KR101707424B1 - Evaluating method of adhesion property of film and process for manufacturing laminated body - Google Patents

Abstract

A first film not containing a material capable of emitting fluorescence by irradiation of ultraviolet rays and a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays are bonded to each other through a curable resin composition, An adhesion evaluation method for evaluating adhesion of a film in a laminate obtained by curing,
A step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,
A step of curing the curable resin composition in the un-cured laminate to obtain a laminate by irradiating the laminate with light or by heating the laminate,
A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,
And evaluating the adhesiveness between the first film and the second film in the laminate based on the measurement result of the fluorescence intensity.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of evaluating adhesiveness of a film and a method of manufacturing a laminated body,

The present invention relates to a method for evaluating the adhesiveness of a film and a method for producing a laminate.

Japanese Unexamined Patent Application Publication No. 2008-299175 discloses a method for evaluating adhesion of a film in a laminate in which a plurality of films typified by polarizing plates are laminated. In Japanese Unexamined Patent Application Publication No. 2008-299175, only a protective film in a polarizing plate is cut using a cutter knife, And evaluating whether or not the protective film can be peeled off from the cut portion thereof.

However, the above method is a method of cutting a protective film in a polarizing plate, and there is a demand for an adhesive property evaluation method for evaluating the adhesion between each film in a polarizing plate without involving destruction of the laminated body such as cutting the protective film .

Under such circumstances, the present inventors have made extensive studies and have reached the present invention.

That is,

[1] A method for producing a curable film, which comprises: curing a first film containing no material capable of emitting fluorescence by ultraviolet irradiation and a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays through a curable resin composition; An adhesive property evaluation method for evaluating adhesion of a film in a laminate obtained by curing a resin composition,

A step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,

A step of curing the curable resin composition in the laminate to obtain a laminate by irradiating the laminate with light or by heating the laminate,

A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,

A step of evaluating the adhesiveness between the first film and the second film in the laminate based on the measurement result of the fluorescence intensity;

[2] A method of producing a film, comprising the steps of: preparing a first film containing no material capable of emitting fluorescence by irradiation with ultraviolet rays, a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays and a material emitting fluorescence by irradiation of ultraviolet radiation Is bonded to the first film and the third film through the curable resin composition so that the second film is sandwiched between the first film and the third film and the adhesive properties of the film in the laminate obtained by curing the curable resin composition A method for evaluating an adhesion property,

A step of joining the first film and the second film with the curable resin composition interposed therebetween,

A step of bonding a third film to a second film through a curable resin composition on the side opposite to the side where the first film is bonded to obtain a laminate,

A step of curing the curable resin composition in the laminate to obtain a laminate by irradiating the laminate with light or by heating the laminate,

A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,

An adhesive property evaluation method comprising a step of evaluating the adhesion between the first film and the second film in the laminate and the adhesion between the second film and the third film based on the measurement result of fluorescence intensity;

[3] The adhesive property evaluation method according to [1], wherein the second film is a polarizer;

[4] an adhesion evaluation method described in [2] in which the second film is a polarizer;

[5] The adhesive property evaluation method according to any one of [1] to [4], wherein the first film is a protective film for protecting the second film.

[6] The adhesive property evaluation method according to [2], [4] or [5], wherein the third film is a protective film for protecting the second film;

[7] The film according to any one of [1] to [6], wherein the first film is a film comprising at least one resin selected from the group consisting of a cellulose acetate resin, an amorphous polyolefin resin, a crystalline polyolefin resin, An adhesion evaluation method described in any one of claims 1 to 3;

[8] The adhesive property evaluation method according to any one of [1] to [7], wherein the second film is a film made of a polyvinyl alcohol resin;

[9] The adhesive property evaluation method according to any one of [1] to [8], wherein the second film is a film made of a resin in which a dichroic dye is adsorbed and oriented.

[10] The adhesive property evaluation method according to any one of [1] to [9], wherein the second film is a film obtained by uniaxially stretching a resin;

[11] The film according to [2] or [4] to [10], wherein the third film is a film comprising at least one resin selected from the group consisting of a cellulose acetate resin, an amorphous polyolefin resin, a crystalline polyolefin resin, An adhesion evaluation method described in any one of claims 1 to 5;

[12] The adhesive property evaluation method according to any one of [1] to [11], wherein the curable resin composition comprises a monomer and / or an oligomer and a polymerization initiator that emits fluorescence by irradiation with an active energy ray.

A first film not containing a material capable of emitting fluorescence by irradiation of ultraviolet rays and a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays are bonded to each other through a curable resin composition, A method of producing a laminate for curing a composition,

(A) a step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,

(B) curing the curable resin composition in the laminate by irradiating the laminate with light or by heating the laminate to obtain a laminate,

(C) irradiating the cured curable resin composition layer in the laminate with an active energy ray,

(D) measuring fluorescence intensity of fluorescence emitted from the curable resin composition layer by receiving the active energy ray irradiated in the step (C); and

(E) evaluating the adhesiveness between the first film and the second film in the laminate based on the fluorescence intensity measured in the step (D), and judging whether the quality of the laminate is good or bad A method for producing a laminate characterized by;

[14] A method of producing a film comprising a first film containing no material capable of emitting fluorescence by irradiation with ultraviolet rays, a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays, and a material emitting fluorescence by irradiation of ultraviolet radiation Wherein the second film is cured by being sandwiched between the first film and the third film via the curable resin composition and the curable resin composition is cured,

(A'-1) bonding the first film and the second film via the curable resin composition,

(A'-2) a step of joining a third film to the second film via a curable resin composition on the side opposite to the side where the first film is bonded, to obtain a laminate;

(B ') laminate, or by heating the laminate to obtain a laminate by curing the curable resin composition in the laminate,

(C ') irradiating the cured curable resin composition layer in the laminate with an active energy ray,

(D ') measuring a fluorescence intensity of fluorescence emitted from the curable resin composition layer by receiving an active energy ray irradiated in the step (C');

(E ') Based on the fluorescence intensity measured in the step (D'), the adhesion between the first film and the second film in the laminate and the adhesion between the second film and the third film are evaluated And judging whether the quality of the laminate is good or bad; And the like.

According to the present invention, a first film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays and a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays are bonded through a curable resin composition, The adhesiveness of the film in the layered product obtained by curing the curable resin composition can be easily evaluated without destroying the layered product.

Fig. 1 is a schematic view showing the layered product 1. Fig.
Fig. 2 is a schematic view showing the layered product 5. Fig.

(Mode for carrying out the invention)

In the first adhesive property evaluation method of the present invention,

A first film not containing a material capable of emitting fluorescence by irradiation of ultraviolet rays and a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays are bonded to each other through a curable resin composition, An adhesion evaluation method for evaluating adhesion of a film in a laminate obtained by curing,

A step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,

A step of curing the curable resin composition in the laminate to obtain a laminate by light irradiation or heating of the laminate,

A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,

And evaluating the adhesiveness between the first film and the second film in the laminate based on the measurement result of the fluorescence intensity.

In the second adhesive property evaluation method of the present invention,

A first film that does not contain a material that emits fluorescence by ultraviolet irradiation, a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays, and a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays Bonding the third film so that the second film is sandwiched between the first film and the third film through the curable resin composition and curing the curable resin composition to thereby evaluate the adhesive property of the film in the laminate As a property evaluation method,

A step of joining the first film and the second film with the curable resin composition interposed therebetween,

A step of bonding a third film to a second film through a curable resin composition on the side opposite to the side where the first film is bonded to obtain a laminate,

A step of curing the curable resin composition in the laminate to obtain a laminate by light irradiation or heating of the laminate,

A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,

And evaluating the adhesiveness between the first film and the second film in the laminate and the adhesion between the second film and the third film based on the measurement result of the fluorescence intensity.

In the present specification, the term "laminate" is used in a generic sense including both a laminate in which the curable resin composition is not cured and a laminate in which a part or all of the curable resin composition is cured.

<Curable resin composition>

The curable resin composition is a resin composition which is cured by light irradiation or heating and includes a monomer and / or an oligomer and a polymerization initiator that emits fluorescence by light irradiation or heating.

