence intensity during (V) by the curing that obtains in the above-mentioned operation (III), the pairing fluorescence intensity of accumulation light quantity when selecting the abundant fusible curing of the performance selected in the above-mentioned operation (IV) is as benchmark (threshold value).

(evaluation procedure)

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

Specifically, if the fluorescence intensity ratio of measuring in the operation (D) selected benchmark (threshold value) height in the selected step of benchmark, then can be evaluated as cohesive good for this laminated body.In addition, if the benchmark (threshold value) that the fluorescence intensity ratio of measuring in the operation (D) is selected in the selected step of benchmark is low, then the cohesive of this laminated body can be evaluated as bad.Like this, can not cause by disbonded test etc. under the damaged situation laminated body being carried out the cohesive evaluation.

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

In addition owing to utilized and comparison as the threshold value of benchmark, therefore can also easily estimate with respect to as the threshold value of benchmark, the solid state of hardening resin composition relatively, that is, and the cohesive of the 1st film and the 2nd film.In addition, have or not the threshold value that deviates from as benchmark, can find the unusual of hardening resin composition etc. in early days by monitoring.Thus, a large amount of generations of substandard products etc. can be suppressed, the raising of production qualification rate can be realized.

For as laminated body 5, across hardening resin composition the 1st film and the 2nd film are fitted and across hardening resin composition in the opposition side of a side of applying the 1st film of the 2nd film laminated body that the 3rd film forms of fitting, can utilize the manufacture method that contains following operation to make

(A '-2) at the opposition side of a side the 2nd film, that fitted the 1st film, across hardening resin composition fit the 3rd film and the 2nd film, obtains the operation of laminated body;

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

Operation (A '-1) and operation (A '-2) are implemented equally with above-mentioned operation (A).Operation (A '-2) is in the fit operation of the 3rd film of the opposition side of a side of the 2nd film, the 1st film of having fitted.And operation (A '-2) can be carried out afterwards in operation (A '-1), also can carry out simultaneously with operation (A '-1).

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

(evaluating apparatus)

Carry out following explanation for evaluating apparatus as an embodiment realizing evaluation method of the present invention.

Evaluating apparatus comprises fluorometric assay head, evaluation portion.Fluorometric assay is instructed according to the irradiation that receives from evaluation portion with head, the mensuration active energy beam that is used to measure fluorescence to the laminated body irradiation, on the other hand, it accepts the fluorescence that radiates from hardening resin composition, and the fluorescence intensity of measuring is exported to evaluation portion.

Evaluation portion gives fluorometric assay and instructs with the head irradiation according to the irradiating state signal from rayed or heating arrangement.

Rayed or heating arrangement comprise rayed or heating part and control part.Rayed or heating part produce light or the heat that is used to make hardening resin composition curing according to the irradiation instruction from control part.Control part applies the irradiation instruction according to the instruction from outsides such as users to rayed or heating arrangement, synchronously the irradiating state signal is outputed to evaluation portion with this irradiation instruction simultaneously.

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

CPU indicates with ultraviolet irradiation with head output fluorometric assay fluorometric assay according to from the operation of operating portion indication with from the irradiating state signal of rayed or heating arrangement.CPU, lights irradiation warning portion or makes its flicker in order to impel the protection of the fluorometric assay of radiating with head from fluorometric assay being used active energy beam corresponding to fluorometric assay is indicated with the irradiation of active energy beam with the fluorometric assay of head.CPU accepts the fluorescence intensity measured with head by fluorometric assay, the cohesive as the laminated body of object is estimated, and this evaluation result etc. is exported to display part.Meanwhile, CPU will represent that the signal (simulation, numeral) of the fluorescence intensity measured with head by fluorometric assay is to external device (ED) outputs such as (not diagrams).And then CPU reads the various data that pre-deposit from storage part, deposits in storage part such as data of instrumentation.

