KR102312162B1 - Laminate production method - Google Patents

Abstract

Provided is a method for manufacturing a laminate in which substrates are adhered to each other by sufficient adhesive force using only a photocuring process. A step of applying the photocurable resin composition to the substrate 1 to form an application layer, a step of irradiating the application layer with light having an ultraviolet irradiation intensity of less than 100 mW/cm 2 to form a temporary curing resin layer, and the substrate 2 on the temporary curing resin layer A method for producing a laminate, comprising: a step of bonding;

Description

The manufacturing method of a laminated body {LAMINATE PRODUCTION METHOD}

The present invention relates to a method for manufacturing a laminate, and specifically to a method for manufacturing a laminate which is an image display device.

BACKGROUND ART In image display devices used in smartphones and the like, a light-transmitting member is usually provided on a display body such as a liquid crystal display panel or an organic EL panel. It is known to use a photocurable resin composition for adhesion|attachment of a display body and a light transmissive member. In an image display apparatus, in order to aim at a contrast improvement etc., the light shielding layer like a black matrix is provided in the peripheral part of a light transmissive member in many cases. Therefore, even if the display body and the light-transmitting member are overlapped through the photocurable resin composition and irradiated with light, the light is blocked by the presence of the light-shielding layer, curing does not proceed sufficiently, leakage occurs, or lack of adhesion situation may arise.

In order to solve such a problem, after mix|blending a thermal polymerization initiator with a photocurable resin composition and light-irradiating, the method of further thermosetting is proposed (patent document 1).

In addition, as a method of using only a photocuring process without using a thermosetting process, the photocurable resin composition is applied to the surface of the display body thicker than the thickness of the light shielding layer, and ultraviolet rays are applied to a curing rate of 10 to 80%. After irradiating and making it temporarily harden, the method of overlapping a light-transmitting member and irradiating an ultraviolet-ray and making it main-cure is proposed (patent document 2).

International Publication No. 2008/126860 Japanese Patent Laid-Open No. 2013-151151

However, in the method of Patent Document 2, if the curing rate in the provisional curing is increased, sufficient adhesive force is not exhibited when the light-transmitting members are laminated thereafter and the light-transmitting member is main-cured, while the curing rate in the provisional curing is low. When it does, there existed a problem that the part where hardening did not fully advance by the presence of a light shielding layer generate|occur|produces as in the prior art.

An object of the present invention is to solve the above problems and provide a method for manufacturing a laminate, for example, an image display device, in which substrates are adhered to each other by sufficient adhesive force using only a photocuring process.

The present invention 1 is a step of forming a coating layer by applying a photocurable resin composition to the substrate 1, a step of irradiating the coating layer with light having an ultraviolet irradiation intensity of less than 100 mW/cm 2 to form a temporary curing resin layer, the number of temporary curing It is related with the manufacturing method of a laminated body including the process of bonding the base material 2 on a base layer, and the process of irradiating light to the temporarily cured resin layer between the base material 1 and the base material 2 and making it main-cure.

This invention 2 relates to the manufacturing method of the laminated body of this invention 1, wherein the light in the process of forming a temporary hardening resin layer is light with an ultraviolet irradiation intensity of 1-50 mW/cm<2>.

The present invention 3 is the present invention 1 or 2, wherein the provisional cured resin layer is formed by irradiating light having an ultraviolet irradiation intensity of less than 100 mW/cm 2 so that the curing rate of the photocurable resin composition in the application layer is 40 to 90%. A method for manufacturing a laminate of

In the present invention 4, the light having an ultraviolet irradiation intensity of less than 100 mW/cm 2 is the LED having a peak of 365 nm and/or an LED having a peak of 405 nm as a light source. It relates to a manufacturing method.

In the present invention 5, the present inventions 1 to 4, wherein the light having an ultraviolet irradiation intensity of less than 100 mW/cm 2 is light passed through an optical filter that cuts light of a wavelength of 300 nm or less and/or an optical filter that cuts a wavelength of 500 nm or more It relates to the manufacturing method of any one of a laminated body.

This invention 6 relates to the manufacturing method of the laminated body in any one of this invention 1-5, in which a photocurable resin composition contains a (meth)acrylate oligomer and a photoinitiator.

