TWI671205B - Manufacturing method of laminated body - Google Patents

Abstract

The present invention provides a method for manufacturing a laminated body, which uses only a photo-hardening process, and the substrates are adhered to each other with a sufficient adhesive force.

The manufacturing method of the laminated body includes the step of applying a photocurable resin composition on the base material (1) to form a coating layer. The coating layer is irradiated with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² to form preliminary curing. The resin layer step, the step of bonding the base material (2) on the preliminary hardened resin layer, and the preliminary hardened resin layer between the base material (1) and the base material (2) is irradiated with light to formally harden it. step.

Description

Laminated body manufacturing method

The present invention relates to a method for manufacturing a multilayer body, and more particularly, to a method for manufacturing a multilayer body used as an image display device.

In an image display device used in a smart phone or 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 bonding a display body and a light transmissive member. In an image display device, in order to improve contrast and the like, a light-shielding layer such as a black matrix is often provided in a peripheral portion of a light-transmitting member. Therefore, the display and the light-transmitting member are overlapped with each other through the light-curable resin composition, and even if light is irradiated, the light is blocked by the presence of the light-shielding layer. The curing is not sufficiently performed, and outflow may occur, or insufficient bonding may occur. And so on.

In order to solve such a problem, a method of blending a thermal polymerization initiator into a photocurable resin composition and performing light curing after light irradiation has been proposed (Patent Document 1).

In addition, as a method of using only a light hardening process without using a heat hardening process, it has been proposed to apply a thickness greater than the thickness of the light-shielding layer on the surface of the display body. A thick photo-curable resin composition is irradiated with ultraviolet rays so as to have a curing rate of 10 to 80%, and after being initially cured, a light-transmitting member is superimposed and then irradiated with ultraviolet rays to formally harden (Patent Document 2).

[Prior technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2008/126860

[Patent Document 2] JP 2013-151151

However, in the method of Patent Document 2, if the hardening rate of the preliminary hardening is increased, when the light-transmitting member is subsequently superimposed for the full hardening, sufficient adhesion is not exerted. On the other hand, if the preliminary hardening is reduced, The problem is that, as in the past, the presence of a light-shielding layer causes a problem that a portion where curing is not sufficiently performed occurs.

In order to solve the above-mentioned problems, the present invention aims to provide a method for manufacturing a laminated body such as an image display device, which uses only a photo-hardening process and adheres the substrates to each other with a sufficient adhesive force.

The present invention 1 relates to a method for manufacturing a laminated body, which comprises the steps of coating a photocurable resin composition on a substrate 1 to form a coating layer; and irradiating light with an ultraviolet irradiation intensity of less than 100 mW / cm ² to the coating layer. A step of forming a preliminary hardened resin layer; a step of bonding the base material 2 on the preliminary hardened resin layer; and a step of irradiating the preliminary hardened resin layer between the base material 1 and the base material 2 with light to formally harden .

The present invention 2 relates to the method for manufacturing a laminated body according to the present invention 1, wherein the light in the step of forming the preliminary hardened resin layer is light having an ultraviolet irradiation intensity of 1 to 50 mW / cm ² .

This invention 3 relates to the manufacturing method of the laminated body of this invention 1 or 2, Comprising: The hardening rate of the photocurable resin composition in a coating layer becomes 40-90%, and the irradiation intensity is less than 100mW / cm ² of light to form a preliminary hardened resin layer.

The present invention 4 relates to the method for manufacturing a multilayer body according to any one of the present inventions 1 to 3, wherein the light system whose ultraviolet irradiation intensity is less than 100 mW / cm ² has an LED with a peak at 365 nm and / or an LED with a peak at 405 nm light source.

The present invention 5 relates to the method for manufacturing a laminated body according to any one of the present inventions 1 to 4, wherein the light having an ultraviolet irradiation intensity of less than 100 mW / cm ^{2 is} a filter that cuts off light having a wavelength of 300 nm or less and / Or the light of the filter whose wavelength is above 500nm is cut off.

This invention 6 is a manufacturing method of the laminated body as described in any one of this invention 1-5 whose photocurable resin composition contains a (meth) acrylate oligomer and a photoinitiator.

This invention 7 relates to the manufacturing method of the laminated body of this invention 6, Comprising: The (meth) acrylate oligomer has (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, or a polyamine group in a skeleton. (Methyl) formate structure Acrylate oligomers.

The present invention 8 relates to the method for manufacturing a laminated body according to any one of the present inventions 1 to 7, wherein one of the substrate 1 or the substrate 2 is a liquid crystal display panel, an organic EL display panel, a protective panel, or a touch panel. The other is a light-transmitting member.

The present invention 9 relates to a method for manufacturing a laminated body according to any one of the present inventions 1 to 8, wherein the laminated system image display device.

By the method for manufacturing a laminated body of the present invention, it is possible to provide a method for manufacturing a laminated body such as an image display device, which uses only a photo-hardening process and adheres the substrates to each other with a sufficient adhesive force.

1‧‧‧ glass plate

2‧‧‧ coated layer

3‧‧‧ preliminary hardened resin layer

4‧‧‧Tensile testing machine (model drawing)

FIG. 1 is a procedure for evaluating the adhesion of the embodiment.

FIG. 2 is a light emission spectrum of light used for preliminary hardening in Examples and Comparative Examples.

[Mode for Carrying Out the Invention]

The method for producing a laminated body according to the present invention includes the following steps (A) to (D).

Step (A): A step of applying a photocurable resin composition on the substrate 1 to form a coating layer. Step (B): The coating layer is irradiated with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² to form preliminary hardening. Steps of the resin layer, step (C): a step of bonding the base material 2 on the preliminary hardened resin layer, and step (D): the preliminary hardened resin layer between the base material 1 and the base material 2 is irradiated with light and Steps to formally harden.

<Layered body>

The laminated body of the object of the manufacturing method of this invention uses the photocurable resin composition and the base material 1 and the base material 2 together. The substrate 1 and the substrate 2 are not particularly limited, and may be the same substrate or different substrates. In step D, at least one of the base material 1 and the base material 2 is preferably a light-transmitting member in terms of irradiating light to the preliminary hardened resin layer. The laminated system may include other substrates in addition to the substrate 1 and the substrate 2. The method for adhering the substrate is not particularly limited.

For example, by using one of the substrate 1 or the substrate 2 as a display body and the other as a light-transmitting member, a laminate of various image display devices can be manufactured. For example, by making one of the substrate 1 or the substrate 2 a liquid crystal display panel and the other one a light-transmitting member, a liquid crystal display device can be manufactured, and one of the substrates 1 and 2 being an organic EL display panel. This becomes a light-transmitting member, and an organic EL display device can be manufactured.

For example, a touch panel can be manufactured by making one of the base material 1 or the base material 2 a light-transmitting substrate on which a transparent electrode is formed, and making the other a light-transmitting member. Furthermore, one of the base material 1 and the base material 2 may be made into contact. The control panel makes the other one an icon sheet or a decorative sheet.

For example, by using one of the substrate 1 or the substrate 2 as a protective panel and the other as an image display device or various substrates, an image display device with a protective panel or a substrate with a protective panel can be manufactured. . The substrate 1 may be a protective panel, and the substrate 2 may be a light-transmitting member.

When using a light-transmitting member, the light-transmitting member only needs to have a light-transmitting property that conforms to the purpose of the laminated body. For example, when the laminated body is an image display device, it only needs to have a degree that can visually recognize the image formed on the display The light transmittance is sufficient. Examples of the light-transmitting member include glass, (meth) acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyester, and cycloolefin polymerization. Plate-like material or sheet-like material. These can also be subjected to hard coating treatment, anti-reflection treatment, anti-glare treatment, anti-fouling treatment, anti-fog treatment, polarization treatment, wavelength cut-off treatment, etc. on one or both sides. A light-shielding layer may be formed on the light-transmitting member.

<Step A>

Step A is a step of applying a photocurable resin composition to the substrate 1 to form a coating layer. As the photocurable resin composition, a composition containing a (meth) acrylate oligomer and a photopolymerization initiator can be used.

The (meth) acrylate oligomer is not particularly limited, and examples thereof include (form) having (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, or polyurethane in the backbone. ) Acrylate oligomers. These (meth) acrylate oligomers can be used singly or in combination of two or more kinds. Here, the (hydrogenated) polyisoprene includes polyisoprene and / or hydrogenated polyisoprene, and the (hydrogenated) polybutadiene includes polybutadiene and / or hydrogenated polybutadiene.

The (meth) acrylate oligomer having (hydrogenated) polyisoprene in the skeleton is also called (meth) acrylic modified polyisoprene, and preferably has a molecular weight of 1,000 to 100,000, More preferably, it has a molecular weight of 10,000 to 50,000. A commercially available product is, for example, "UC-1" (molecular weight: 25,000) manufactured by Kuraray Corporation.

(Meth) acrylate oligomers having (hydrogenated) polybutadiene in the skeleton, also known as (meth) acrylic modified polybutadiene, preferably having a molecular weight of 500 to 100,000, more preferably It has a molecular weight of 1,000 to 30,000. A commercially available product is, for example, "TE2000" (molecular weight 2000) manufactured by Japan Petroleum Corporation.

A (meth) acrylate oligomer having a polyurethane in the skeleton is also known as a (meth) acrylic modified polyurethane, preferably having a molecular weight of 1,000 to 100,000, more Preferably it has a molecular weight of 10,000 to 50,000. Examples of commercially available products include "UA-1" manufactured by Light Chemical, and "UV3630ID80" manufactured by Nippon Synthetic Chemical Industry.

The (meth) acrylate oligomer is particularly preferably a (meth) acrylate oligomer having a polyurethane in the skeleton.

The (meth) acrylate oligomer system may be used alone or in combination of two or more.

The photopolymerization initiator is not particularly limited, and examples include 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1 -Hydroxy-cyclohexyl-phenyl-one, diphenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 2,4,6-trimethylbenzidine Diphenylphosphine oxide, 2,4,6-trimethylbenzylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholine Phenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4-methylthio] phenyl] -2-? Phenylpropan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4,6-trimethylbenzene (Methylamino) -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-acetone, isopropylthioxanthone, o-benzoyl benzoic acid Methyl ester, [4- (methylphenylthio) phenyl] phenylmethane, 2,4-diethylthioxanthone, 2-chlorothioxanthone, diphenyl ketone, ethyl anthraquinone, diphenyl Ammonium ketone, thioxanthone ammonium salt, bis ( 2,6-dimethoxybenzyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dimethoxybenzyl) -2,4, 4-trimethyl-pentylphosphine oxide, 2,4,6-trimethyldiphenyl ketone, 4-methyldiphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone , 1,4-Dibenzobenzylbenzene, 10-butyl-2-chloroacridone, 2,2'-bis (o-chlorophenyl) 4,5,4 ', 5'-tetra (3, 4,5-trimethoxyphenyl) 1,2'-bisimidazole, 2,2'-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-bis Imidazole, 2-benzylidene naphthalene, 4-benzylidene biphenyl, 4-benzylidene diphenyl ether, acrylated diphenyl ketone, bis (η5-2,4-cyclopentadiene- 1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, o-methylbenzyl benzoate, p-dimethylaminobenzene Ethyl formate, isoamyl ethyl p-dimethylaminobenzoate, living tertiary amine, carbazole · benzophenone-based photopolymerization initiator, acridine-based photopolymerization initiator, three Based photopolymerization initiator, benzamidine based photopolymerization initiator, and the like.

The photopolymerization initiator is preferably 1-hydroxy-cyclohexyl-phenyl-one, 2,4,6-trimethylbenzylphenylethoxyphosphine oxide, or the like.

The photopolymerization initiator may be used alone or in combination of two or more.

The photopolymerization initiator is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (meth) acrylate oligomer, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass.

The photocurable resin composition may include a (meth) acrylate monomer as a reactive diluent. Examples of the diluent include 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylate. (Meth) acrylic acid, isobutyl acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, etc .; (meth) acrylic acid alkyl esters, etc. Alkoxy-substituted alkyl acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. Esters; benzyl (meth) acrylate, phenyl (meth) acrylate, etc .; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (methyl) ) Acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Di (meth) acrylates such as hexanediol di (meth) acrylate; dicyclopentadienyloxyethyl (meth) acrylate, norbornene (meth) acrylate, (meth) acrylic acid Dicyclopentyl ester, (methyl) Isobornyl acrylate and the like.

As the (meth) acrylate monomer, alkyl (meth) acrylate such as lauryl (meth) acrylate, methoxyethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate are preferred. Esters, dicyclopentyl (meth) acrylate, and the like.

The (meth) acrylate single system may be used alone or in combination of two or more.

The (meth) acrylate monomer is preferably 1 to 250 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 50 to 150 parts by mass, with respect to 100 parts by mass of the (meth) acrylate oligomer.

The photocurable resin composition may include a plasticizer. Examples of the plasticizer include dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, Phthalates such as butyl benzyl phthalate; dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate, 1,2-ring Polycarboxylic acid esters such as diisononyl hexanedicarboxylate; Phosphates such as tricresyl phosphate, tributyl phosphate; trimellitic acid esters; polyisoprene, polybutadiene, polybutene Rubber polymers; thermoplastic elastomers; petroleum resins; alicyclic saturated hydrocarbon resins; terpene resins such as terpene resins, terpene phenol resins, modified terpene resins and hydrogenated terpene resins; rosin phenols, etc. Rosin-based resins; disproportionated rosin-based resins, polymerized rosin-based resins, and rosin-based resins such as hydrogenated (hydrogenated) rosin-based resins.

The plasticizer is preferably a polycarboxylic acid ester, a rosin ester resin, and the like, and more preferably 1,2-cyclohexanedicarboxylic acid diisononyl ester and a (hydrogenated) rosin ester resin.

The plasticizer system may be used alone or in combination of two or more.

The plasticizer is preferably 10 to 500 parts by mass, more preferably 30 to 400 parts by mass, and even more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the (meth) acrylate oligomer.

The photocurable resin composition may further include a tackifier. Examples of the tackifier include silane coupling agents such as vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryl Oxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryl Methoxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl, methyl Methoxy Silane, 3-mercaptopropyl trimethoxy Silane, bis (triethoxysilylpropyl silicon alkyl) tetrasulfide, 3-isocyanate propyl triethoxy silane-yl and the like.

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

The tackifier is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 100 parts by mass of (meth) acrylate oligomer. 1 to 5 parts by mass.

The photocurable resin composition may contain an antioxidant. Examples of the antioxidant include BHT and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylaniline) -1,3,5-tris. , Pentaerythritol, tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylidenebis [3- (3,5-di Third butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-third butyl-5-methyl-4-hydroxyphenyl) propionate], 1 , 6-hexanediol-bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-third-butyl- 4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamonamine), 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -heterotrimer Cyanate, octylated diphenylamine, 2,4, -bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, dibutylhydroxytoluene.

The antioxidant is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylate oligomer.

In the photocurable resin composition, an antifoaming agent, a pigment, a filler, a chain transfer agent, a light stabilizer, a surface tension adjusting agent, a leveling agent, and ultraviolet rays can be blended as long as the effects of the present invention are not impaired. Absorbent, suds suppressor, etc.

The photocurable resin composition can be prepared by mixing the components. The method of mixing is not particularly limited, and various metals, plastic containers, stirring wings, and mixers can be used.

The method for applying the photocurable resin composition to the substrate 1 is not particularly limited, and a method such as a die coater, a dispenser, and screen printing can be used.

The thickness of the coating layer is not particularly limited, and may be, for example, 10 to 500 μm, and preferably 30 to 350 μm.

<Step B>

Step (B) is a step of forming a preliminary hardened resin layer by irradiating the coating layer with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² .

In the case where the irradiation intensity of the optical ultraviolet rays used in the step (B) is less than 100 mW / cm ² , from the point of strength display after the formal hardening, it is preferably 50 mW / cm ² or less, and more preferably 30 mW / cm ² Hereinafter, it is more preferable that it is 1 mW / cm ² or more from the viewpoint of the time from when the resin layer can be initially cured. In this specification, the ultraviolet irradiation intensity is the maximum intensity measured using a light meter, which can be measured by a light meter, which corresponds to the wavelength of the light source with the highest irradiation intensity in a wavelength distribution of 300 to 500 nm. There is sensitivity in the wavelength range. The light source may have single or plural peaks in a wavelength distribution of 300 to 500 nm, but as long as the highest irradiation intensity does not reach 100 mW / cm ² . By using such a light source, it is possible to prevent the dripping and outflow of the initially hardened liquid and the strength display after the formal hardening.

Regarding the light used in the irradiation in step (B), the cumulative value of the irradiation intensity at a wavelength of 300 to 500 nm is not particularly limited with respect to the cumulative value of the irradiation intensity at all wavelengths, but it is expressed from the point of intensity after formal hardening In view of this, it is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more.

As the light source, an ultraviolet (UV) light source 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. The light emitted by these light sources can also be adjusted to light of a specific wavelength by passing through a filter. Specifically, it can be adjusted by passing a filter capable of cutting light having a wavelength of 300 nm or less and / or a filter capable of cutting light having a wavelength of 500 nm or more. Examples of such filters include quartz interference filters (model: A7028-05, manufactured by Hamamatsu Photonics Corporation), LT filters, RT filters (all manufactured by HOYA Corporation), and bandpass filters (Eye Graphics Corporation)制) and so on. It is also possible to use LEDs as light sources. Examples of the light sources include LEDs with a peak of 365 nm, LEDs with a peak of 405 nm, LEDs with a peak of 375 nm, LEDs with a peak of 385 nm, and LEDs with a peak of 395 nm. Wait.

The coating layer is irradiated with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² to initially harden the resin composition of the coating layer to form a preliminary hardened resin layer. The irradiation method is not particularly limited, and for example, irradiation can be performed so that the cumulative amount of ultraviolet light becomes 30 to 7,500 mJ / cm ² . The cumulative light amount is preferably 50 to 5000 mJ / cm ² , and more preferably 100 to 2000 mJ / cm ² .

From the point of strength display or outflow after full hardening, and prevention of liquid dripping, the hardening rate of the preliminary hardening resin layer is preferably 40 to 90%, more preferably 45 to 80%, and even more preferably 50 to 70%. Light-curing resin The reduction rate of the (meth) acrylic group before and after the ultraviolet irradiation of the composition is defined and can be measured by FT-IR.

<Step C>

Step C is a step of bonding the substrate 2 on the preliminary hardened resin layer. Place the substrate 2 on the substrate 1 on which the preliminary hardened resin layer is formed, and place the substrate 2 in a manner to be connected to the preliminary hardened resin layer. Depending on the situation, the substrate 1 and the substrate 2 can be pressed to attach the substrate 1 and the substrate. 2. The pressing method is not particularly limited, and a rubber roller, a flat plate pressing device, or the like can be used.

<Step D>

Step D is a step of hardening the preliminary hardened resin layer between the base material 1 and the base material 2 by irradiating it with light. When any one of the base material 1 and the base material 2 is a light-transmitting member, light can be irradiated from the base material side that becomes the light-transmitting member to harden it formally.

The optical system is not particularly limited, and active energy rays such as visible rays, ultraviolet rays, X-rays, and electron rays can be used, and ultraviolet rays are preferred. As the light source, metal halide lamps, high-pressure mercury lamps, xenon lamps, halogen lamps, pulsed xenon lamps, and the like can be used.

The method of irradiating light is not particularly limited, and for example, it may be a method with a cumulative light amount of 500 to 10,000 mJ / cm ² and irradiate light with an intensity of 10 to 1500 mW / cm ² . The intensity is preferably 100 to 1000 mW / cm ² , more preferably 200 to 500 mW / cm ² , and the cumulative light amount is preferably 1000 to 6000 mJ / cm ² , and more preferably 1500 to 4500 mJ / cm ² .

[Example]

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited by these examples. Unless otherwise specified, it means mass parts and mass%.

Each component shown in Table 1 was weighed in a polyethylene container, and a Sany motor (manufactured by Tokyo Science Equipment Co., Ltd., MAZELA) was used to uniformly mix using a stirring blade to prepare a photocurable resin composition.

<Example 1>

On a 26mm × 75mm × 1.1mmt glass, a 150 μmt-thick interval made of 3 pieces of celluloid tape (50 μmt) was pasted so that the coated portion of the photocurable resin became a square shape of 10 mm × 10 mm. After forming a photocurable resin composition coating layer using a metal blade, the spacers are removed (Fig. 1 (1)).

Under the preliminary hardening conditions shown in Table 2, the measurement was performed using a mercury-xenon lamp (Execure4000, manufactured by HOYA Corporation, and the emission spectrum shown in Fig. 2) at an ultraviolet irradiation intensity (365 nm) of 30 mW / cm ² (measured by Hamamatsu PHOTONICS Corporation) Irradiate to form a preliminary hardened resin layer. The cumulative value of the irradiation intensity at a wavelength of 300 to 500 nm with respect to the cumulative value of the irradiation intensity at the full wavelength is the luminous intensity in the cumulative wavelength distribution measurement, and the result shows that it is about 85%.

The hardening rate of the preliminary hardened resin layer was measured by measuring the reduction rate of the acrylic group before and after ultraviolet irradiation of the photocurable resin composition by FT-IR (Spectrum 100, manufactured by Perkin Elmer). The reduction rate is determined by measuring the absorption peak height (X) of 800 to 820 cm ^-1 from the baseline in the FT-IR measurement of the resin composition layer before ultraviolet irradiation and the FT-IR measurement of the resin composition layer after ultraviolet irradiation. The absorption peak height (Y) from 800 to 820 cm ^-1 from the baseline in the figure is obtained by substituting it into the following formula (1).

Hardening rate (%) = ((X-Y) / X) × 100‧‧‧ (1)

Another 26 mm × 75 mm × 1.1 mmt glass was prepared, and it was placed on the glass on which the preliminary hardened resin layer was formed so as to be in contact with the preliminary hardened resin layer, and then pressed and bonded (FIG. 1 (2)).

The outflow of the preliminary hardened resin layer and the dripping of the liquid were observed, and the following criteria were used for evaluation. The results are shown in Table 2.

Outflow‧Dripping liquid: ×

Outflow‧liquid dripping small: △

Outflow‧No dripping of liquid: ○

A metal halide lamp (200 to 400 mW / cm ² ) was used to irradiate light to the preliminary hardened resin layer through glass at 3000 mJ / cm ² to formally harden.

The following glass laminate was measured for tensile strength at 10 mm / min in the shearing direction using a tensile tester (Technograph TG-2kN manufactured by MINEBEA) and evaluated using the following criteria (Figure 1 (3)) . The results are shown in Table 2.

Less than 0.3MPa: ×

0.3 to less than 0.5MPa: △

Above 0.5MPa: ○

<Example 2>

In the preliminary hardening conditions shown in Table 3, a mercury-xenon lamp (Execure4000, manufactured by HOYA Corporation, and the emission spectrum shown in FIG. 2) was used to irradiate with a UV irradiation intensity (365 nm) of 100 W / cm ² to form a preliminary hardened resin layer. In the same manner as in Example 1, a glass laminate was prepared and the tensile strength was measured.

<Comparative example 1>

Under the preliminary hardening conditions shown in Table 4, a mercury-xenon lamp (Execure4000, manufactured by HOYA Co., Ltd., shown in Fig. 2) is used to irradiate with an ultraviolet irradiation intensity (365nm) of 100 mW / cm ² to form a preliminary hardened resin layer. In the same manner as in Example 1, a glass laminate was prepared and the tensile strength was measured.

In Examples 1 and 2, it can be seen that even if the resin layer is cured initially, A high rate also gives a laminated body in which glass is adhered to each other with a sufficient adhesive force.

[Industrial availability]

According to the method for manufacturing a laminated body of the present invention, since it is possible to provide a method for manufacturing a laminated body such as an image display device, which uses only a photo-hardening process and the substrates are adhered to each other with a sufficient adhesive force, industrial usefulness high.

Claims (9)

A method for producing a laminated body, comprising the steps of applying a photocurable resin composition on a substrate 1 to form a coating layer, and irradiating light with an ultraviolet irradiation intensity of 30 mW / cm ² or less to the coating layer to form a preliminary cured resin. A step of laminating, a step of laminating the base material 2 on the preliminary hardening resin layer, and a step of irradiating the preliminary hardening resin layer between the base material 1 and the base material 2 with light to formally harden it. For example, the method for producing a laminated body according to claim 1, wherein the light in the step of forming the preliminary hardened resin layer is light having an ultraviolet irradiation intensity of 1 to 30 mW / cm ² . For example, the method for manufacturing a laminated body according to claim 1 or 2, wherein the curing rate of the photocurable resin composition in the coating layer is 40 to 90%, and light having an intensity of 1 to 30 mW / cm ² is irradiated with ultraviolet rays. To form a preliminary hardened resin layer. For example, the method for manufacturing a laminated body according to claim 1 or 2, wherein the light having an ultraviolet irradiation intensity of 1 to 30 mW / cm ² is an LED with a peak of 365 nm and / or an LED with a peak of 405 nm as a light source. For example, a method for manufacturing a laminated body according to claim 1 or 2, wherein the light having an ultraviolet irradiation intensity of 1 to 30 mW / cm ^{2 is} a filter that cuts light having a wavelength of less than 300 nm and / or cuts a wavelength of more than 500 nm. Filter light. The manufacturing method of the laminated body of Claim 1 or 2 whose photocurable resin composition contains a (meth) acrylate oligomer and a photoinitiator. The method for producing a laminated body according to claim 6, wherein the (meth) acrylate oligomer has a (hydrogenated) polyisoprene, (hydrogenated) polybutadiene or polyurethane structure in the skeleton. (Meth) acrylate oligomers. For example, a method for manufacturing a laminated body according to claim 1 or 2, wherein one of the substrate 1 or the substrate 2 is a liquid crystal display panel, an organic EL display panel, a protective panel, or a touch panel, and the other is a light transmitting member . The method for manufacturing a laminated body according to claim 1 or 2, wherein the laminated system image display device.