Display part contains for example display of LCD (Liquid Crystal Display), CRT (Cathode Raytube) etc., the curve that the fluorescence intensity that its demonstration is accepted from CPU changes etc.

Operating portion comprises various switches etc., and it accepts the operation from the user, and will operate corresponding operation indication with this and export to CPU.

Irradiation warning portion comprises for example LED, lamp etc., and it is for being near the user of the position of evaluating apparatus etc., the prompting fluorometric assay with active energy beam in irradiation.

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

Fluorometric assay 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) with head.

The light projector driving circuit applies the voltage of pulse type according to the irradiation indication of the fluorometric assay of accepting from CPU with active energy beam to light-projecting component with the cycle of stipulating.Light-projecting component comprises for example ultraviolet LED, and it also radiates with active energy beam and produce fluorometric assay according to the pulse voltage that is added by the light projector driving circuit.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 the same optical axis, it sees through the fluorometric assay active energy beam that radiates from light-projecting component, on the other hand, it makes from the travel path of the fluorescence that radiates as the hardening resin composition the laminated body of determination object and changes, and guides light filter into.For example, the reflecting surface of half-reflecting mirror forms by metal evaporation.

Light filter disposes in order to eliminate by the fluorometric assay of the light-projecting component irradiation stray light with active energy beam 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, light filter is that transmission peak wavelength is the filtrator of the dielectric multilayer film of the above light of 410nm.

An example of photo detector comprises photodiode, and it produces electric current according to the intensity of fluorescence that sees through light filter incident, and exports to HPF.

In the fluorescence intensity signals that HPF will be accepted by photo detector, flip-flop and low-frequency component remove, and the above signal of assigned frequency is passed through, and solidifies the composition that produces with ultraviolet ray to extract out to utilize.

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

Come synchronously the luminous opportunity of S/H circuit and light-projecting component sampled by light intensity signal, the signal value that keeps collection, when sampling next time, be determined at the peak swing value of the signal in each cycle in each specified period of carrying out the pulse type light projector thus, in each cycle, keep the peak swing value of mensuration.

Analog-to-digital conversion portion will be converted to numerical value by the voltage signal (simulating signal) of S/H circuit output, and export to CPU.

Then, probably describe for the optical system of fluorometric assay with head.

Fluorometric assay also has convergent lens with head.Form following structures, promptly, light-projecting component, half-reflecting mirror, convergent lens and be configured on the same straight line as the hardening resin composition of object are converged to specific diameter range by convergent lens at hardening resin composition with active energy beam from the fluorometric assay of light-projecting component irradiation.Propagate in opposite direction in same path with active energy beam from fluorescence and fluorometric assay that hardening resin composition radiates, and change travel path with the half-reflecting mirror reflection.And then, fluorescence by light filter to photo detector incident.And, roughly the same to the distance of convergent lens with distance from convergent lens to hardening resin composition from the shadow surface of light-projecting component.

(the cohesive evaluation of laminated body)

For example, according to following such processing, carry out the cohesive evaluation of the selected and laminated body of reference value.And, below handle at estimating as the fusible example of laminated body 1, laminated body that the 1st film and the 2nd film are formed across the hardening resin composition applying, even but for laminated body 5 such, across hardening resin composition the 1st film and the 2nd film are fitted, and across hardening resin composition in the applying of the 2nd film the opposition side of one side of the 1st film laminated body that the 3rd film forms of fitting, also carry out the cohesive evaluation of the selected and laminated body of reference value according to the processing same with it.

(selecting of reference value)

At first, CPU is according to judging from the irradiating state signal of rayed or heating arrangement whether rayed or heating have begun.For rayed or heating situation about not beginning, CPU is back to starting point (below be referred to as step S1).

When rayed or when beginning heating, CPU applies irradiation instruction (below be referred to as step S2) to fluorometric assay with head.So fluorometric assay is shone the fluorometric assay active energy beam with head to the hardening resin composition as object.CPU obtains fluorescence intensity from fluorometric assay with head, and described fluorescence intensity is to be subjected to fluorometric assay makes the polymerization initiator that contains in this hardening resin composition radiate with the irradiation of active energy beam intensity of fluorescence.