In the present invention 7, the (meth)acrylate oligomer is a (hydrogenated) polyisoprene, (hydrogenated) polybutadiene or a (meth)acrylate oligomer having a polyurethane structure in the backbone, production of the laminate of the present invention 6 it's about how

In the present invention 8, one of the base material 1 or the base material 2 is a liquid crystal display panel, an organic EL display panel, a protection panel, or a touch panel, and the other is a light transmitting member, manufacturing the laminate according to any one of the present inventions 1 to 7 it's about how

This invention 9 relates to the manufacturing method of the laminated body in any one of Inventions 1-8 whose laminated body is an image display device.

ADVANTAGE OF THE INVENTION According to the manufacturing method of the laminated body of this invention, the laminated body which base materials adhere|attached by sufficient adhesive force using only the photocuring process, for example, an image display apparatus is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is the evaluation process of the adhesive force of an Example.
2 is an emission spectrum of light used in the provisional curing of Examples and Comparative Examples.

The manufacturing method of the laminated body of this invention includes the following processes (A)-(D).

Step (A): A step of applying a photocurable resin composition to the substrate 1 to form an application layer,

Step (B): A step of irradiating the application layer with light having an ultraviolet irradiation intensity of less than 100 mW/cm 2 to form a temporarily cured resin layer,

Step (C): a step of bonding the base material 2 on the temporarily cured resin layer, and

Process (D): The process of irradiating light to the temporarily cured resin layer between the base material 1 and the base material 2, and making it main-cure.

<Laminate>

The laminate, which is the object of the production method of the present invention, is adhered to the substrate 1 and the substrate 2 using a photocurable resin composition. The base material 1 and the base material 2 are not specifically limited, The same base material may be sufficient, and a different base material may be sufficient as them. It is preferable that at least one of the base material 1 and the base material 2 is a light-transmitting member at the point which irradiates light to the temporarily cured resin layer in process D. In addition to the base material 1 and the base material 2, the laminated body may contain the additional base material, and the adhesion|attaching method of the base material is not specifically limited.

For example, the laminated body which is various image display apparatuses can be manufactured by making one of the base material 1 or the base material 2 into a display body, and making the other into a light transmissive member. For example, a liquid crystal display device can be manufactured by making one of the base material 1 or base material 2 a liquid crystal display panel, and making the other a light transmissive member, let one be an organic electroluminescent display panel, and make the other light transmissive. By setting it as a member, an organic electroluminescence display can be manufactured.

For example, a touch panel can be manufactured by making one of the base material 1 or the base material 2 into the light transmissive board|substrate with a transparent electrode, and making the other into a light transmissive member. Moreover, one of the base material 1 or the base material 2 can be used as a touch panel, and the other can be used as an icon sheet or a decorative board.

For example, by using one of the base material 1 or the base material 2 as a protection panel and the other as an image display device or various board|substrates, the image display apparatus which has a protection panel, or the board|substrate which has a protection panel can be manufactured. Moreover, the base material 1 can be used as a protective panel, and the base material 2 can also be used as a light-transmitting member.

When a light-transmitting member is used, the light-transmitting member just needs to have light transmittance according to the purpose of the laminate. For example, when the laminate is an image display device, the image formed on the display body has light transmittance to the extent that it is visible. there should be Examples of the light-transmitting member include plate-like materials and sheet-like materials such as glass, (meth)acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyester, and cycloolefin polymer. These may be subjected to a hard coat treatment, an antireflection treatment, an antiglare treatment, an antifouling treatment, an antifogging treatment, a polarization treatment, or a wavelength cut treatment on one or both surfaces. Moreover, the light shielding layer may be formed in the light transmissive member.

<Process A>

Process A is a process of apply|coating a photocurable resin composition to the base material 1, and forming an application layer. As a photocurable resin composition, the composition containing a (meth)acrylate oligomer and a photoinitiator can be used.

It does not specifically limit as a (meth)acrylate oligomer, The (meth)acrylate oligomer which has (hydrogenation) polyisoprene, (hydrogenation) polybutadiene, or polyurethane in frame|skeleton is mentioned. One type or two or more types can be used for these (meth)acrylate oligomers. Here, (hydrogenated) polyisoprene includes polyisoprene and/or hydrogenated polyisoprene, and (hydrogenated) polybutadiene includes polybutadiene and/or hydrogenated polybutadiene.

(Hydrogenation) The (meth)acrylate oligomer having polyisoprene in the skeleton is also called (meth)acryl-modified polyisoprene, and preferably has a molecular weight of 1000 to 100000, more preferably 10000 to 50000. As a commercial item, there exists "UC-1" (molecular weight 25000) by the Kuraray company, for example.

(Hydrogenation) The (meth)acrylate oligomer which has polybutadiene in backbone is also called (meth)acryl modified polybutadiene, Preferably it is 500-100000, More preferably, it has a molecular weight of 1000-30000. As a commercial item, there exists "TE2000" (molecular weight 2000) by Nippon Sekiyu Co., Ltd., for example.

The (meth)acrylate oligomer having polyurethane in its skeleton is also called (meth)acrylic-modified polyurethane, and preferably has a molecular weight of 1000 to 100000, more preferably 10000 to 50000. As a commercial item, there exist "UA-1" by a light chemical company, and "UV3630ID80" by a Nippon Kosei Chemical Industry Co., Ltd. product, for example.

As a (meth)acrylate oligomer, the (meth)acrylate oligomer which has a polyurethane in frame|skeleton is especially preferable.

The (meth)acrylate oligomer may use 1 type or 2 or more types together.

It does not specifically limit as a photoinitiator, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxy Phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl -1-[4-methylthio]phenyl]-2-morpholinopropan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4 ,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, 2-hydroxy-2-methyl-[4-(1-) Methylvinyl)phenyl]propanol oligomer, 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthone, methyl o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethane; 2,4-diethylthioxanthone, 2-chlorothioxanthone, benzophenone, ethylanthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, bis(2,6-dimethoxybenzoyl)-2,4,4- Trimethyl-pentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4 '-Bisdiethylaminobenzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2,2'bis(o-chlorophenyl)4,5,4',5'-tetrakis (3,4,5-trimethoxyphenyl)1,2'-biimidazole, 2,2'bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'- Biimidazole, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, acrylated benzophenone, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-di Fluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamylethyl ester, active tert-amine; Carbazole-phenone-based photopolymerization initiator, acridine-based photopolymerization initiator, triazine-based photoinitiator A photoinitiator, a benzoyl type photoinitiator, etc. can be illustrated.

The photoinitiator is preferably 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, or the like.

A photoinitiator may use 1 type or 2 or more types together.

It is preferable that a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of (meth)acrylate oligomers, More preferably, it is 0.5-15 mass parts, More preferably, it is 1-10 mass parts.

The photocurable resin composition may include a (meth)acrylate monomer as a reaction diluent, for example, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylic Alkyl (meth)acrylates, such as a rate, t-butyl (meth)acrylate, and lauryl (meth)acrylate; alkoxy-substituted alkyl (meth)acrylates such as methoxyethyl (meth)acrylate; Hydroxy-substituted alkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, and the like; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylates such as di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate; Dicyclopentenyloxyethyl (meth)acrylate, norbornene (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, etc. can be illustrated.

As a (meth)acrylate monomer, alkyl (meth)acrylates, such as lauryl (meth)acrylate, methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dicyclopentanyl (meth)acryl rate and the like are preferred.

The (meth)acrylate monomer may be used 1 type or 2 or more types together.

It is preferable that a (meth)acrylate monomer is 1-250 mass parts with respect to 100 mass parts of (meth)acrylate oligomers, More preferably, it is 20-200 mass parts, More preferably, it is 50-150 mass parts.

The photocurable resin composition may include a plasticizer. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, and butyl benzyl phthalate; polyhydric carboxylic acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, and diisononyl 1,2-cyclohexanedicarboxylic acid; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester; rubber polymers such as polyisoprene, polybutadiene, and polybutene; thermoplastic elastomers; petroleum resin; alicyclic saturated hydrocarbon resins; terpene resins such as terpene resins, terpene phenol resins, modified terpene resins, and hydrogenated terpene resins; rosin-based resins such as rosin phenol; and rosin ester-based resins such as disproportionated rosin ester-based resins, polymerized rosin ester-based resins, and hydrogenated (hydrogenated) rosin ester-based resins.

As a plasticizer, polyhydric carboxylic acid ester, rosin ester type resin, etc. are preferable, and 1,2-cyclohexanedicarboxylic acid diisononyl and (hydrogenation) rosin ester type resin are more preferable.

A plasticizer may use 1 type or 2 or more types together.

It is preferable that a plasticizer is 10-500 mass parts with respect to 100 mass parts of (meth)acrylate oligomers, More preferably, it is 30-400 mass parts, More preferably, it is 50-300 mass parts.

The photocurable resin composition may further include an adhesion imparting agent. As adhesion-imparting agent, silane coupling agent, for example vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycy Doxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N -2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrie Toxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-mercaptopropyl, methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. can be exemplified.

An adhesive agent may use 1 type or 2 or more types together.

It is preferable that an adhesion-imparting agent is 0.01-15 mass parts with respect to 100 mass parts of (meth)acrylate oligomers, More preferably, it is 0.1-10 mass parts, More preferably, it is 1-5 mass parts.

The photocurable resin composition may include an antioxidant. As antioxidant, BHT, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaeryth Trityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t) -Butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol -bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)prop Cypionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3, 5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, octylated diphenylamine, 2,4- bis[(octylthio)methyl]-O-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and dibutylhydroxytoluene can be exemplified.

It is preferable that antioxidant is 0.01-15 mass parts with respect to 100 mass parts of (meth)acrylate oligomers, More preferably, it is 0.1-10 mass parts, More preferably, it is 1-5 mass parts.

An antifoaming agent, a pigment, a filler, a chain transfer agent, a light stabilizer, a surface tension regulator, a leveling agent, a ultraviolet absorber, a bubble inhibitor, etc. can be mix|blended with the photocurable resin composition in the range which does not impair the effect of this invention.

The photocurable resin composition can be manufactured by mixing each component. The method of mixing is not specifically limited, Various metal and plastic containers, a stirring blade, and a stirrer can be used.

The method of apply|coating the photocurable resin composition to the base material 1 is not specifically limited, The method by a die coater, a dispenser, screen printing, etc. can be used.

The thickness of an application layer is not specifically limited, For example, it can be 10-500 micrometers, and 30-350 micrometers is preferable.

<Process B>

A process (B) is a process of irradiating the light whose ultraviolet irradiation intensity is less than 100 mW/cm<2> to an application layer, and forming a provisionally cured resin layer.

The light used for irradiation in the step (B) has an ultraviolet irradiation intensity of less than 100 mW/cm 2 , in terms of intensity expression after main curing, preferably 50 mW/cm 2 or less, more preferably 30 mW/cm 2 or less, Moreover, from the point of time until a temporary hardening resin layer can be formed, Preferably it is 1 mW/cm<2> or more. In the present specification, the ultraviolet irradiation intensity is the maximum intensity measured using the illuminometer, and in the wavelength distribution of 300 to 500 nm of the light source used, the illuminometer having sensitivity in the wavelength region corresponding to the wavelength with the highest irradiation intensity. can be measured The light source may have a single or a plurality of peaks in a wavelength distribution of 300 to 500 nm, but the highest irradiation intensity may be less than 100 mW/cm 2 . By using such a light source, prevention of liquid sagging and outflow in temporary hardening and intensity|strength expression after main hardening can be made compatible.

With respect to the light used for irradiation in the step (B), the integrated value of the irradiation intensity of the wavelength of 300 to 500 nm with respect to the integrated value of the irradiation intensity of all wavelengths is not particularly limited, In terms of intensity expression after main curing, Preferably it is 90 % or more, More preferably, it is 95 % or more, More preferably, it is 98 % or more.

As the light source, a light source emitting ultraviolet (UV) light can be used, and examples thereof include a metal halide lamp, a high-pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a halogen lamp, and a pulsed xenon lamp. You may adjust the light emitted from these light sources to light of a specific wavelength by passing an optical filter. Specifically, it can adjust by passing the optical filter which cuts the light of wavelength 300 nm or less, and/or the optical filter which cuts the wavelength of 500 nm or more. Examples of such an optical filter include a quartz interference filter (model number: A7028-05, manufactured by Hamamatsu Photonics), an LT filter, an RT filter (all manufactured by HOYA), and a band pass filter (manufactured by Eye Graphics, Inc.). . Light using an LED as a light source can also be used, and as light sources, an LED having a peak at 365 nm, an LED having a peak at 405 nm, an LED having a peak at 375 nm, an LED having a peak at 385 nm, and an LED having a peak at 395 nm. and the like.

By irradiating the light whose ultraviolet irradiation intensity is less than 100 mW/cm<2> with respect to an application layer, the resin composition of an application layer is provisionally hardened, and a provisional hardening resin layer is formed. The irradiation method is not specifically limited, For example, it can irradiate so that the amount of ultraviolet accumulated light may be 30-7500 mJ/cm<2>. The amount of accumulated light is preferably 50 to 5000 mJ/cm 2 , more preferably 100 to 2000 mJ/cm 2 .

The curing rate of the temporary curable resin layer is preferably 40 to 90%, more preferably 45 to 80%, and still more preferably 50 to 70% from the viewpoint of strength expression after main curing, outflow, and prevention of liquid sagging. %am. The curing rate is defined as the decrease rate of the (meth)acryl group before and after ultraviolet irradiation of the photocurable resin composition, and can be measured by FT-IR.

<Process C>

Step C is a step of bonding the base material 2 on the temporarily cured resin layer. On the substrate 1 on which the temporary curing resin layer is formed, the substrate 2 is placed so as to be in contact with the temporary curing resin layer, and if necessary, the substrate 1 and the substrate 2 can be bonded by pressing from the substrate 1 side and/or the substrate 2 side. . The pressurization method is not specifically limited, A rubber roller, a flat plate press apparatus, etc. can be used.

<Process D>

Step D is a step of further irradiating light to the temporarily cured resin layer between the base material 1 and the base material 2 for main curing. When either of the base material 1 and the base material 2 is a light transmissive member, it can irradiate light from the base material side which is a light transmissive member, and can make it main-cured.

Light is not specifically limited, Active energy rays, such as a visible light ray, an ultraviolet-ray, X-ray, and an electron beam, can be used, Preferably it is an ultraviolet-ray. As a light source, a metal halide lamp, a high pressure mercury lamp, a xenon lamp, a halogen lamp, a pulsed xenon lamp, etc. can be used.

The irradiation method of light is not specifically limited, For example, it can irradiate light with intensity|strength of 10-1500 mW/cm<2> so that it may become an accumulated light amount of 500-10000 mJ/cm<2>. The intensity is preferably 100 to 1000 mW/cm 2 , more preferably 200 to 500 mW/cm 2 , and the amount of accumulated light is preferably 1000 to 6000 mJ/cm 2 , more preferably 1500 to 4500 mJ/cm 2 .

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Unless otherwise specified, the indications are parts by mass and % by mass.

Each component of the formulation shown in Table 1 was weighed in a polyethylene container, and it mixed uniformly using a three-one motor (made by Tokyo Rika Kiki, MAZELA) and a stirring blade, and the photocurable resin composition was manufactured.

<Example 1>

A spacer with a thickness of 150 µm produced by using 3 sheets of cellophane tape (50 µmt) on 26 mm×75 mm×1.1 mmt glass so that the photocurable resin coated portion has a square shape of 10 mm×10 mm. , and after forming a photocurable resin composition application layer using a metal squeegee, the spacer was removed (FIG. 1 (1)).

Under the provisional curing conditions shown in Table 2, using a mercury xenon lamp (manufactured by HOYA, EXECURE4000, the emission spectrum is shown in Fig. 2), ultraviolet irradiation intensity (365 nm) 30 mW/cm 2 (measured by Hamamatsu Photonics Co., Ltd.) was irradiated to form a temporarily cured resin layer. When the integrated value of the irradiation intensity of a wavelength of 300-500 nm with respect to the integrated value of the irradiation intensity of all wavelengths was calculated|required by integrating the emission intensity in wavelength distribution measurement, it turns out that it is about 85 %.

The curing rate of the temporarily cured resin layer was measured by FT-IR (Perkin Elmer, Spectrum100) as a decrease rate of the acrylic group before and after ultraviolet irradiation of the photocurable resin composition. The reduction rate is the absorption peak height (X) ^{of 800 to 820 cm -1} from the baseline in the FT-IR measurement chart of the resin composition layer before ultraviolet irradiation and the FT-IR measurement chart of the resin composition layer after ultraviolet irradiation The absorption peak height (Y) of 800 to 820 cm ^-1 from the baseline was calculated by substituting the following formula (1).