(Monomer)

Examples of the monomer include acrylic monomers such as polyester acrylate, urethane acrylate, polybutadiene acrylate, silicone acrylate and epoxy acrylate, and epoxy-based monomers. The monomer is also referred to as a monomer, and is a raw material in the case of synthesizing a resin by a curing reaction.

Examples of the epoxy-based monomer include hydrogenated epoxy-based monomers, alicyclic epoxy-based monomers and aliphatic epoxy-based monomers. As the epoxy-based monomer, an epoxy-based monomer not containing an aromatic ring is preferable.

The hydrogenated epoxy-based monomer is obtained by subjecting an aromatic epoxy-based monomer to a hydrogenation reaction selectively under pressure in the presence of a catalyst. Examples of the aromatic epoxy-based monomer include bisphenol-based monomers such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S;

Monomers constituting a novolak type epoxy resin such as a monomer constituting a phenol novolak epoxy resin, a monomer constituting a cresol novolak epoxy resin, and a monomer constituting a hydroxybenzaldehyde phenol novolac epoxy resin;

Polyfunctional epoxy type monomers such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxylated polyvinylphenol;

, And diglycidyl ether of bisphenol A is preferable.

As the alicyclic epoxy-based monomer, a compound represented by the formula (I):

(Wherein m represents an integer of 2 to 5, the hydrogen atom contained in the ring is substituted with an alkyl group having 1 to 4 carbon atoms, or one of the hydrogen atoms contained in the methylene group forming the ring is eliminated, And can be combined with other groups.)

And the like.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group and an ethyl group.

As the structure represented by the formula (I), an oxycyclohexane structure (m = 3) and an oxycycloheptane structure (m = 4) are preferable.

Examples of the compound having the structure represented by the formula (I) include the following compounds.

Formula (II):

(Wherein R ¹ and R ² represent, independently of each other, a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms)

Lt; RTI ID = 0.0 &gt; cyclohexylmethyl &lt; / RTI &gt; epoxycyclohexanecarboxylate:

Formula (III):

(Wherein R &lt; ³ &gt; And R ⁴ independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 20.

Bis (epoxycyclohexanecarboxylate) of an alkanediol represented by the following formula:

Formula (IV):

(Wherein R &lt; ⁵ &gt; And R ⁶ independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms, and p represents an integer of 2 to 20.

Of an alkanedicarboxylic acid represented by the following formula:

(V):

(Wherein R &lt; ⁷ &gt; And R ⁸ independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms, and q represents an integer of 2 to 10.)

Epoxy cyclohexyl methyl ether of polyethylene glycol represented by the formula:

Equation (VI):

(Wherein R &lt; ⁹ &gt; And R ¹⁰ independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms, and r represents an integer of 2 to 20.)

&Lt; / RTI &gt; epoxycyclohexylmethyl ether of an alkanediol represented by the formula:

Formula (VII):

(Wherein R &lt; ¹¹ &gt; And R ¹² independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms.

Diepoxy trispyro compounds represented by the following formula:

Formula (VIII):

(Wherein R &lt; ¹³ &gt; And R ¹⁴ independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms.

The diepoxy monospiro compound represented by the formula:

Equation (IX):

(Wherein R ¹⁵ represents a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms)

0.0 &gt; cyclohexene diepoxide &lt; / RTI &gt; represented by:

Formula (X):

(Wherein R &lt; ¹⁶ &gt; And And R ¹⁷ independently represent a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms.

Lt; RTI ID = 0.0 &gt;

Equation (XII):

(In the formula, R ¹⁸ represents a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms.)

Lt; / RTI &gt;

Among these,

Esters derived from 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxabicyclo [4.1.0] hepto-3-yl) methanol (wherein R ¹ and R ² are hydrogen atoms II)),

4-methyl-7-oxa-bicyclo [4.1.0] heptane-3-carbon acid (4-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) ester derived from methanol, (R ¹ is A compound represented by the formula (II) in which the methyl group is bonded at the 4-position and R ² is bonded at the 4-position as the methyl group)

Esters derived from 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethanediol (compounds represented by the formula (III) in which R ³ and R ⁴ are hydrogen atoms and n is 2)

(Compound represented by the formula (IV) in which R ⁵ and R ⁶ are hydrogen atoms and p is 2), an ester derived from (7-oxabicyclo [4.1.0] hept-3-yl) methanol and adipic acid,

(R ⁵ is bonded at the 4-position as a methyl group, and R ⁶ is a methyl group at the 4-position as a methyl group), an ester derived from (4-methyl-7-oxabicyclo [4.1.0] hepto- A compound represented by the formula (IV) wherein p is 2), and

(7-oxabicyclo [4.1.0] hept-3-yl) methanol and an ether derived from 1,2-ethanediol (R ⁹ And a compound represented by the formula (VI) in which R ¹⁰ is a hydrogen atom and r is 2).

Examples of the aliphatic epoxy-based monomer include aliphatic polyhydric alcohols and polyglycidyl ethers thereof, which are alkylene oxide adducts thereof. Specific examples thereof include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, di Glycidyl ether, and diglycidyl ether of propylene glycol.

(Oligomers)

The oligomer is also called a low polymer and is a resin having a degree of polymerization of about 2 to 20 and a relatively low degree of polymerization. As the oligomer, oligomers of the above-mentioned monomers can be mentioned, and epoxy-type oligomers which do not contain an aromatic ring are preferable. An epoxy-based oligomer not containing an aromatic ring is an oligomer derived from a monomer having an epoxy group and not containing an aromatic ring in its structure.

The epoxy equivalents of the monomers and oligomers are usually 30 to 3,000 g / equivalent, preferably 50 to 1,500 g / equivalent.

The monomers and oligomers may be used alone or in combination of two or more thereof.

(Polymerization initiator)

Examples of the polymerization initiator that emits fluorescence by irradiation of an active energy ray include (1) a radical polymerization initiator that generates radicals by light irradiation or heating, and (2) a radical polymerization initiator that generates radicals by cationic polymerization initiators (Large). The radical polymerization initiator is used, for example, in the case where the curable resin composition contains an acrylic monomer and / or an oligomer, and the cationic polymerization initiator is, for example, an epoxy-based monomer, a vinyl ether- Or an oligomer. Initiation of a polymerization reaction by light irradiation is referred to as a photopolymerization initiator and initiation of polymerization reaction by heating is referred to as a thermal polymerization initiator. When the photopolymerization initiator is used, the curable resin composition can be cured at room temperature, and it is unnecessary to consider deformation due to heat resistance or expansion of the first film and the second film, and the film can be favorably adhered .

Examples of the active energy ray include visible ray, ultraviolet ray, X-ray and electron (electron) ray.

(1) Radical polymerization initiator

The radical polymerization initiator is roughly classified into a hydrogen withdrawing type and an intramolecular cleavage type depending on the generation process of the radical. Examples of the hydrogen-derived radical polymerization initiator include benzophenone and methyl orthobenzoylbenzoate. Examples of intramolecular cleavable radical polymerization initiators include benzoin ethers, benzyl dimethyl ketal,? -Hydroxyalkylphenones,? -Aminoalkylphenones, methyl oxovbenzoylbenzoates, 4-benzoyl-4'-methyldiphenylsulfides, Hydroxy-2-methyl-1-phenyl-propanone, benzyldimethylketal and 1,2-hydroxyalkylphenones, .

(2) Cation polymerization initiator

As the cationic polymerization initiator, a diphenyliodonium salt can be mentioned. The term &quot; photopolymerization initiator &quot; in the present specification is not limited to the one in which the photopolymerization initiator remains capable of initiating the photopolymerization reaction, and the monomer or oligomer to be subjected to the photopolymerization reaction may be changed Is not present in the photopolymerization reaction, and thus it is used as a meaning that it has already become a substance which does not contribute to initiation of the photopolymerization reaction. The cationic polymerization initiator after the contribution to the photopolymerization initiating reaction is usually divided into two or more molecules, and it is considered that at least a part of the molecules after cleavage contributes to fluorescence emission.