Then, CPU deposits the fluorescence intensity that obtains in storage part, judges whether accumulated the above fluorescence intensity data of stated number in the storage part simultaneously.When the fluorescence intensity data that do not accumulate more than the stated number, CPU is back to step S2.

When having accumulated the fluorescence intensity data more than the stated number, CPU reads the fluorescence intensity data from the stated number of storage part, carries out equalization and handles (moving average), and calculate the fluorescence intensity in this moment.

And then CPU obtains the fluorescence intensity calculated and by the customizing messages of the evaluation results such as disbonded test of inputs such as user, and based on the customizing messages that obtains carry out reference value selected (below be referred to as step 3).

For example work as fluorescence intensity and surpass P ^aThe time, the evaluation result of disbonded test etc. is good, when fluorescence intensity does not surpass P ^aThe time, not good if peel off the evaluation result of research, then CPU selectes P ^aAs reference value.

(the cohesive evaluation of laminated body)

CPU is according to judging from the irradiating state signal of rayed or heating arrangement whether rayed or heating have begun.For rayed or heating situation about not beginning, CPU is back to starting point (below be referred to as step S11).

When rayed or when beginning heating, CPU applies irradiation instruction (below be referred to as step S12) to fluorometric assay with head.So fluorometric assay is shone the fluorometric assay active energy beam with head to the hardening resin composition as object.CPU obtains fluorescence intensity from fluorometric assay with head, and described fluorescence intensity is to be subjected to measuring the intensity of fluorescence that the Photoepolymerizationinitiater initiater that contains in this hardening resin composition is radiated.

Then, CPU deposits the fluorescence intensity that obtains in storage part, judges whether accumulated the above fluorescence intensity data of stated number in the storage part simultaneously.When the fluorescence intensity data that do not accumulate more than the stated number, CPU is back to step S12.

When having accumulated the fluorescence intensity data more than the stated number, CPU reads the fluorescence intensity data from the stated number of storage part, carries out equalization and handles (moving average), calculates the fluorescence intensity in this moment.

And then CPU is according to the fluorescence intensity calculated, the fusible evaluation of carrying out laminated body handle (below be referred to as step 13).Specifically, CPU calls the subroutine that contains following treatment scheme and carries out.

CPU obtain by the customizing messages of thickness of the coated film of the kind of the hardening resin composition of inputs such as user, the 1st film and the 2nd film and hardening resin composition etc. (below be referred to as step 14), and, read reference value P as the specific fluorescence intensity of benchmark from storage part according to the customizing messages that in step 14, obtains ^a(below be referred to as step 15).Whether CPU surpasses the reference value P that reads in the step 15 to the fluorescence intensity of calculating ^aJudge (below be referred to as step 16).And reference value also can be specified by the user in advance.When the fluorescence intensity of measuring surpasses reference value P ^aThe time, it is good that CPU is considered as the cohesive of laminated body, and be back to processing (step S11) originally.

On the other hand, the fluorescence intensity when mensuration surpasses reference value P ^aThe time, CPU is considered as the poor adhesion of laminated body, and is back to processing (step S11) originally.

Then, CPU to outputs such as display parts, and judges whether fusible evaluation result etc. to satisfy and measures termination condition.Measure termination condition and can suitably adopt following condition, that is, through official hour, for example obtain judging the condition that reaches the such particular result of maximum degree of cure etc. after rayed or the heating beginning.When not satisfying the mensuration termination condition, CPU is back to step 12.On the other hand, when satisfying the mensuration termination condition, CPU is back to starting point (step 11).