Curing rate (%)={(X-Y)/X}×100 … (One)

Another 26 mm x 75 mm x 1.1 mmt glass was prepared, and on the glass on which the temporary hardening resin layer was formed, it was mounted so that a temporarily hardened resin layer might contact, and it pressurized and joined (FIG. 1 (2)).

The outflow and liquid sagging of the temporary cured resin layer were observed, and the following criteria evaluated. A result is shown in Table 2.

Large spillage/liquid sagging: ×

Small spillage/liquid sagging: △

No spillage or sagging: ○

At 3000 mJ/cm 2 with a metal halide lamp (200 to 400 mW/cm 2 ), the temporary curing resin layer was irradiated with light over the glass, and main-cured.

With respect to the adhered glass laminate, the tensile strength was measured at 10 mm/min in the shear direction using a tensile tester (manufactured by Minevea, Technograph TG-2kN), and evaluated according to the following criteria (( in FIG. 1 ) 3)). A result is shown in Table 2.

Less than 0.3 MPa: ×

0.3 to less than 0.5 MPa: △

0.5 MPa or more: ○

<Example 2>

Under the provisional curing conditions shown in Table 3, using a mercury xenon lamp (manufactured by HOYA, EXECURE4000, the emission spectrum is shown in Fig. 2) was irradiated at an ultraviolet irradiation intensity (365 nm) of 10 mW/cm 2 , and the provisionally cured resin layer Except having formed, it carried out similarly to Example 1, the glass laminated body was manufactured, and the tensile strength was measured.

<Comparative Example 1>

Under the provisional curing conditions shown in Table 4, using a mercury xenon lamp (manufactured by HOYA, EXECURE4000, the emission spectrum is shown in Fig. 2) was used, and irradiation was performed at an ultraviolet irradiation intensity (365 nm) of 100 mW/cm 2 , and the provisional curing resin layer Except having formed, it carried out similarly to Example 1, the glass laminated body was manufactured, and the tensile strength was measured.

In Examples 1 and 2, it turns out that even if the curing rate of a temporary hardening resin layer is high, the laminated body which the glass adhere|attached with sufficient adhesive force is obtained.

According to the manufacturing method of the laminated body of this invention, since the laminated body which base materials adhere|attached by sufficient adhesive force using only a photocuring process, for example, an image display apparatus, is provided, industrial utility is high.

1: glass plate
2: coating layer
3: Temporarily cured resin layer
4: Tensile tester (schematic diagram)

Claims (9)

A step of applying a photocurable resin composition to the substrate 1 to form an application layer,
A step of irradiating the application layer with light having an ultraviolet irradiation intensity of 10 to 30 mW/cm 2 to form a provisionally cured resin layer;
A step of bonding the substrate 2 on the temporarily cured resin layer, and
A method for producing a laminate comprising a step of irradiating light to the temporarily cured resin layer between the base material 1 and the base material 2 for main curing, the method comprising:
One of the substrate 1 or the substrate 2 is a display body and the other is a light-transmitting member,
The photocurable resin composition includes a (meth)acrylate oligomer, a photopolymerization initiator and a plasticizer, and the (meth)acrylate oligomer is a (meth)acrylate oligomer having a polyurethane structure in its backbone,
The light having an ultraviolet irradiation intensity of 10 to 30 mW/cm 2 passes through an optical filter that cuts light of a wavelength of 300 nm or less and an optical filter that cuts a wavelength of 500 nm or more, or an LED having a peak of 365 nm and / or light using an LED having a peak at 405 nm as a light source,
Forming the temporary cured resin layer by irradiating light with an ultraviolet irradiation intensity of 10 to 30 mW/cm 2 so that the curing rate of the photocurable resin composition in the application layer is 40 to 80%,
The manufacturing method of the laminated body which is an image display apparatus. The manufacturing method of the laminated body of Claim 1 whose one of the base material 1 or the base material 2 is a liquid crystal display panel, an organic electroluminescent display panel, a protection panel, or a touch panel, and the other is a light transmissive member. delete delete delete delete delete delete delete

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