Examples of the photopolymerization initiator that generates a cationic species or Lewis acid by light irradiation include an onium salt such as an aromatic diazonium salt, an aromatic iodonium salt and an aromatic sulfonium salt, and an iron-arene complex. It is not. Since the photopolymerization initiator acts catalytically to light, it is excellent in storage stability and workability even when mixed with monomers and / or oligomers.

Examples of the aromatic diazonium salt include benzene diazonium hexafluoroantimonate, benzene diazonium hexafluorophosphate and benzene diazonium hexafluoroborate.

Examples of the aromatic iodonium salt include diphenyl iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, and di (4-nonylphenyl) iodo Heptafluoroborate, and heptafluorobutylphosphate.

Examples of the aromatic sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4'-bis [diphenylsulfone Bis [di (? - hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluoroantimonate, 4,4'-bis [Di (? - hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthene hexafluoro (Pentafluorophenyl) borate, 4-phenylcarbonyl-4 ' -diphenylsulfamoyl-4,4'-diphenylsulfonium - diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfo-diphenylsulfide hexapropionate (Pentafluorophenyl) borate and 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenylsulfide tetrakis (pentafluorophenyl) borate.

Examples of the iron-arene complexes include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate and xylene-cyclopentadienyl iron (II) And tris (trifluoromethylsulfonyl) methanide.

(KAYARAD PCI-220), &quot; KAYARAD PCI-620 &quot; (manufactured by Nippon Kayaku Kabushiki Kaisha), &quot; UVI-6990 &quot; (manufactured by Nippon Kayaku Kabushiki Kaisha) as commercial products, (ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170 manufactured by Asahi Denka Kogyo Kabushiki Kaisha), CI-5102, CIT-1370 and CIT- DPI-101 "," DPI-102 "," DPI-103 "and" DPI-2064S "(all manufactured by Nippon Soda Co., Ltd.)," CIP- 102, "" BBI-103 "," BBI-105 "," TPS-101 "," TPS-102 "," MPI- , "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102", "DTS-103" (manufactured by Midori Kagaku Co., -2074 &quot; (manufactured by Rhodia), and &quot; CI-5102 &quot; manufactured by Nippon Soda Co., All.

When a photopolymerization initiator is used, a photosensitizer may be used in combination. When the photosensitizer is used in combination, the reactivity of the monomer and / or the oligomer is improved, and the mechanical strength and adhesive strength of the resulting cured product can be improved.

Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfate compound, a redox compound, an azo and diazo compound, a halogen compound, and a photoreducible dye.

Specifically, benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and?,? -Dimethoxy-? -Phenylacetophenone;

Benzophenone derivatives such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone;

Thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone;

Anthraquinone derivatives such as 2-chloro anthraquinone and 2-methyl anthraquinone;

Acridone derivatives such as N-methyl acridone and N-butyl acridone;

Other examples include?,? -Diethoxyacetophenone, benzyl, fluorenone, xanthene, uranyl compounds, and halogen compounds. These may be used alone or in combination. The content of the photosensitizer is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the curable resin composition.

The thermal polymerization initiator is a compound which generates a cationic species or a Lewis acid upon heating and specifically includes a benzylsulfonium salt, a thiophenium salt, a thioronium salt, a benzylammonium salt, a pyridinium salt, a hydrazinium salt, a carbonic acid ester, a sulfonic acid ester And amine imides. ADEKA OPTON CP-77 &quot; and &quot; ADEKA OPTON CP-66 &quot; (both manufactured by Asahi Denka Kogyo K.K.) and CI-2639 (trade name, available from Asahi Denka Kogyo K.K.) as commercial products, SANAID SI-80L &quot;, and &quot; SANAID SI-100L &quot; (all manufactured by SANSHIN KAGAKU KOGYO KABUSHIKI KAISHA) manufactured by Nippon Soda Co., ).

The polymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, per 100 parts by weight of the curable resin composition.

The curable resin composition may further contain a compound that promotes polymerization such as an oxetane compound or a polyol compound. The oxetane compound is a compound having a 4-membered ring ether in the molecule and specifically includes 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) (3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl ) Oxetane and phenol novolac oxetane. Aron Oxetane OXT-121 &quot;, &quot; Aron Oxetane OXT-211 &quot;, &quot; Aron Oxetane OXT-221 &quot;, and &quot; Aron Oxetane OXT-221 &quot;, all of which are commercially available products, And &quot; Aron Oxetane OXT-212 &quot; (manufactured by Toagosei Co., Ltd.). The content of the oxetane compound is usually 5 to 95% by weight, preferably 30 to 70% by weight in the curable resin composition. As the polyol compound, a polyol compound having no acidic group other than the phenolic hydroxyl group is preferable, and specifically, a polyol compound having no functional group other than a hydroxyl group, a polyester polyol compound, a polycaprolactone polyol compound, a polyol compound having a phenolic hydroxyl group, And polycarbonate polyol. The molecular weight of the polyol compound is preferably 62 to 1,000. The content of the polyol compound is usually 0 to 50% by weight, preferably 0 to 30% by weight in the curable resin composition.

The curable resin composition may further contain other additives such as an ion trap agent and an antioxidant. As the ion trap agent, inorganic compounds such as a powdery bismuth ion trapping agent, an antimony ion trapping agent, a magnesium ion trapping agent, an aluminum ion trapping agent, a calcium ion trapping agent, a titanium ion trapping agent, . As the antioxidant, a hindered phenol-based antioxidant may be mentioned.

<First film>

The first film does not contain a material that emits fluorescence by irradiation with ultraviolet rays. Examples of the material that emits fluorescence by irradiation with ultraviolet rays include polyethylene terephthalate, polycarbonate, and polyethersulfone.

The first film is preferably a protective film for protecting the second film.

Examples of the first film include an amorphous polyolefin resin film such as a cellulose acetate resin film such as a triacetyl cellulose film and a diacetyl cellulose film and an amorphous cycloolefin polymer film, an acrylic resin film such as a polymethyl methacrylate film, a polycarbonate resin film , A polysulfone resin film and an alicyclic polyimide resin film, and a cellulose acetate resin film and an amorphous polyolefin resin film are preferable.

The amorphous polyolefin resin is a resin having a structural unit derived from a cyclic olefin such as norbornene or a polycyclic norbornene monomer, and may be a copolymer of a cyclic olefin and a chain olefin. Specifically, thermoplastic saturated norbornene resins can be mentioned. Examples of commercially available amorphous polyolefin resins include "ARTON" manufactured by JSR Corporation, "ZEONEX" and "ZEONOR" manufactured by Nippon Zeon Co., Ltd., and "APO" and "APL" manufactured by Mitsui Kagaku Kogyo K.K. An amorphous polyolefin resin is formed by a known method such as a solvent casting method or a melt extrusion method to obtain a first film.

The first film is preferably a film having a low moisture permeability, specifically, a film made of a transparent resin having lower moisture permeability than triacetyl cellulose. The moisture permeability of triacetyl cellulose is about 400 g / m 2/24 hr.

The film thickness of the first film is usually about 5 to 200 mu m, preferably 10 to 120 mu m, and more preferably 10 to 85 mu m.

&Lt; Second film &

The second film does not contain a material that emits fluorescence upon irradiation with ultraviolet rays.

The second film is preferably a polarizer, preferably a film made of a polyvinyl alcohol resin, preferably a film made of a resin in which a dichroic dye is adsorbed and oriented, and is preferably a film obtained by uniaxially stretching the resin.

The polyvinyl alcohol resin is obtained by saponification of a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include copolymers of vinyl acetate and vinyl acetate, which are homopolymers of vinyl acetate, and other monomers copolymerizable with vinyl acetate.

Other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers and unsaturated sulfonic acids. The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 to 100 mol%. The polyvinyl alcohol resin may be further modified, specifically, polyvinyl foams and polyvinyl acetals modified with aldehydes. The weight average molecular weight of the polyvinyl alcohol resin is usually 1,000 to 10,000, preferably 1,500 to 10,000.

The film obtained by uniaxially stretching a polyvinyl alcohol resin film in which a dichroic dye is adsorbed and oriented is characterized by comprising a step of uniaxially stretching a polyvinyl alcohol resin film, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye, a step of dying a polyvinyl alcohol resin A step of treating the film with an aqueous solution of boric acid, and a step of washing with water after the treatment with an aqueous solution of boric acid.

Uniaxial stretching can be performed before dyeing or simultaneously with dyeing, and can be performed after dyeing. In the case of uniaxially stretching after dyeing, it may be carried out before the boric acid treatment or during the boric acid treatment. In addition, uniaxial stretching can be performed in a plurality of these steps. Examples of the uniaxial stretching method include a method of uniaxially stretching between rolls having different peripheral speeds, and a method of uniaxially stretching using a heat roll. Further, a dry stretching method of stretching in air, a wet stretching method of stretching in the state of being pushed by a solvent, and the like can be given. The stretching magnification is usually about 4 to 8 times.

Examples of the dyeing method include a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing a dichroic dye. Examples of dichroic dyes include iodine and dichromatic dyes.

When iodine is used as the dichroic dye, it is preferable to dyesthe polyvinyl alcohol resin film by immersing it in an aqueous solution containing iodine and potassium iodide. The content of iodine in the aqueous solution is usually about 0.01 to 0.5 parts by weight per 100 parts by weight of water, and the content of potassium iodide is usually about 0.5 to 10 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution is usually about 20 to 40 占 폚, and the immersion time in the aqueous solution is usually about 30 to 300 seconds.

When a dichroic dye is used as the dichroic dye, it is preferable to dyesthe polyvinyl alcohol resin film by immersing it in an aqueous solution containing a dichroic dye. The content of the dichroic dye in the aqueous solution is usually about 1 × 10 ^{-3 to} 1 × 10 ^-2 parts by weight per 100 parts by weight of water. The aqueous solution may also contain an inorganic salt such as sodium sulfate. The temperature of the aqueous solution is usually about 20 to 80 DEG C, and the immersion time for the aqueous solution is usually about 30 to 300 seconds.

The boric acid treatment is preferably carried out by immersing the dyed polyvinyl alcohol resin film in an aqueous solution of boric acid. The content of boric acid in the boric acid aqueous solution is usually about 2 to 15 parts by weight, preferably about 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as the dichroic dye, the aqueous boric acid solution preferably contains potassium iodide. The content of potassium iodide in the aqueous boric acid solution is usually about 2 to 20 parts by weight, preferably 5 to 15 parts by weight, per 100 parts by weight of water. The immersing time in the aqueous boric acid solution is usually about 100 to 1,200 seconds, preferably about 150 to 600 seconds, and more preferably about 200 to 400 seconds. The temperature of the boric acid aqueous solution is usually 50 占 폚 or higher, preferably 50 to 85 占 폚.

The water washing treatment after the boric acid treatment is preferably carried out by immersing the boric acid treated polyvinyl alcohol resin film in water. After washing with water, drying treatment is carried out to obtain a film. The temperature of the water in the water washing treatment is usually about 5 to 40 캜, and the immersing time is usually about 2 to 120 seconds. The subsequent drying process is usually carried out using a hot air dryer or a far-infrared heater. The drying temperature is usually 40 to 100 ° C. The treatment time in the drying treatment is usually about 120 to 600 seconds.

<Third film>

The third film does not contain a material that emits fluorescence upon irradiation with ultraviolet rays.

As the third film, a cellulose acetate resin film, an acrylic resin film, and a crystalline polyolefin resin film can be used in addition to the low moisture permeability resin film such as the amorphous polyolefin resin film exemplified in the first film. The third film is also preferably a protective film for protecting the second film.

The first film and the third film may be the same kind or different from each other.

<Laminate>

1, a first film not containing a material that emits fluorescence by irradiation of ultraviolet rays and a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays are bonded to each other through a curable resin composition, A schematic diagram of an example of the laminate obtained by curing the resin composition is shown. The laminate 1 shown in Fig. 1 is a laminate in which the first film 4 and the second film 2 are bonded to each other with the curable resin composition 3 interposed therebetween.

Fig. 2 shows a first film which does not contain a material that emits fluorescence by ultraviolet irradiation, a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays, and a material that emits fluorescence by irradiation of ultraviolet rays Is bonded to the first film and the third film through the curable resin composition such that the second film is sandwiched between the first film and the third film and the curable resin composition is cured to give a schematic view of one example of the laminate. The laminate 5 shown in Fig. 2 is obtained by bonding the film 10 of the first film and the second film 8 with the curable resin composition 9 interposed therebetween, And a third film (6) is bonded to the side of the film opposite to the side to which the first film (10) is bonded.

The method for producing the laminate of the present invention will be described below.

As in the case of the layered product (1), a laminate obtained by bonding a first film and a second film to each other through a curable resin composition,

(A) a step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,

(B) curing the curable resin composition in the laminate by irradiating the laminate with light or by heating the laminate to obtain a laminate,

(C) irradiating the cured curable resin composition layer in the laminate with an active energy ray,

(D) measuring a fluorescence intensity of fluorescence emitted from the curable resin composition layer by receiving an active energy ray irradiated in the step (C); and

(E) a step of evaluating the adhesiveness between the first film and the second film in the laminate based on the fluorescence intensity measured in the step (D), and judging whether the quality of the laminate is good or bad . &Lt; / RTI &gt;

&Lt; Process (A) &gt;

The step (A) is carried out, for example, by attaching a first film to a coating film of a curable resin composition obtained by applying a curable resin composition on a second film.

The method of applying the curable resin composition is not limited, and it can be applied by using various applicators such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater. The viscosity of the curable resin composition can be adjusted by using a solvent.

The solvent is not limited as long as it dissolves the curable resin composition. Hydrogenated hydrocarbon organic solvents such as toluene, and ester organic solvents such as ethyl acetate. The thickness of the coating film obtained by applying the curable resin composition is usually 0.1 to 50 占 퐉, preferably 0.1 to 20 占 퐉, and more preferably 0.1 to 10 占 퐉.

Before bonding the first film and the second film, the surface of the first film to which the second film is bonded may be subjected to a treatment such as a saponification treatment, a corona treatment, a primer treatment, and an anchor coating treatment. Various treatment layers such as a hard coating layer, an antireflection layer, and an antiglare layer can be formed on the surface of the first film opposite to the surface to which the second film is bonded.

&Lt; Process (B) &gt;

The step (B) is a step of irradiating light to the laminate obtained in the step (A) or heating to cure the curable resin composition in the laminate to obtain a laminate. When the curable resin composition is cured, the first film and the second film are fixed to each other.

When the curable resin composition in the laminate is cured by light irradiation, the light source to be used is not limited, but a light source having a light emission distribution with a wavelength of 400 nm or less is preferable. Specific examples thereof include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps and metal halide lamps. The light irradiation intensity varies depending on the kind of the curable resin composition, in particular, the kind of the polymerization initiator, but a polymerization initiator having a light irradiation intensity in the wavelength range effective for activating the polymerization initiator is preferably 0.1 to 100 mW / cm2. The light irradiation time varies depending on the kind of the curable resin composition, in particular, the kind of the polymerization initiator, but it is preferable to set the integrated light amount as a product of the light irradiation intensity and the light irradiation time to 10 to 5000 mJ / cm 2.

When the curable resin composition in the laminate is cured by heat, it can be heated by a generally known method so that the conditions and the like are not limited. Usually, the heat polymerization initiator is heated at a temperature higher than the temperature at which the cationic species or Lewis acid is generated, Lt; 0 &gt; C.

&Lt; Process (C) &gt;

Step (C) is a step of irradiating the cured curable resin composition layer in the laminate obtained in the step (B) with an active energy ray.

The cured curable resin composition layer emits fluorescence by irradiation of active energy rays. Examples of the active energy ray include visible rays, ultraviolet rays, X-rays and electron beams as described above.

&Lt; Process (D) &gt;

The step (D) is a step of receiving the active energy ray irradiated in the step (C) and measuring the fluorescence intensity of fluorescence emitted from the curable resin composition layer.

The fluorescence intensity is measured by a conventional measuring device.

&Lt; Process (E) &gt;

The step (E) is a step of evaluating the adhesiveness between the first film and the second film in the laminate based on the fluorescence intensity measured in the step (D), and judging whether the quality of the laminate is good or bad. It is considered that the intensity (fluorescence intensity) of the emitted fluorescence changes according to the chemical state of the polymerization initiator. Therefore, by measuring the fluorescence intensity, it is possible to evaluate the degree of adhesion of the polymerization initiator to a certain amount, that is, the degree to which the first film and the second film are adhered to each other to some extent. When the lamination body in which the first film and the second film are sufficiently bonded in advance is used at the time when the polymerization initiator is substantially consumed, that is, when the laminate has sufficient fluorescence intensity at the time when adhesion between the first film and the second film is sufficient And comparing the reference value with the measured fluorescence intensity, the adhesion between the first film and the second film in the laminate is evaluated to determine whether the laminate quality is good or bad. Since the curable resin composition often contains an amount of the polymerization initiator multiplied by a predetermined allowance relative to the theoretical required amount in consideration of yield and temperature fluctuations, the term &quot; substantially consumed &quot; Means a state in which enough active species (such as a radical or an acid) is generated from the polymerization initiator.

The present process includes a reference selection step and an evaluation step. In the following steps, step (B) is performed by irradiating light onto the laminate obtained in step (A). When the step (B) is carried out by heating the laminate obtained in the step (A), a parameter obtained from the heating temperature and the heating time can be used instead of the integrated light amount.

(Reference selection step)

The &quot; reference selection step &quot; is a step for selecting a criterion for judging good and bad adhesion, and for example, criteria are selected in the following order.

(I) A curable resin composition is applied on a second film so as to have a constant film thickness, and a first film is bonded on the coated film to prepare a model sample.

(II) irradiating the model sample produced in the above process (I) with light at an arbitrary integrated light quantity, and irradiating the cured resin composition to a different model sample, for example, from a (not yet) cured state to a completely cured state &Lt; / RTI &gt; in a curing step. Subsequently, by changing the integrated light quantity, a model sample having different curing steps is produced by the same method. In this way, a plurality of model samples in different curing stages are produced.

(III) For each of the plurality of model samples prepared in the step (II), the intensity of the fluorescence emitted by receiving the active energy ray irradiated using the fluorescence spectrum analyzer is measured as a fluorescence spectrum, Obtain the relationship with strength.

(IV) A plurality of fabricated model samples were evaluated for their adhesiveness by a known adhesive property evaluation method to obtain the relationship between the integrated light quantity and the adhesive property at the time of curing, and the integrated light quantity at the time of curing . Examples of known adhesiveness evaluation methods include peel test such as cutter knife test and peel test.

(V) From the relationship between the integrated light quantity at the time of curing and the fluorescence intensity obtained in the step (III), the fluorescent intensity for the integrated amount of light at the time of curing exhibiting sufficient adhesiveness selected in the above step (IV) ).

(Evaluation step)

The "evaluation step" is an evaluation (evaluation) for evaluating the adhesion between the first film and the second film by comparing the reference (threshold value) selected in the reference selection step with the fluorescence intensity measured in the step (D) Step.

Specifically, if the fluorescence intensity measured in the step (D) is higher than the criterion (threshold value) selected in the reference selection step, the laminate can be evaluated as having good adhesiveness. Further, if the fluorescence intensity measured in the step (D) is lower than the criterion (threshold value) selected in the reference selection step, it can be estimated that the adhesiveness of the laminate is not good. In this manner, the laminate can be evaluated for adhesiveness without being broken by a peeling test or the like.

Further, in a production line or the like, the same kind of curable resin composition is used under substantially the same irradiation conditions. Therefore, the threshold value of the fluorescence intensity is previously obtained for each curable resin composition, and the threshold value of the fluorescence intensity to be measured and the threshold value of the fluorescence intensity to be the reference It is practical and effective to estimate the cured state of the curable resin composition in the laminate to evaluate the adhesiveness.

Further, since the comparison with the reference threshold value is performed, the cured state of the curable resin composition relative to the reference threshold value, that is, the adhesion between the first film and the second film, can be easily evaluated. In addition, abnormalities such as the curable resin composition can be detected early by monitoring the deviation from the reference threshold value as a reference. As a result, it is possible to suppress the occurrence of large quantities of defective products and the like, and to improve the production yield.

The first film and the second film are bonded to each other with the curable resin composition interposed therebetween as in the case of the layered product (5), and the third film is provided on the side opposite to the side where the first film is bonded to the second film via the curable resin composition The bonded stacked body,

(A'-1) bonding the first film and the second film via the curable resin composition,

(A'-2) a step of bonding a third film and a second film to each other with a curable resin composition interposed therebetween on the side opposite to the side where the first film is bonded, to obtain a laminate,

(B ') laminate, or by heating the laminate to obtain a laminate by curing the curable resin composition in the laminate,

(C ') irradiating the cured curable resin composition layer in the laminate with an active energy ray,

(D ') measuring a fluorescence intensity of fluorescence emitted from the curable resin composition layer by receiving an active energy ray irradiated in the step (C');

(E ') Based on the fluorescence intensity measured in the step (D'), the adhesion between the first film and the second film in the laminate and the adhesion between the second film and the third film are evaluated And judging whether the quality of the laminate is good or bad.

The steps (A'-1) and (A'-2) are carried out in the same manner as in the step (A).

Step (A'-2) is a step of bonding the third film to the side of the second film opposite to the side to which the first film is bonded. Further, the step (A'-2) may be performed after the step (A'-1) or simultaneously with the step (A'-1).

The step (B ') is carried out in the same manner as the step (B). The step (C ') is carried out in the same manner as the step (C). The step (D ') is carried out in the same manner as the step (D). The step (E ') is carried out in the same manner as the step (E).

(Evaluation apparatus)

An evaluation apparatus which is one embodiment for realizing the evaluation method of the present invention will be described below.

The evaluation apparatus comprises a head for fluorescence measurement and an evaluation unit. The fluorescence measuring head part irradiates a measurement active energy ray for measuring fluorescence to the laminate in accordance with an irradiation command received from the evaluating part and receives the fluorescence intensity measured by receiving fluorescence emitted from the curable resin composition And outputs it to the evaluation unit.

The evaluating section gives an irradiation command to the head for fluorescence measurement based on the irradiation state signal from the light irradiation or heating apparatus.

The light irradiation or heating device comprises a light irradiation or heating section and a control section. The light irradiation or heating section generates light or heat for curing the curable resin composition in accordance with an irradiation command from the control section. The control unit gives an irradiation command to the light irradiation or heating device in accordance with a command from the outside of the user or the like, and outputs the irradiation status signal to the evaluation unit in synchronism with the irradiation command.

The evaluation unit includes a CPU (Central Processing Unit), a display unit, an operation unit, a storage unit, and an irradiation warning unit.

The CPU outputs an irradiation instruction of ultraviolet rays for fluorescence measurement to the head for fluorescence measurement in accordance with an operation instruction from the operation unit and an irradiation state signal from the light irradiation or heating apparatus. The CPU turns on or blinks the irradiation warning section in order to promote protection of the active energy ray for fluorescence measurement emitted from the fluorescent measurement head section in response to the irradiation instruction of the active energy ray for fluorescence measurement to the fluorescent measurement head section. The CPU receives the fluorescence intensity measured by the fluorescence measurement head, evaluates the adhesiveness of the laminate to be evaluated, and outputs the evaluation result or the like to the display unit. At the same time, the CPU outputs a signal (analog, digital) indicating the fluorescence intensity measured by the head for fluorescence measurement to an external device (not shown) or the like. Further, the CPU reads various data previously stored from the storage unit, and stores the measured data and the like in the storage unit.

The display unit includes, for example, a display such as a liquid crystal display (LCD) or a cathode ray tube (CRT), and displays a graph of fluorescence intensity change received from the CPU.

The operation unit is made up of various switches and receives an operation from the user and outputs an operation instruction to the CPU in accordance with the operation.

The irradiation warning section is composed of, for example, an LED or a lamp, and indicates that the active energy ray for fluorescence measurement is irradiated to a user at a position close to the evaluation apparatus.

The storage unit is composed of, for example, an EEPROM (Electrically Erasable and Programmable Read Only Memory) or the like, and stores measurement data and various kinds of data correlated with the types of the curable resin composition.

The fluorescence measurement head section includes a light projecting driving circuit, a light projecting element, a half mirror, an optical filter, a light receiving element, a HPF (High Pass Filter), an amplifying circuit, a Sample and Hold (S / H) And a conversion unit (ADC).

The projection driving circuit applies a pulse-like voltage to the light-projecting element at a predetermined cycle in accordance with an instruction to irradiate an active energy ray for fluorescence measurement received from the CPU. The light emitting element is made of, for example, an ultraviolet LED, and emits and emits an active energy ray for fluorescence measurement in accordance with a pulse voltage applied by the light projection drive circuit. In the embodiment of the present invention, the light emitting element irradiates an active energy ray for fluorescence measurement having a main emission peak at 365 nm.

The half mirror is disposed on the same optical axis as the light projecting element and transmits the active energy ray for fluorescence measurement emitted from the light transmitting element while changing the propagation path of fluorescence emitted from the curable resin composition in the laminate to be measured do. For example, the reflecting surface of the half mirror is formed by metal deposition.

The optical filter is arranged to remove disturbance light such as an active energy ray for fluorescence measurement emitted from the light emitting element, and is configured to attenuate light in the ultraviolet region while transmitting light in the visible region. In the embodiment of the present invention, the optical filter is a filter of a dielectric multilayer film transmitting light having a wavelength of 410 nm or more.

The light receiving element is composed of a photodiode as an example, generates a current according to the intensity of the fluorescent light transmitted through the optical filter, and outputs it to the HPF.

The HPF removes the direct current component and the low frequency component from the fluorescence intensity signal received from the light receiving element, and allows only the signal exceeding the predetermined frequency to pass through to extract the component generated by the ultraviolet ray for curing.

The amplifying circuit amplifies the signal having passed through the HPF at a predetermined amplification rate (current-voltage conversion rate), and outputs the amplified signal to the S / H circuit.

The S / H circuit samples the received light intensity signal in synchronization with the light emission timing of the light emitting element and holds the sampled signal value until the next sampling time so that the signal in each period Measure the maximum amplitude value and keep the measured maximum amplitude value within each period.

The analog-to-digital converter converts the voltage signal (analog signal) output from the S / H circuit into a digital value and outputs it to the CPU.

Next, the outline of the optical system of the head for fluorescence measurement will be described.

The head for fluorescence measurement further comprises a focusing lens. A curing resin composition for a light-emitting element, a half mirror, a focusing lens, and a target are arranged on the same straight line, and an active energy ray for fluorescence measurement emitted from the light-transmitting element is passed through a focusing lens to a specific diameter range Respectively. The fluorescence emitted from the curable resin composition propagates in the same direction as the active energy ray for fluorescence measurement in the opposite direction and is reflected by the half mirror to change the propagation path. Further, the fluorescence is incident on the light receiving element through the optical filter. Further, the distance from the irradiation surface of the light emitting element to the focusing lens and the distance from the focusing lens to the curable resin composition are made substantially equal.

(Evaluation of adhesiveness of laminate)

For example, the reference value is selected according to the following process, and the adhesion of the laminate is evaluated. The following process is for a case where the adhesion is evaluated with respect to the laminate obtained by bonding the first film and the second film to each other through the curable resin composition like the laminate (1). However, as in the case of the laminate (5) , A laminated body in which a first film and a second film are bonded to each other with a curable resin composition interposed therebetween and a cured resin composition is interposed and a third film is bonded to the side of the second film opposite to the side to which the first film is bonded According to the same process, the reference value is selected and the adhesion of the laminate is evaluated.

(Selection of reference value)

First, the CPU judges whether or not light irradiation or heating is started based on the irradiation state signal from the light irradiation or heating device. When light irradiation or heating is not started, the CPU returns to the starting point (hereinafter referred to as step S1).

When light irradiation or heating is started, the CPU gives an irradiation command to the fluorescent measurement head (hereinafter referred to as step S2). Then, the head for fluorescence measurement irradiates the active energy ray for fluorescence measurement to the target curable resin composition. Then, the CPU receives the active energy ray for fluorescence measurement and acquires the fluorescence intensity of the fluorescence emitted by the polymerization initiator contained in the curable resin composition from the fluorescence measurement head.

Subsequently, the CPU stores the acquired fluorescence intensity in the storage section and determines whether or not a predetermined number of fluorescence intensity data is stored in the storage section. If a predetermined number or more of fluorescent intensity data is not accumulated, the CPU returns to step S2.

When a predetermined number or more of fluorescence intensity data is stored, the CPU reads a predetermined number of fluorescence intensity data from the storage section and performs an averaging process (moving average) to calculate the fluorescence intensity at that time point.

The CPU acquires the calculated fluorescence intensity and specific information of the evaluation results such as the peeling test inputted from the user, and selects the reference value based on the acquired specific information (hereinafter referred to as step S3).

For example, when the fluorescence intensity exceeds P ^a , the evaluation result such as peeling test is good, and when the fluorescence intensity does not exceed P ^a , the peeling is performed, and if the evaluation result is not good, P ^a is selected as the reference value.

(Evaluation of adhesiveness of laminate)

The CPU judges whether or not light irradiation or heating is started based on the irradiation state signal from the light irradiation or heating device. When light irradiation or heating is not started, the CPU returns to the starting point (hereinafter referred to as step S11).

When light irradiation or heating is started, the CPU gives an irradiation command to the fluorescent measurement head (hereinafter referred to as step S12). Then, the head for fluorescence measurement is irradiated with a curable resin composition which is an active energy ray for fluorescence measurement. The CPU receives the active energy ray for measurement and acquires the fluorescence intensity of the fluorescence emitted by the photopolymerization initiator contained in the curable resin composition from the fluorescence measurement head.

Subsequently, the CPU stores the acquired fluorescence intensity in the storage section and determines whether or not a predetermined number of fluorescence intensity data is stored in the storage section. If a predetermined number or more of fluorescent intensity data is not accumulated, the CPU returns to step S12.

When a predetermined number or more of fluorescence intensity data is stored, the CPU reads a predetermined number of fluorescence intensity data from the storage section and performs an averaging process (moving average) to calculate the fluorescence intensity at that time point.

Further, the CPU executes the adhesion evaluation process of the laminate based on the calculated fluorescence intensity (hereinafter referred to as step 13). Specifically, the CPU invokes and executes a subroutine including the following processing flow.

The CPU obtains specific information such as the type of the curable resin composition, the first film and the second film, and the film thickness of the coating film of the curable resin composition inputted from a user or the like (hereinafter referred to as step 14) Based on the specific information, a reference value P ^a of a specific fluorescence intensity serving as ^a reference is read from the storage section (hereinafter referred to as step 15). The CPU determines whether the calculated fluorescence intensity exceeds the reference value P ^a read in step 15 (hereinafter referred to as step 16). The reference value may be specified by the user in advance. And, if the measured fluorescence intensity that is greater than the reference value (P ^a), CPU is considered to be excellent in adhesion between the layered product and the process returns to the original processing (step 11).

On the other hand, when the measured fluorescence intensity does not exceed the reference value P ^a , the CPU regards the adhesion of the laminate as poor and returns to the original process (step 11).

Subsequently, the CPU outputs a result of evaluation of adhesiveness to the display unit or the like to determine whether or not the measurement end condition is satisfied. As the measurement termination condition, a predetermined time has elapsed since the start of light irradiation or heating, for example, a specific result such as a determination that the maximum curing degree has been reached is suitably adopted. If the measurement end condition is not satisfied, the CPU returns to Step 12. On the other hand, when the measurement end condition is satisfied, the CPU returns to the starting point (step 11).

The adhesiveness of the first film and the second film changes depending on the light irradiation condition or the heating condition, and the following problems may arise. For example, when light irradiation or heating is insufficient, defects such as peeling, discoloration and / or discoloration of the film may occur in the resulting laminate. Further, for example, if light irradiation or heating is excessive, there is a possibility that defects such as wrinkles and curls may occur in the resulting laminate. In order to quickly detect such defects and to control the adhesiveness of the film, it is necessary to evaluate the adhesiveness of the laminate in the production line as it is without destroying the laminate.

Thus, an evaluation apparatus having a head for fluorescence measurement and an evaluation unit is introduced into the production line. Specifically, it is as follows. First, the curable resin composition is applied to the first film to be fed from a predetermined position. The second film is bonded to the first film simultaneously with the application or further downstream of the production line. The thus obtained laminate is subjected to light or heat for curing the curable resin composition from a light irradiation or heating unit located further downstream of the production line and a light irradiation or heating unit comprising a control unit.

An evaluation device is disposed on the downstream side of the light irradiation or heating device. The evaluating apparatus evaluates the adhesiveness of the laminate which is arranged and transported in the direction orthogonal to the carrying direction. The evaluation apparatus evaluates the adhesion of the first film and the second film in real time (in-line). Further, if there is any problem in the adhesiveness, processing according to the cause of the problem, for example, replacement of the ultraviolet lamp constituting the light irradiation apparatus, is performed.

Example

An outline of an embodiment for realizing the evaluation of adhesion of the laminate according to the embodiment of the present invention will be described below.

In the method for evaluating adhesion of a laminate according to the embodiment of the present invention, an evaluation device and a curing ultraviolet irradiation device are used, and the adhesiveness of the laminate placed on a sample object is evaluated.

The evaluation apparatus comprises a head for fluorescence measurement and an evaluation unit. The fluorescence measurement head section irradiates an active energy ray for fluorescence measurement for measuring fluorescence in accordance with an irradiation instruction of the active energy ray for fluorescence measurement received from the evaluation section toward the layered product and measures fluorescence emitted from the curable resin composition in the layered product And outputs the measured fluorescence intensity to the evaluation unit.

The evaluating section gives an instruction to irradiate the fluorescence measurement head to the fluorescence measurement active energy ray based on the irradiation state signal from the light irradiation apparatus. Then, the evaluating unit evaluates the adhesiveness of the laminate based on the fluorescence intensity measured in the head for fluorescence measurement.

The light irradiation apparatus comprises a light irradiation head unit and an irradiation control unit. The light irradiation head unit irradiates curing ultraviolet rays to the laminate in accordance with an irradiation instruction of curing ultraviolet ray from the irradiation control unit. The irradiation control section gives an irradiation instruction of the ultraviolet ray for hardening to the ultraviolet ray irradiation head section and outputs an irradiation state signal of the ultraviolet ray for hardening to the evaluation section in synchronization with the irradiation instruction in accordance with an instruction from the outside such as a user.

10.0 g of a hydrogenated epoxy resin (diglycidyl ether of bisphenol A, trade name: Epikote YX 8000, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 205 g / eq.) And 10.0 g of a photocationic polymerization initiator (aromatic sulfonium salt, trade name; SP-500, manufactured by ADEKA Corporation) were mixed in a brown screw tube (No. 5) to prepare a curable resin composition (X1).

(3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), trade name: Aron Oxetane OXT 101 (trade name), trade name: Epikote YX 8000, manufactured by Japan Epoxy Resin Co., 3.0 g) and 4.0 g of a cationic polymerization initiator (trade name: SP-500, manufactured by ADEKA Corporation) were mixed in a brown screw tube (No. 5) to obtain a curable resin composition (X2) It was prepared.

10.0 g of a hydrogenated epoxy resin (trade name: Epikote YX 8000, manufactured by Japan Epoxy Resins Co., Ltd.) and 4.0 g of a cationic ion polymerization initiator (compound of aromatic sulfonium salt, trade name: SP-152, manufactured by ADEKA Corporation) And a brown screw tube No. 5 to prepare a curable resin composition (X3).

As a first film, a cellulose ester film (trade name: 8UX-TAC, hereinafter referred to as A1) was used,

As the second film, a polyvinyl alcohol 1 dye-based polarizer (hereinafter referred to as B1) was used,

As a third film, an amorphous polyolefin resin film (trade name: ZEONOR, manufactured by Nippon Zeon Co., Ltd., hereinafter referred to as C1) or a cellulose ester film (trade name: New-nTAC, manufactured by Konica K.K. ). These A1, B1, C1 and C2 all do not contain a material that emits fluorescence by irradiation with ultraviolet rays.

&Lt; Preparation of laminate &gt;

The first, second and third films shown in Table 1 and the curable resin composition were used to produce laminated bodies S1 to S5 as follows. After the curable resin composition was applied onto the first film, the second film was bonded. Further, after the curable resin composition was applied on the surface of the second film opposite to the surface to which the first film was bonded, the third film was bonded.

The film thickness of the curable resin composition layer was calculated by the following method using a contact type film thickness meter (manufactured by Nikon Corporation).

The thicknesses of the first film, the second film and the third film that have been measured in advance are subtracted from the film thickness obtained by measuring the film thickness of the laminate thus formed, and the obtained value is divided by 2. In addition, since the obtained film thickness showed uniformity of the order of 占 20% according to the measurement point, the average value of the values measured at three points by changing the measurement points was determined as the film thickness of the curable resin composition layer. The film thicknesses are shown in Table 1.

<Measurement of fluorescence intensity>

The laminate was laminated to an ultraviolet irradiator (trade name: CV-1100-G, manufactured by Fusion UV Systems, Japan K.K., using D valve, output 80%, height 4 cm, speed 11 m / min) Irradiation side) and passed a predetermined number of times. When the laminate was passed through an ultraviolet irradiator four times, the integrated light quantity was about 600 mJ / cm 2 (UVB). The fluorescence intensity was measured by changing the output, the speed and the number of passing times of the ultraviolet irradiating device with respect to each laminate.

The fluorescence intensity (unit: V) emitted from the curable resin composition was measured by a fluorescence intensity measurement method using a fluorescence intensity measuring apparatus (trade name: OL 201-1, manufactured by KABUSHIKI KAISHA). The fluorescence intensity was measured using an LED 365D-S (excitation wavelength 365 nm) as the light source and OL 201 (detection wavelength 420 to 700 nm) as the detector. The distance between the lens and the object to be measured was about 35 mm The light amount was set at 10%, the sensitivity was set at 60%, and the sensitivity was set at 9.00. In addition, the offset was set so that the device display value became zero when only the stainless steel plate was placed on the measurement. At this time, the device display value when measuring "ND-40", which is a standard fluorescent light emitting material, was about 5.00 V. In addition, the measurement was carried out with the third film on the upper side (irradiation side). Since the measured value showed an unevenness of about 20% depending on the measurement point, the average value of the values obtained by measuring the three points by changing the measurement points was regarded as the fluorescence intensity.

<Adhesive Property Test 1>

The adhesion of the first film to the second film was evaluated by a cutter knife test method. The results are shown in Table 2.

&Lt; Adhesion Test 2 &

The adhesion of the third film to the second film was evaluated by a cutter knife test method. The results are shown in Table 2.

In the method of the cutter knife test, first, a groove reaching from the surface to the second film with a cutter knife is applied to the first film surface of the laminate at about 1 cm, and then the angle of the cutter knife blade is made substantially parallel to the surface , The cutter knife was inserted into the center of the groove and the blade was passed between the first film and the second film so that the cutter knife was pushed forward (inside) as it was.

At this time, when the blade advances without applying force, the adhesion is poor and the result is x. If a little force is applied, when the blade is about 5 mm in diameter, the adhesion is good and the result is rated. In the case where the blade does not enter well even if the force is applied considerably, and the film itself is directly cut off, the adhesion is very good. This test was conducted after about 1 hour, about 3 hours, and about 1 day (24 hours) after ultraviolet irradiation. The surface of the third film of the layered product was also evaluated in the same manner as above.