For laminated body, according to the difference of rayed conditioned disjunction heating condition, the cohesive of the 1st film and the 2nd film changes, and produces following problem sometimes.For example when rayed or heat when insufficient, the laminated body that obtains has the possibility of shortcomings such as the peeling off of film, variable color taking place and/or fade.In addition, for example when rayed or over-heating, the laminated body that obtains has the possibility of shortcomings such as producing wrinkle or curl on film.Find this shortcoming for timely, and the cohesive of controlling diaphragm, need under the state that does not destroy laminated body and in production line, the cohesive of laminated body be estimated.

Therefore, introducing has the evaluating apparatus of fluorometric assay with head and evaluation portion in production line.Specifically, as described below.At first, the position from regulation is coated with hardening resin composition on the 1st film of output.In this coating or in the more downstream of production line, the 2nd film engages with the 1st film.The laminated body that obtains like this accepts to be used to light or heat that hardening resin composition is solidified from the rayed that comprises rayed or heating part, control part in the more downstream that is positioned at production line or heating arrangement.

At the downstream of this rayed or heating arrangement configuration evaluating apparatus.Arrange with the direction of throughput direction quadrature on the evaluating apparatus edge, and estimate the cohesive of the laminated body of carrying.Evaluating apparatus is estimated 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 handling accordingly with the reason that produces this shortcoming, for example change the UV-lamp of formation light irradiation device etc.

Embodiment

Below recorded and narrated the summary of realization according to an embodiment of the cohesive evaluation of the laminated body of embodiment of the present invention.

In cohesive evaluation method according to the laminated body of embodiment of the present invention, can the in-service evaluation device and solidify and use ultraviolet lamp, the cohesive that is configured in the laminated body on the sample bench is estimated.

Evaluating apparatus comprises fluorometric assay head and evaluation portion.Fluorometric assay is instructed with the irradiation of active energy beam according to the fluorometric assay that receives from evaluation portion with head, and be used to measure the fluorometric assay active energy beam of fluorescence to laminated body irradiation, on the other hand, it accepts the fluorescence that the hardening resin composition from laminated body radiates, and the fluorescence intensity of measuring is exported to evaluation portion.

Evaluation portion applies fluorometric assay irradiation instruction with active energy beam to fluorometric assay with head according to the irradiating state signal from light irradiation device.Evaluation portion estimates the cohesive of laminated body according to the fluorescence intensity of measuring with head in fluorometric assay.

Light irradiation device comprises rayed head and irradiation control part.The rayed head is according to indicating with ultraviolet irradiation from the curing of irradiation control part, and irradiation is solidified with ultraviolet ray to laminated body.The irradiation control part gives ultraviolet ray irradiation head and solidifies with the ultraviolet irradiation indication according to from outside indications such as users, will solidify synchronously with the ultraviolet irradiation status signal with this irradiation indication simultaneously and export to evaluation portion.

Brown spiral pipe (ス Network リユ one pipe) (No.5) in, with the hydrogenated epoxy resin (diglycidyl ether of bisphenol-A, trade name: エピコ one ト YX8000, ジヤパ Application エ Port キシレジ Application (strain) system, epoxide equivalent: the 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), with hydrogenated epoxy resin (trade name: エピコ one ト YX8000, ジヤパ Application エ Port キシレジ Application (strain) system) 7.0g, oxetane resin (3-ethyl-3-methylol oxetanes (oxa-cyclobutanol (オキセタ Application ア Le コ one Le)), trade name: アロ Application オキセタ Application OXT 101, East Asia synthetic (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), with hydrogenated epoxy resin (trade name: エピコ one ト YX8000, ジヤパ Application エ Port キシレジ Application (strain) system) 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 below is referred to as A1) as the 1st film,

Use the polyvinyl alcohol (PVA) dyestuff be polarizer (below be referred to as B1) as the 2nd film,

Use amorphous polyolefins resin molding (trade name: ZEONOR, Japanese ゼオ Application (strain) system below is referred to as C1) or cellulose ester membrane (trade name: New-nTAC, コニカ (strain) system below is referred to as C2) as the 3rd film.These A1, B1, C1 and C2 do not contain by the ultraviolet ray irradiation material of radiofluorescence.

