JP2016036780A - Method of manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a laminate in which base materials are adhered to each other by sufficient adhesive force by using only a photocuring process.SOLUTION: A method of manufacturing a laminate includes: a process of forming a coating layer by coating a base material with a photocurable resin composition; a process of forming a temporarily cured resin layer by irradiating with light having ultraviolet ray irradiation intensity of less than 100 mW/cm; a process of adhering the base material on the temporarily cured resin layer; a process of finally curing by irradiating the base materials and the temporarily cured resin layer between the base materials with light. The photocurable resin composition contains (meth)acrylate oligomer having (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, or a polyurethane structure in a skeleton, and a photopolymerization initiator.SELECTED DRAWING: None

Description

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

  In an image display device used for a smartphone or the like, a light transmissive 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 between a display body and a light transmissive member. In image display devices, a light shielding layer such as a black matrix is often provided at the periphery of the light transmissive member in order to improve contrast and the like. Therefore, even if the display body and the light transmissive member are overlapped with each other through the photocurable resin composition and irradiated with light, the light is blocked by the presence of the light shielding layer, and the curing does not proceed sufficiently, resulting in flow out. Or a lack of adhesion may occur.

  In order to solve such a problem, a method has been proposed in which a thermopolymerization initiator is blended in a photocurable resin composition, light-irradiated, and further heat-cured (Patent Document 1).

  Further, as a method using only the photocuring process without using the thermosetting process, the photocurable resin composition is applied to the surface of the display body to be thicker than the thickness of the light shielding layer, and ultraviolet rays are 10 to 80%. There has been proposed a method in which light curing is performed so as to achieve a curing rate, and then a light transmissive member is stacked and then ultraviolet light is irradiated to perform main curing (Patent Document 2).

International Publication No. 2008/126860 JP 2013-151151 A

  However, in the method of Patent Document 2, if the curing rate in temporary curing is increased, then, when the light transmissive member is stacked and main curing is performed, sufficient adhesive force is not exhibited, while the curing rate in temporary curing is increased. When it is lowered, there is a problem that a portion where curing does not proceed sufficiently occurs due to the presence of the light-shielding layer as in the past.

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

The present invention 1 is a step of applying a photocurable resin composition to a substrate 1 to form a coating layer, and irradiating the coating layer with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² to temporarily cure the resin layer Laminating, including the step of bonding the base material 2 onto the temporarily cured resin layer, and the step of irradiating the temporary cured resin layer between the base material 1 and the base material 2 with light and performing the main curing. The present invention relates to a method for manufacturing a body.
This invention 2 relates to the manufacturing method of the laminated body of this invention 1 whose light of the process of forming a temporary-hardening resin layer is light with an ultraviolet irradiation intensity of 1-50 mW / cm < ² >.
Invention 3 forms the temporary cured resin layer 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 coating layer is 40 to 90%. The manufacturing method of the laminated body of this invention 1 or 2.
The present invention 4 is the production of the laminate according to any one of the present inventions 1 to 3, wherein light having an ultraviolet irradiation intensity of less than 100 mW / cm ² is an LED having a peak at 365 nm and / or an LED having a peak at 405 nm. Regarding the method.
The present invention 5 is the present invention, wherein light having an ultraviolet irradiation intensity of less than 100 mW / cm ² is light that has passed through an optical filter that cuts light having a wavelength of 300 nm or less and / or an optical filter that cuts wavelength of 500 nm or more. The present invention relates to a method for producing any one of the laminates 1 to 4.
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.
This invention 7 is related with the manufacturing method of the laminated body of this invention 6 whose (meth) acrylate oligomer is the (meth) acrylate oligomer which has (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, or a polyurethane structure in frame | skeleton.
Invention 8 is any one of 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, and the other is a light transmissive member. The present invention relates to a method for producing a laminate.
This invention 9 relates to the manufacturing method of the laminated body in any one of this invention 1-8 whose laminated body is an image display apparatus.

  According to the method for manufacturing a laminate of the present invention, a laminate in which substrates are bonded to each other with a sufficient adhesive force using only a photocuring process, for example, an image display device is provided.

It is an evaluation process of the adhesive force of an Example. It is the emission spectrum of the light used by the temporary hardening of an Example and a comparative example.

The manufacturing method of the laminated body of this invention includes the following process (A)-(D).
Step (A): A step of applying a photocurable resin composition to the substrate 1 to form a coating layer,
Step (B): A step of irradiating the coating 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 onto the temporarily cured resin layer, and Step (D): The temporary cured resin layer between the base material 1 and the base material 2 is irradiated with light to be fully cured. Process.

<Laminate>
As for the laminated body which is the target object of the manufacturing method of this invention, the base material 1 and the base material 2 are adhere | attached using the photocurable resin composition. The substrate 1 and the substrate 2 are not particularly limited, and may be the same substrate or different substrates. In the step D, it is preferable that at least one of the base material 1 and the base material 2 is a light transmissive member from the viewpoint of irradiating the temporarily cured resin layer with light. In addition to the base material 1 and the base material 2, the laminated body may contain the further base material, and the adhesion method of the base material is not specifically limited.

  For example, the laminated body which is various image display apparatuses can be manufactured by using either the base material 1 or the base material 2 as a display body, and making the other into a light transmissive member. For example, a liquid crystal display device can be manufactured by using one of the substrate 1 or the substrate 2 as a liquid crystal display panel and the other as a light transmissive member, one as an organic EL display panel, and the other as a light transmissive member. By doing so, an organic EL display device can be manufactured.

  For example, a touch panel can be manufactured by using one of the substrate 1 or the substrate 2 as a light-transmitting substrate on which a transparent electrode is formed and the other as a light-transmitting member. Furthermore, one of the substrate 1 or the substrate 2 can be a touch panel, and the other can be an icon sheet or a decorative board.

  For example, an image display device with a protection panel or a substrate with a protection panel can be manufactured 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 substrates. . Furthermore, the base material 1 can be a protective panel, and the base material 2 can be a light transmissive member.

  When the light transmissive member is used, the light transmissive member only needs to have light transmittance according to the purpose of the laminated body. For example, when the laminated body is an image display device, an image formed on the display body is not necessary. What is necessary is just to have the light transmittance of the grade which can be visually recognized. Examples of the light transmissive member include glass, (meth) acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyester, cycloolefin polymer, and other plate-like materials and sheet-like materials. These may be subjected to hard code processing, antireflection processing, antiglare processing, antifouling processing, antifogging processing, polarization processing, wavelength cut processing, or the like on one side or both sides. In addition, a light shielding layer may be formed on the light transmissive member.

<Process A>
Step A is a step of forming a coating layer by applying a photocurable resin composition to the substrate 1. As a photocurable resin composition, the composition containing a (meth) acrylate oligomer and a photoinitiator can be used.

  The (meth) acrylate oligomer is not particularly limited, and examples thereof include (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, and (meth) acrylate oligomer having a skeleton as a skeleton. These (meth) acrylate oligomers can be used alone or in combination of two or more. Here, (hydrogenated) polyisoprene includes polyisoprene and / or hydrogenated polyisoprene, and (hydrogenated) polybutadiene includes polybutadiene and / or hydrogenated polybutadiene.

  The (meth) acrylate oligomer having a (hydrogenated) polyisoprene as a skeleton is also called a (meth) acryl-modified polyisoprene, and preferably has a molecular weight of 1000 to 100,000, more preferably 10,000 to 50,000. As a commercial item, there exists "UC-1" (molecular weight 25000) made from Kuraray, for example.

  The (meth) acrylate oligomer having a (hydrogenated) polybutadiene as a skeleton is also referred to as (meth) acryl-modified polybutadiene, and preferably has a molecular weight of 500 to 100,000, more preferably 1,000 to 30,000. An example of a commercially available product is “TE2000” (molecular weight 2000) manufactured by Nippon Oil Corporation.

  The (meth) acrylate oligomer having a polyurethane as a skeleton is also called a (meth) acryl-modified polyurethane, and preferably has a molecular weight of 1000 to 100,000, more preferably 10,000 to 50,000. Examples of commercially available products include “UA-1” manufactured by Light Chemical Co., Ltd. and “UV3630ID80” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

  As the (meth) acrylate oligomer, a (meth) acrylate oligomer having a polyurethane as a skeleton is particularly preferable.

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

  The photopolymerization initiator is not particularly limited, and is 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl- Ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine 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, Nzoin 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, ethyl anthraquinone, benzophenone ammonium salt, thioxanthone ammonium salt, bis (2,6-dimethoxybenzo) ) -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-benzoyl biphenyl, 4-benzoyl diphenyl ether, acrylated benzophenone, bis ( 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, o-methylbenzoylbenzoate, p-dimethylaminobenzoic acid Examples include ethyl ester, p-dimethylaminobenzoic acid isoamyl ethyl ester, active tertiary amine, carbazole / phenone photopolymerization initiator, acridine photopolymerization initiator, triazine photopolymerization initiator, benzoyl photopolymerization initiator, etc. it can.

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

  A photoinitiator may be 1 type or may use 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. Part by mass.

  The photocurable resin composition can contain a (meth) acrylate monomer as a reaction diluent, for example, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate. Alkyl (meth) acrylates such as tert-butyl (meth) acrylate and lauryl (meth) acrylate; alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate and 2-hydroxy Hydroxy-substituted alkyl (meth) acrylates such as propyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, etc .; ethylene glycol di (meth) acrylate, diethylene glycol Cold di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, Examples include di (meth) acrylates such as 6-hexanediol di (meth) acrylate; dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate. it can.

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

  The (meth) acrylate monomer 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 still more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the (meth) acrylate oligomer. is there.

  The photocurable resin composition can contain a plasticizer. Plasticizers include dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc .; dioctyl adipate, diisononyl adipate, dioctyl sebacate, diisononyl sebacate Polycarboxylic esters such as 1,2-cyclohexanedicarboxylic acid diisononyl; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Rubber polymers such as polyisoprene, polybutadiene and polybutene; Thermoplastic elastomers Petroleum resin; alicyclic saturated hydrocarbon resin; terpene resin such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin; Rosin resins such Lumpur; disproportionated rosin ester resin, polymerized rosin ester resin, hydrogenated (hydrogenated) rosin ester resins such as rosin ester resins.

  As the plasticizer, polyvalent carboxylic acid ester, rosin ester-based resin and the like are preferable, and 1,2-cyclohexanedicarboxylic acid diisononyl, (hydrogenated) rosin ester-based resin are more preferable.

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

  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 can further contain an adhesion-imparting agent. Silane coupling agents such as vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldisilane as adhesion promoters Ethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxy Lan, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl- Butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl, methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples thereof include bis (triethoxysilylpropyl) tetrasulfide and 3-isocyanatopropyltriethoxysilane.

  The adhesion imparting agent may be used alone or in combination of two or more.

  The adhesion-imparting agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylate oligomer. Part.

  The photocurable resin composition can contain an antioxidant. Antioxidants include BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl. 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-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethyle Bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2,4, -bis [(octylthio) methyl] -O-cresol, isooctyl- Examples include 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and dibutylhydroxytoluene.

  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 masses. Part.

  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, an ultraviolet absorber, and an antifoam are within the range not impairing the effects of the present invention. An agent or the like can be blended.

  A photocurable resin composition can be prepared by mixing each component. The mixing method is not particularly limited, and various metals, plastic containers, stirring blades, and a stirrer can be used.

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

  The thickness of a coating layer is not specifically limited, For example, it can be set as 10-500 micrometers, and 30-350 micrometers is preferable.

<Process B>
Step (B) is a step of irradiating the coating layer with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² to form a temporarily cured resin layer.

The light used for the irradiation in the step (B) has an ultraviolet irradiation intensity of less than 100 mW / cm ² , and is preferably 50 mW / cm ² or less, more preferably from the viewpoint of intensity development after the main curing. Is 30 mW / cm ² or less, and is preferably 1 mW / cm ² or more from the point of time until the provisionally cured resin layer can be formed. In this specification, the ultraviolet irradiation intensity is the maximum intensity measured using an illuminometer, and the illuminance having sensitivity in the wavelength range corresponding to the wavelength with the highest irradiation intensity in the wavelength distribution of 300 to 500 nm of the light source used. It can be measured by a meter. The light source may have a single peak or a plurality of peaks in a wavelength distribution of 300 to 500 nm, but it is sufficient that the highest irradiation intensity is less than 100 mW / cm ² . By using such a light source, it is possible to prevent dripping and flow-out during temporary curing and to develop strength after main curing.

  Regarding the light used for the 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, but is preferable from the viewpoint of the intensity expression after the main curing. Is 90% or more, more preferably 95% or more, and still more preferably 98% or more.

  As the light source, a light source that emits 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 pulse xenon lamp. The light emitted from these light sources may be adjusted to light of a specific wavelength by passing through an optical filter. Specifically, it can be adjusted by passing 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. Examples of such optical filters include quartz interference filters (model number: A7028-05, manufactured by Hamamatsu Photonics), LT filters, RT filters (both manufactured by HOYA), bandpass filters (produced by Eye Graphics), and the like. It is done. Light with LED as light source can also be used. LED with 365 nm peak, LED with 405 nm peak, LED with 375 nm peak, LED with 385 nm peak, LED with 395 nm peak, etc. Can be mentioned.

By irradiating the coating layer with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² , the resin composition of the coating layer is temporarily cured to form a temporarily cured resin layer. The irradiation method is not particularly limited, and for example, the irradiation can be performed so that the ultraviolet ray accumulated light amount is 30 to 7500 mJ / cm ² . Integrated light quantity is preferably 50 to 5000 mJ / cm ^2, more preferably at 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 from the viewpoints of strength development and flow-out after main curing, and prevention of dripping. ~ 70%. The curing rate is defined by the rate of decrease of (meth) acrylic groups 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. The substrate 2 is placed on the substrate 1 on which the temporarily cured resin layer is formed so as to be in contact with the temporarily cured resin layer, and in some cases, the substrate 1 and the substrate 2 are pressurized by pressing from the substrate 1 side and / or the substrate 2 side. Can be pasted together. The pressurizing method is not particularly limited, and a rubber roller, a flat plate press device or the like can be used.

<Process D>
Process D is a process in which the temporarily cured resin layer between the base material 1 and the base material 2 is further cured by irradiating light. When either of the base material 1 and the base material 2 is a light transmissive member, light can be irradiated from the base material side which is a light transmissive member, and this can be hardened.

  The light is not particularly limited, and active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams can be used, and preferably ultraviolet rays. As the light source, a metal halide lamp, a high-pressure mercury lamp, a xenon lamp, a halogen lamp, a pulse xenon lamp, or the like can be used.

Irradiation method of light is not particularly limited, for example, the light intensity 10~1500mW / cm ^2, can be irradiated so that the integrated light quantity 500~10000mJ / cm ^2. Strength, preferably 100~1000mW / cm ^2, more preferably 200~500mW / cm ^2, integrated light quantity is preferably 1000~6000mJ / cm ^2, more preferably a 1500~4500mJ / cm ^2.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The indications are parts by mass and% by mass unless otherwise specified.

  Each component of the composition shown in Table 1 was weighed into a polyethylene container and uniformly mixed using a three-one motor (manufactured by Tokyo Science Equipment Co., Ltd., MAZELA) and a stirring blade to prepare a photocurable resin composition.

<Example 1>
A metal squeegee is pasted on a 26mm x 75mm x 1.1mmt glass with a 150μm thick spacer created using 3 pieces of cellophane tape (50μmt) so that the coated part of the photo-curing resin becomes a 10mm x 10mm square shape. After the photocurable resin composition coating layer was formed using, the spacer was removed (FIG. 1 (1)).
Under the temporary curing conditions shown in Table 2, using a mercury xenon lamp (manufactured by HOYA, EXECURE 4000, emission spectrum shown in FIG. 2), ultraviolet irradiation intensity (365 nm) 30 mW / cm ² (measured by Hamamatsu Photonics) Was irradiated to form a temporarily cured resin layer. When 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 obtained by integrating the emission intensity in the wavelength distribution measurement, it is found to be about 85%.
The curing rate of the temporarily cured resin layer was measured by FT-IR (Perkin Elmer, Spectrum 100) as a decrease rate of the acrylic group before and after the ultraviolet irradiation of the photocurable resin composition. The rate of decrease 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 of the resin composition layer after ultraviolet irradiation. It calculated | required by substituting the absorption peak height (Y) of 800-820 cm < ^-1 > from the base line in a chart to the following Numerical formula (1).

Curing rate (%) = {(XY) / X} × 100 (1)

Another 26 mm × 75 mm × 1.1 mmt glass was prepared, placed on the glass on which the temporarily cured resin layer was formed so that the temporarily cured resin layer was in contact, and pressed and bonded together (FIG. 1 (2)). ).
The flow of the temporarily cured resin layer and the dripping were observed and evaluated according to the following criteria. The results are shown in Table 2.
Flowing out and dripping large: ×
Small outflow and dripping: △
No outflow or dripping: ○
In 3000 mJ / cm ² at a metal halide lamp (200~400mW / cm ^2), and irradiated with light temporarily cured resin layer through the glass, was cured.
About the bonded glass laminate, the tensile strength was measured at 10 mm / min in the shear direction using a tensile tester (Minebea, Technograph TG-2kN), and evaluated according to the following criteria (FIG. 1 (3)). ). The results are shown in Table 2.
Less than 0.3 MPa: x
0.3 to less than 0.5 MPa: Δ
0.5 MPa or more: ○

<Example 2>
Under the temporary curing conditions shown in Table 3, using a mercury xenon lamp (manufactured by HOYA, EXECURE 4000, emission spectrum is shown in FIG. 2), irradiation with ultraviolet irradiation intensity (365 nm) of 10 mW / cm ² is performed to perform temporary curing resin A glass laminate was prepared and the tensile strength was measured in the same manner as in Example 1 except that the layer was formed.

<Comparative Example 1>
Under the temporary curing conditions shown in Table 4, a mercury xenon lamp (manufactured by HOYA, EXECURE 4000, emission spectrum is shown in FIG. 2) was irradiated at an ultraviolet irradiation intensity (365 nm) of 100 mW / cm ² to provide a temporary cured resin. A glass laminate was prepared and the tensile strength was measured in the same manner as in Example 1 except that the layer was formed.

  In Examples 1 and 2, it can be seen that even when the curing rate of the temporarily cured resin layer is high, a laminated body in which the glasses are bonded to each other with sufficient adhesive strength can be obtained.

  According to the method for producing a laminate of the present invention, a laminate in which substrates are bonded to each other with sufficient adhesive force using only a photocuring process, for example, an image display device is provided. high.

DESCRIPTION OF SYMBOLS 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 a coating layer;
A step of irradiating the coating layer with light having an ultraviolet irradiation intensity of less than 100 mW / cm ² to form a temporarily cured resin layer;
Including a step of bonding the base material 2 on the temporarily cured resin layer, and a step of irradiating light to the temporary cured resin layer between the base material 1 and the base material 2 to perform main curing.
A manufacturing method of a layered product. The manufacturing method of the laminated body of Claim 1 whose light of the process of forming a temporarily-cured resin layer is light with an ultraviolet irradiation intensity of 1 to 50 mW / cm ² . The temporary-curing 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 photo-curable resin composition in the coating layer is 40 to 90%. Or the manufacturing method of the laminated body of 2. The method for producing a laminate according to any one of claims 1 to 3, wherein light having an ultraviolet irradiation intensity of less than 100 mW / cm ² uses an LED having a peak at 365 nm and / or an LED having a peak at 405 nm as a light source. . The light having an ultraviolet irradiation intensity of less than 100 mW / cm ² is light that has 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. The manufacturing method of the laminated body of Claim 1.   The manufacturing method of the laminated body of any one of Claims 1-5 in which a photocurable resin composition contains a (meth) acrylate oligomer and a photoinitiator.   The manufacturing method of the laminated body of Claim 6 whose (meth) acrylate oligomer is a (meth) acrylate oligomer which has (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, or a polyurethane structure in frame | skeleton.   The laminate according to any one of claims 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, and the other is a light transmissive member. Body manufacturing method.   The manufacturing method of the laminated body of any one of Claims 1-8 whose laminated body is an image display apparatus.