<Adhesion Test 3>

The adhesion of the first film to the second film was evaluated by the fill test method and the peel strength (unit: N) was measured. The results are shown in Table 2.

The peel test was carried out using Autograph AGS-100D (trade name, manufactured by Shimadzu Seisakusho Co., Ltd.). The two adhered films (the first film and the second film) were partially peeled and peeled, and the adherend was fixed to one end and the adhesive was fixed to the other end, The peel strength is calculated by measuring the force. In order to calculate the peel strength between the first film and the second film, a sample in which the first film and the second film were partially peeled off was prepared and cut to a size of about 2.5 cm x 15 cm. At this time, the peeling portion and the non-peeling portion were brought in the major axis direction. The first film in the peeled portion of this sample was fixed on the upper side of the peel test apparatus, and the sample after the first film peel was fixed on the lower side of the peel test apparatus.

The peeling strength was defined as an average value of the force applied when the peeling was performed at a peeling speed of 1 cm / min and a load cell of 25 N (about 5 minutes).

Also, - in the table means an unmeasured measurement.

From this result, it can be understood that the laminate S1 has good adhesiveness when the fluorescence intensity is 1.95 V or more. It can be seen that the laminate S2 has very good adhesiveness when the fluorescence intensity is 2.14 V or more. It can be seen that the layered product S3 has good adhesiveness when the fluorescence intensity is 2.38 V or more. It can be seen that the layered product S4 has good adhesiveness when the fluorescence intensity is 2.28 V or more. It can be seen that the layered product S5 has good adhesiveness when the fluorescence intensity is 4.81 V or more. Therefore, the adhesiveness of each laminate can be evaluated by appropriately setting the reference (threshold value) of the fluorescent intensity for each laminate based on the above-described results.

According to the adhesion evaluation method of the present invention, the adhesion of the laminate can be evaluated without peeling.

1, 5: laminate
2, 8: Second film
3, 7, 9: Curable resin composition
4, 10: First film
6: Third film

Claims (14)

A first film not containing a material capable of emitting fluorescence by irradiation of ultraviolet rays and a second film containing no material capable of emitting fluorescence by irradiation of ultraviolet rays are bonded to each other through a curable resin composition, An adhesion evaluation method for evaluating adhesion of a film in a laminate obtained by curing,
A step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,
A step of curing the curable resin composition in the laminate to obtain a laminate by irradiating the laminate with light or by heating the laminate,
A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,
And evaluating the adhesiveness between the first film and the second film in the laminate based on the measurement result of the fluorescence intensity,
The above evaluation is performed by comparing the fluorescence intensity measured with the reference value by setting the fluorescence intensity at the time when the adhesiveness is sufficient to the reference value,
The reference value is obtained by obtaining the relationship between the integrated light quantity at the time of curing and the fluorescence intensity and the adhesive property for a plurality of model samples at different curing stages and comparing the fluorescence intensity with the integrated light quantity at the time of curing And a strength of the adhesive. A first film that does not contain a material that emits fluorescence by ultraviolet irradiation, a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays, and a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays Bonding the third film so that the second film is sandwiched between the first film and the third film through the curable resin composition and curing the curable resin composition to thereby evaluate the adhesive property of the film in the laminate As a property evaluation method,
A step of joining the first film and the second film with the curable resin composition interposed therebetween,
A step of bonding a third film to a second film through a curable resin composition on the side opposite to the side where the first film is bonded to obtain a laminate,
A step of curing the curable resin composition in the laminate to obtain a laminate by irradiating the laminate with light or by heating the laminate,
A step of irradiating an active energy ray to the cured curable resin composition layer in the laminate to measure the fluorescence intensity of fluorescence emitted from the curable resin composition layer,
And evaluating the adhesion between the first film and the second film in the laminate and the adhesion between the second film and the third film based on the measurement result of the fluorescence intensity,
The above evaluation is performed by comparing the fluorescence intensity measured with the reference value by setting the fluorescence intensity at the time when the adhesiveness is sufficient to the reference value,
The reference value is obtained by obtaining the relationship between the integrated light quantity at the time of curing and the fluorescence intensity and the adhesive property for a plurality of model samples at different curing stages and comparing the fluorescence intensity with the integrated light quantity at the time of curing And a strength of the adhesive. The method according to claim 1,
And the second film is a polarizer. 3. The method of claim 2,
And the second film is a polarizer. 3. The method according to claim 1 or 2,
Wherein the first film is a protective film for protecting the second film. 3. The method of claim 2,
And the third film is a protective film for protecting the second film. 3. The method according to claim 1 or 2,
Wherein the first film is a film comprising at least one resin selected from the group consisting of a cellulose acetate resin, an amorphous polyolefin resin, a crystalline polyolefin resin and an acrylic resin. 3. The method according to claim 1 or 2,
And the second film is a film made of a polyvinyl alcohol resin. 3. The method according to claim 1 or 2,
Wherein the second film is a film made of a resin in which a dichroic dye is adsorbed and oriented. 3. The method according to claim 1 or 2,
Wherein the second film is a film obtained by uniaxially stretching the resin. 3. The method of claim 2,
Wherein the third film is a film comprising at least one resin selected from the group consisting of a cellulose acetate resin, an amorphous polyolefin resin, a crystalline polyolefin resin and an acrylic resin. 3. The method according to claim 1 or 2,
Wherein the curable resin composition comprises a monomer or oligomer and either or both of the monomer and oligomer and a polymerization initiator that emits fluorescence upon irradiation with an active energy ray. A first film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays and a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays are bonded to each other through a curable resin composition to cure the curable resin composition As a method for producing a laminate,
(A) a step of bonding a first film and a second film to each other through a curable resin composition to obtain a laminate,
(B) curing the curable resin composition in the laminate by irradiating the laminate with light or by heating the laminate to obtain a laminate,
(C) irradiating the cured curable resin composition layer in the laminate with an active energy ray,
(D) measuring fluorescence intensity of fluorescence emitted from the curable resin composition layer by receiving the active energy ray irradiated in the step (C); and
(E) evaluating the adhesiveness between the first film and the second film in the laminate based on the fluorescence intensity measured in the step (D), and judging whether the quality of the laminate is good or bad,
The above evaluation is performed by comparing the fluorescence intensity measured with the reference value by setting the fluorescence intensity at the time when the adhesiveness is sufficient to the reference value,
The reference value is obtained by obtaining the relationship between the integrated light quantity at the time of curing and the fluorescence intensity and the adhesive property for a plurality of model samples at different curing stages and comparing the fluorescence intensity with the integrated light quantity at the time of curing And the strength of the laminated body. A first film that does not contain a material that emits fluorescence by ultraviolet irradiation, a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays, and a second film that does not contain a material that emits fluorescence by irradiation of ultraviolet rays A method for producing a laminated body in which a third film is cemented through a curable resin composition so that a second film is sandwiched between a first film and a third film, and the curable resin composition is cured,
(A'-1) bonding the first film and the second film via the curable resin composition,
(A'-2) a step of joining a third film to the second film via a curable resin composition on the side opposite to the side where the first film is bonded, to obtain a laminate;
(B ') laminate, or by heating the laminate to obtain a laminate by curing the curable resin composition in the laminate,
(C ') irradiating the cured curable resin composition layer in the laminate with an active energy ray,
(D ') measuring a fluorescence intensity of fluorescence emitted from the curable resin composition layer by receiving an active energy ray irradiated in the step (C');
(E ') Based on the fluorescence intensity measured in the step (D'), the adhesion between the first film and the second film in the laminate and the adhesion between the second film and the third film are evaluated And judging whether the quality of the laminate is good or bad,
The above evaluation is performed by comparing the fluorescence intensity measured with the reference value by setting the fluorescence intensity at the time when the adhesiveness is sufficient to the reference value,
The reference value is obtained by obtaining the relationship between the integrated light quantity at the time of curing and the fluorescence intensity and the adhesive property for a plurality of model samples at different curing stages and comparing the fluorescence intensity with the integrated light quantity at the time of curing And the strength of the laminated body.

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