The making of＜laminated body 〉

Use shown in the table 1, the 1st, the 2nd and the 3rd film and hardening resin composition, following making laminated body S1～S5.Behind coating hardening resin composition on the 1st film, the 2nd film of fitting.And then, behind coating hardening resin composition on the face of the opposition side of face the 2nd film, that fit the 1st film, the 3rd film of fitting.

The thickness that is noted that cured resin composition layer uses contact film thickness gauge ((strain) ニコ Application society system), calculates according to method shown below.

Measure the thickness of the laminated body of making, deduct the thickness of the 1st film, the 2nd film and the 3rd film of mensuration in advance respectively by the thickness that obtains, the value of using gained is divided by 2.And the thickness that obtains is according to locating, and shows as ± about 20% deviation, therefore changes to locate, and carries out 3 places and measures, and the mean value of the value when this 3 place is measured is as the thickness of cured resin composition layer.Thickness is shown in table 1.

Table 1

＜fluorescent strength determining 〉

With laminated body so that the 3rd film is in the state of upside (irradiation oral-lateral), in ultraviolet lamp (trade name: CV-1100-G, Off ュ one ジヨ Application UV システ system ズジヤパ Application (strain) system is used the D valve, power 80%, the height 4cm, speed 11m/ minute) in by the regulation number of times.Laminated body accumulation light quantity during by 4 times in ultraviolet lamp is about 600mJ/cm2 (UVB).For each laminated body, the power, speed and the number of pass times that change ultraviolet lamp carry out the mensuration of fluorescence intensity.

Use fluorescent strength determining device (trade name: OL201-1, (strain) セ Application テ Star Network society system), measure the fluorescence intensity (unit: V) that radiates by hardening resin composition by the fluorescent strength determining method.Fluorescent strength determining is following to carry out, promptly, use LED365D-S (excitation wavelength is 365nm) (to detect wavelength and be 420～700nm) as detecting device as light source, OL201, and set, the distance that makes lens and measured object is for about 35mm, value for the projection quantity are 10%, sensitivity is 60%, sensitivity is 9.00.In addition, setting compensation value (オ Off セ Star ト) is so that the device displayed value when only placing corrosion resistant plate and measuring is zero.Device displayed value when at this moment, measuring " ND-40 " as the standard fluorescence luminescent substance is about 5.00V.And measuring all is so that the 3rd film is in the state of upside (irradiation oral-lateral) implements.Measured value is according to locating ± about 20% deviation, therefore change is located carry out the value of 3 places when measuring mean value as fluorescence intensity.

＜adhesion test 1 〉

Estimate the cohesive of the 1st film and the 2nd film with the cutter test method(s).The results are shown in table 2.

＜adhesion test 2 〉

Estimate the cohesive of the 3rd film and the 2nd film with the cutter test method(s).The results are shown in table 2.

The cutter test method(s) is following to carry out, promptly, at first on the 1st film surface of laminated body, form the ditch of surface until about the 1cm that reaches the 2nd film with cutter, then make the angle and the surperficial almost parallel (state that blade is lain low) of the blade of cutter, central portion at ditch is put into cutter, and point of a knife is passed through between the 1st film and the 2nd film, directly with cutter (inboard) propelling forwards.

At this moment, even when also advancing without power, blade, cohesive is bad, the note work *.When a little is exerted oneself, when blade entered the 5mm left and right sides, cohesive was good, and note is made △.Even when quite exerting oneself, blade can not enter and film self when being cut off at once well, and cohesive is very good, and note does zero.This test carry out ultraviolet ray irradiation back after about 1 hour, after about 3 hours, implement about 1 day (24 hours) back.For the surface of the 3rd film of laminated body, carry out equally with above-mentioned, and estimate equally.

＜adhesion test 3 〉

Estimate the cohesive of the 1st film and the 2nd film with the disbonded test method, measure peel strength (unit: N).The results are shown in table 2.

Disbonded test uses オ one トグラ Off AGS-100D (trade name, society of (strain) Shimadzu Seisakusho Ltd. system) to carry out.2 bonding films (the 1st film and the 2nd film) part is peeled off, the bonded body of peeling off the place is fixed at one end, adherend is fixed on the other end, used power is calculated peel strength when carrying out tearing by being determined at expansion interval between the two.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 size about 2.5cm * 15cm.This moment, stripping portion and non-stripping portion were in long axis direction.The 1st film at the place of peeling off of this sample is fixed on the peel test device upside, and the sample after the 1st film is peeled off is fixed on the peel test device downside.

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

Table 2

In the table ,-expression undetermined.

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

Industrial applicability

According to method for evaluating adhesion property of the present invention, in the situation of not peeling off laminated body, can estimate its cohesive.

Claims

1. cohesive evaluation method, it is the cohesive evaluation method that the cohesive of film in the laminated body is estimated, described laminated body is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and this hardening resin composition is solidified and the laminated body that obtains

It contains following operation:

2. method for evaluating adhesion property; It is the method for evaluating adhesion property that the cohesive of film in the laminated body is estimated; The 2nd film of the material that described laminated body is the 1st film that will not contain the material of the radiofluorescence by the ultraviolet ray irradiation, do not contain the radiofluorescence by the ultraviolet ray irradiation and the 3rd film that do not contain the material of radiofluorescence by the ultraviolet ray irradiation are fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition; And this hardening resin composition is solidified and the laminated body that obtains

It contains following operation:

3. cohesive evaluation method according to claim 1, wherein, the 2nd film is a polarizer.

4. cohesive evaluation method according to claim 2, wherein, the 2nd film is a polarizer.

5. cohesive evaluation method according to claim 1 and 2, wherein, the 1st film is the diaphragm of protection the 2nd film.

6. cohesive evaluation method according to claim 2, wherein, the 3rd film is the diaphragm of protection the 2nd film.

7. cohesive evaluation method according to claim 1 and 2, wherein, the 1st film is to contain the film that is selected from least a kind of resin in cellulose acetate resin, amorphous polyolefins resin, crystalline polyolefin resin and the acrylic resin.

8. cohesive evaluation method according to claim 1 and 2, wherein, the 2nd film is the film that comprises polyvinyl alcohol resin.

9. cohesive evaluation method according to claim 1 and 2, wherein, the 2nd film is to comprise the film that absorption has been orientated the resin of dichromatism pigment.

10. cohesive evaluation method according to claim 1 and 2, wherein, the 2nd film is that resin is carried out the film that uniaxial tension obtains.

11. cohesive evaluation method according to claim 2, wherein, the 3rd film is to contain the film that is selected from least a kind of resin in cellulose acetate resin, amorphous polyolefins resin, crystalline polyolefin resin and the acrylic resin.

12. cohesive evaluation method according to claim 1 and 2, wherein, hardening resin composition is to contain monomer and/or oligomer and the composition of the polymerization initiator of radiofluorescence by the irradiation active energy beam.

13. the manufacture method of laminated body, it is to fit across hardening resin composition not containing the 1st film of material of the radiofluorescence by the ultraviolet ray irradiation and the 2nd film that does not contain the material of radiofluorescence by the ultraviolet ray irradiation, and make the manufacture method of the laminated body that this hardening resin composition solidifies

It is characterized in that, contain following operation:

14. the manufacture method of laminated body, the 2nd film of the material that it is the 1st film that will not contain the material of the radiofluorescence by the ultraviolet ray irradiation, do not contain the radiofluorescence by the ultraviolet ray irradiation and the 3rd film that do not contain the material of radiofluorescence by the ultraviolet ray irradiation are fitted by the mode that the 1st film and the 3rd film clip with the 2nd film across hardening resin composition, and make the manufacture method of the laminated body that this hardening resin composition solidifies

It is characterized in that, contain following operation: