JP2017149135A - Method for producing layered body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a layered body, including allowing two substrates to adhere to each other to sandwich a layer formed of a photo-curable and thermosetting resin composition between the substrates, in which an overflow of the uncured compositions is reduced in lamination, and the layered body has sufficient adhesive strength.SOLUTION: The method for producing a layered body includes: (A) a step of applying a photo-curable and thermosetting resin composition to a substrate 1 to form a curable resin composition layer; (B) a step of irradiating the curable resin composition layer with energy rays to form a curable resin layer having an elastic modulus of 10Pa to 10Pa; (C) a step of laminating a substrate 2 on the curable resin layer to obtain a laminated body; and (D) a step of heating the laminated body, thereby allowing the curable resin layer to have an elastic modulus of more than 10Pa, to obtain a layered body.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.

  When manufacturing a display element such as a display, it is necessary to bond a cover lens and a display element including a TFT or the like. In Patent Document 1, a thermal polymerization initiator is blended with a photocurable resin composition to form a heat and photocurable resin composition, and the heat and light are applied to the surface of the light-transmitting cover member on which the light shielding layer is formed. Heat applied between the light-shielding layer and the image display member by heating the whole after applying the curable resin composition, layering the application surface on the image display member, irradiating the photo-irradiation with ultraviolet rays and photocuring It has also been proposed to thermally cure the photocurable resin composition.

International Publication No. 2008/126860

  However, since there are materials that do not transmit light, for example, ultraviolet rays, in the cover lens constituting the image display device, there is a problem that curing is not sufficient when using a photocurable resin. As a result, during bonding, the uncured composition wets and spreads out from a predetermined position of the display body or the light transmissive member, which may cause problems in subsequent processes such as contamination of the device.

  The present invention solves the above problems and is a method for producing a laminate in which two substrates are bonded via a layer formed from light and a thermosetting resin composition, and is uncured at the time of bonding An object of the present invention is to provide a method for producing a laminate in which the protrusion of the composition is reduced and the adhesive strength is sufficient.

The present invention has the following configuration.
(1) (A) a step of applying light and a thermosetting resin composition to the substrate 1 to form a curable resin composition layer;
(B) A step of irradiating the curable resin composition layer with energy rays to form a cured resin layer having an elastic modulus of 10 ² Pa to 10 ⁵ Pa, and (C) the substrate 2 on the cured resin layer. A process of obtaining a bonded body,
(D) heating the bonded body, setting the elastic modulus of the cured resin layer to more than 10 ⁵ Pa, and obtaining a laminate;
The manufacturing method of a laminated body containing this.
(2) The production method of (1), wherein the light and thermosetting resin composition is an acrylate resin composition containing a (meth) acrylic resin or a hybrid resin composition containing a (meth) acrylic resin and an epoxy resin.
(3) The manufacturing method of (1) or (2) in which light and a thermosetting resin composition contain 0.1-20 mass parts of photoradical initiators with respect to 100 mass parts of (meth) acrylic resins.
(4) 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 or a member that does not transmit light. The manufacturing method of the laminated body in any one of (3).
(5) A light and thermosetting resin composition for use in the method for producing a laminate according to any one of (1) to (4).

  According to the present invention, there is provided a method for manufacturing a laminate in which two substrates are bonded via a layer formed from light and a thermosetting resin composition, and the uncured composition is not protruded at the time of bonding. There is provided a method for producing a laminate that is reduced and has sufficient adhesive strength.

[Definition of terms]
“(Meth) acrylate” has at least one of acrylate and methacrylate.
The “(meth) acryloyl group” has at least one of an acryloyl group and a methacryloyl group.
“(Meth) acrylated epoxy resin” means a resin in which all epoxy groups in the epoxy resin are reacted with (meth) acrylic acid.
“Partially (meth) acrylated epoxy resin” means a resin in which some epoxy groups in the epoxy resin are reacted with (meth) acrylic acid, that is, epoxy groups and (meth) acryloyl groups in the resin. Have
The “epoxy resin” is not a resin having an epoxy group and a (meth) acryloyl group (that is, a partially (meth) acrylated epoxy resin).

[Manufacturing method of laminate]
The manufacturing method of a laminated body contains the following process (A), (B), (C) and (D).
(A) Applying light and a thermosetting resin composition to the substrate 1 to form a curable resin composition layer;
(B) irradiating the curable resin composition layer with energy rays to form a cured resin layer having an elastic modulus of 10 ² Pa to 10 ⁵ Pa;
(C) The base material 2 is bonded on the cured resin layer to obtain a bonded body, and (D) the bonded body is heated to make the elastic modulus of the cured resin layer exceed 10 ⁵ Pa. The process of obtaining a laminated body.

[Laminate]
As for the laminated body, the base material 1 and the base material 2 are adhere | attached through light and the thermosetting resin composition. The substrate 1 and the substrate 2 are not particularly limited, and may be the same substrate or different substrates. 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.

  The base material 1 and the base material 2 may be a light transmissive member or a member that does not transmit light. The light-transmitting 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, visible light transmission is such that an image formed on the display body is visible. What is necessary is just to have sex. 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. Examples of such a light transmissive member include an icon sheet and a decorative board.

  The member that does not transmit light is not particularly limited as long as it is an organic material that does not transmit light, an inorganic material that does not transmit light, or a combination thereof. As a member that does not transmit light, a plate-like material or sheet-like material of ceramics such as alumina, a metal sheet such as stainless steel subjected to an insulation treatment such as surface oxidation, a plate-like material of thermosetting resin, thermoplastic resin, A sheet-like material is mentioned. Specific examples of such a member that does not transmit light include a liquid crystal display panel, an organic EL display panel, a protective panel, a touch panel, an organic EL element, and a member on which a color filter has already been formed.

For example, by using one of the substrate 1 and the substrate 2 as a display body and the other as a light-transmitting member or a member that does not transmit light, laminates that are various image display devices can be manufactured. Specific embodiments are as follows.
(1) 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-transmitting member.
(2) A so-called top emission type organic EL display device can be manufactured by using one of the substrate 1 and the substrate 2 as an organic EL display panel and the other as a light-transmitting member.
(3) A so-called bottom emission type organic EL display device can be manufactured by using one of the substrate 1 and the substrate 2 as an organic EL display panel and the other as a member that does not transmit light.
(4) 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. it can. Furthermore, one of the substrate 1 and the substrate 2 can be a protective panel and the other can be a light transmissive member.
(5) 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 a light transmissive member.

  Therefore, in the manufacturing method of the laminate, one of the base material 1 and the base material 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 or a member that does not transmit light. Can be.

  The manufacturing method of a laminated body is the combination of the base material 1 and the base material 2, and the base material by which the color filter was laminated | stacked on the base material which is glass, a polyimide, or those combinations, and glass, a polyimide, or those combinations A combination with a base material in which an element such as EL and a protective film are laminated in this order on the base material is more preferable. Here, the light and thermosetting resin composition is preferably applied on a base material on which a color filter is laminated.

[Step (A)]
Step (A) is a step of forming a curable resin composition layer by applying light and a thermosetting resin composition to the substrate 1.

(Light and thermosetting resin composition)
The light and thermosetting resin composition (hereinafter, also simply referred to as “composition”) is not particularly limited as long as it is a composition containing light and thermosetting resin that is cured by energy rays and heat. The light and thermosetting resin is preferably a (meth) acrylic resin, and an epoxy resin having an epoxy group may be used in combination with the (meth) acrylic resin from the viewpoint of further improving the adhesive strength. Therefore, examples of the composition include an acrylate resin composition containing a (meth) acrylic resin, or a hybrid resin composition containing a (meth) acrylate resin and an epoxy resin. In the acrylate resin composition, the curable component is preferably made of a (meth) acrylic resin, and in the hybrid resin composition, the curable component is preferably made of a (meth) acrylic resin and an epoxy resin having an epoxy group. Here, the curable component refers to a component that is polymerized and cross-linked by light irradiation and heating.

<(Meth) acrylic resin>
The (meth) acrylic resin is not particularly limited as long as it is a resin having one or more (meth) acryloyl groups in the molecule. (Meth) acrylate oligomer, monofunctional (meth) acrylate monomer, polyfunctional (meth) acrylate monomer , (Meth) acrylated epoxy resin and one or more selected from the group consisting of partially (meth) acrylated epoxy resin.

<< (Meth) acrylate oligomer >>
The (meth) acrylate oligomer has one or more (meth) acryloyl groups in the molecule. The molecular weight of the (meth) acrylate oligomer is 1,000 to 100,000, preferably 10,000 to 70,000, and more preferably 20,000 to 50,000. In the present specification, the molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.

  The (meth) acrylate oligomer is not particularly limited, and examples thereof include one or more selected from the group consisting of (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, or a (meth) acrylate oligomer having a polyurethane 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.

  Examples of the (meth) acrylate oligomer having (hydrogenated) polybutadiene as a skeleton include (hydrogenated) polybutadiene (meth) acrylate and (hydrogenated) polybutadiene urethane (meth) acrylate. (Hydrogenated) Examples of commercially available (meth) acrylate oligomers having polybutadiene as a skeleton include TE2000 (Nippon Soda Co., Ltd .: molecular weight 2,000).

  Examples of the (meth) acrylate oligomer having a (hydrogenated) polyisoprene as a skeleton include (hydrogenated) polyisoprene (meth) acrylate and (hydrogenated) polyisoprene urethane (meth) acrylate. (Hydrogenated) Examples of commercially available (meth) acrylate oligomers having polyisoprene as a skeleton include UC (manufactured by Kuraray Co., Ltd .: molecular weight 25,000).

  Examples of the (meth) acrylate oligomer having a polyurethane as a skeleton include polyether-based, polycarbonate-based, polyester-based, or a combination thereof. Commercially available products of (A) (meth) acrylate oligomer having a polyurethane skeleton include UA10000B (manufactured by KS Corporation: molecular weight 25,000), UA (manufactured by Light Chemical Industry Co., Ltd.), UV3630ID80 (Nippon Synthetic Chemical Industry Co., Ltd.) Product), UV3700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and the like.

  The (meth) acrylate oligomer is preferably a (meth) acrylate oligomer having a polyurethane as a skeleton, and more preferably a polyether-based polyurethane (meth) acrylate oligomer. The (meth) acrylate oligomer may be used alone or in combination of two or more.

<< Monofunctional (meth) acrylate monomer >>
The monofunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate compound having one (meth) acryloyl group in the molecule, and includes alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate (hydroxy One or more selected from the group consisting of hydroxyl-containing (meth) acrylates other than substituted alkyl (meth) acrylates and hydroxy-substituted alkyl (meth) acrylates), alicyclic (meth) acrylates, alkoxy-substituted alkyl (meth) acrylates, and 1 type or more selected from the group which consists of aromatic (meth) acrylate is mentioned, 1 type selected from the group which consists of alkyl (meth) acrylate, hydroxy substituted alkyl (meth) acrylate, and alicyclic (meth) acrylate The above is preferable.

Alkyl (meth) acrylate is 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, and the like.
Hydroxyl group-containing (meth) acrylates are hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. ) Acrylate; and 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, cyclohexane Examples include hydroxyl group-containing (meth) acrylates other than hydroxy-substituted alkyl (meth) acrylates such as dimethanol mono (meth) acrylate.
Examples of the alicyclic (meth) acrylate include dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate.

<< Polyfunctional (meth) acrylate monomer >>
The polyfunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule. When the composition contains a polyfunctional (meth) acrylate monomer, the crosslinking density tends to increase, and the elastic modulus can be further improved in a small amount as compared with a monofunctional (meth) acrylate monomer. 2-10 are preferable and, as for the number of (meth) acryloyl groups of a polyfunctional (meth) acrylate monomer, ie, a functional number, 2-4 are more preferable.

  Such polyfunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) ) Aliphatic di (meth) acrylates such as acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol diacrylate; dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di ( Alicyclic di (meth) acrylates such as (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Polyols such as tri (meth) acrylates such as tri (meth) acrylates such as carbonates; tri (meth) acrylates of alkylene oxide adducts of trimethylolpropane and tri (meth) acrylates of alkylene oxide adducts of pentaerythritol Tri (meth) acrylates of alkylene oxide adducts; aliphatic tetra (meth) acrylates such as pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate; tetra (meth) acrylates of alkylene oxide adducts of pentaerythritol, ditrimethylolpropane Examples include tetra (meth) acrylates of alkylene oxide adducts of polyols such as tetra (meth) acrylates of alkylene oxide adducts.

<< (Meth) acrylated epoxy resin and partial (meth) acrylated epoxy resin >>
The (meth) acrylated epoxy resin and the partial (meth) acrylated epoxy resin can be obtained by a reaction between the epoxy resin and (meth) acrylic acid.
Specifically, epoxy resin (meth) acrylic acid in a predetermined equivalent ratio and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, , Methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) and, for example, by esterifying at 80 to 110 ° C., all or part of the epoxy group may be (meth) acrylated. it can.
The epoxy resin used as a raw material is not particularly limited, and a bifunctional or higher functional epoxy resin is preferable. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin Aliphatic chain epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and phenol novolac type epoxy resins having a triphenolmethane skeleton. In addition, diglycidyl etherified products of difunctional phenols, diglycidyl etherified products of bifunctional alcohols, their halides, hydrogenated products, and the like can also be used. Multifunctional epoxy resins can also be used, for example, trifunctional and tetrafunctional epoxy resins. Moreover, the epoxy resin of Unexamined-Japanese-Patent No. 2012-070220 can be used.

  In the partially (meth) acrylated epoxy resin, the (meth) acryloyl group is preferably 10 to 90 mol%, more preferably based on the total number of moles of the (meth) acryloyl group and the epoxy group in the resin. It is 40-60 mol%. The partially (meth) acrylated epoxy resin preferably contains a compound containing one or more epoxy groups and (meth) acryloyl groups in one molecule.

  The (meth) acrylic resin is one or more selected from the group consisting of monofunctional (meth) acrylate monomers, and a partially (meth) acrylated epoxy resin, from the viewpoint of efficiently adjusting the viscosity and the elastic modulus after photocuring. A combination with a polyfunctional (meth) acrylate monomer or a partially (meth) acrylated epoxy resin is preferred.

<Epoxy resin>
An epoxy resin can mention 1 or more types selected from the group which consists of an aromatic epoxy compound, an aliphatic epoxy compound, and an alicyclic epoxy compound.

  As aromatic epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol AD type epoxy compounds, bisphenol S type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, polyfunctional Specific examples thereof include bisphenol A type epoxy compounds such as EPICLON850, 850-S, and EXA-850CPR manufactured by DIC Corporation; EPICLON830-S, EXA-830LVP manufactured by DIC Corporation, and the like. Bisphenol F type epoxy compounds; EPICLON HP-4032D, HP-7200H, etc. manufactured by DIC Corporation; Naphthalene type epoxy compounds such as E-7, manufactured by DIC Corporation Phenol novolac type epoxy compounds such as ICLON N-740 and N-770; Cresol novolak type epoxy compounds such as EPICLON N-660, N-670 and N-655-EXP-S manufactured by DIC Corporation; tetra (hydroxyphenyl) Examples thereof include polyfunctional epoxy compounds such as glycidyl ether of alkane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol.

  Examples of the alicyclic epoxy compound include hydrogenated aromatic epoxy compounds, cyclohexane, cyclohexyl methyl ester, cyclohexyl methyl ether, spiro, and tricyclodecane epoxy compounds. Specific examples thereof include: Hydrogenated bisphenol A type epoxy compounds such as KRM-2408, EP-4080E manufactured by ADEKA Corporation, YX-8034 manufactured by JER Corporation; dicyclopentadiene type epoxy compounds such as EP-4088L manufactured by ADEKA Corporation; Daicel CEL2021P and other 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; 1,2: 8,9-diepoxylimonene; 1,2-epoxy-4-vinylcyclohexane; Made of E It can be mentioned 2,2-bis (hydroxymethyl) -1-1,2-epoxy-4- butanol (2-oxiranyl) cyclohexane adduct alicyclic epoxy compounds such as PE3150.

  Examples of the aliphatic epoxy compound include polyglycidyl ethers of polyhydric alcohols or alkylene oxide adducts thereof. Specific examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol A diglycidyl ether etc. can be mentioned.

  The epoxy resin is preferably a combination of an aromatic epoxy compound and an alicyclic epoxy compound from the viewpoint of further improving the adhesiveness by thermosetting.

<Content>
When the composition is a hybrid resin composition containing a (meth) acrylic resin and an epoxy resin (hereinafter also simply referred to as “hybrid resin composition”), the total amount of the (meth) acrylic resin and the epoxy resin is 100% by mass. On the other hand, the content of the (meth) acrylic resin is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 50% by mass or more. The balance is epoxy resin. In the hybrid resin composition, when the content of the (meth) acrylic resin is 10% by mass or more with respect to the total of 100% by mass of the (meth) acrylic resin and the epoxy resin, the elasticity of the cured resin layer in the step (B) The rate tends to be easily controlled to 10 ² Pa or more. In the hybrid resin composition, when a polyfunctional (meth) acrylate monomer is present, the content of the polyfunctional (meth) acrylate monomer is selected from the viewpoint of controlling the elastic modulus of the cured resin layer in the step (B). 0.1-50 mass parts is preferable with respect to a total of 100 mass parts of (meth) acrylic resin, and 0.1-30 mass parts is more preferable.

<Initiator>
The composition can include an initiator to promote curing. Examples of the initiator include one or more selected from the group consisting of a photo radical initiator, a thermal radical initiator, and a thermal cation initiator. When the composition is an acrylate resin composition, the composition preferably includes a photo radical initiator and a thermal radical initiator. Moreover, when a composition is an acrylate resin composition containing a partial (meth) acrylated epoxy resin, it is preferable that a composition contains a photoradical initiator, a thermal cation initiator, and a thermal radical initiator. When the composition is a hybrid resin composition, the composition preferably includes a photo radical initiator, a thermal cation initiator, and optionally a thermal radical initiator.

<< Photoradical initiator >>
The photoradical initiator is not particularly limited as long as it is a compound that generates radicals upon irradiation with light. Photoradical initiators include benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetone, p-dimethylaminoacetophenone, p -Dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2, -Carbonyl group photopolymerization initiators such as diethoxyacetophenone and 4-N, N'-dimethylacetophenone; Sulfide photopolymerization initiators such as diphenyl disulfide and dibenzyl disulfide; Quinone photopolymerization initiators such as benzoquinone and anthraquinone Agents; ultraviolet photoinitiators such as azo photopolymerization initiators such as azobisisobutyronitrile and 2,2′-azobispropane, and
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholinophenyl)- Examples include visible light initiators such as butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

From the viewpoint of increasing the speed of curing and reducing the color after photocuring, the photoradical initiator is 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Is preferred.
A photoinitiator may be 1 type or may use 2 or more types together.

In the composition, the content of the photo radical initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin. It is preferably 1 to 10 parts by mass. When content of a photoradical initiator is the said range, the elasticity modulus of a cured resin layer can be efficiently adjusted to 10 < ² > Pa-10 < ⁵ > Pa in a process (B).

<< Thermal radical initiator >>
The thermal radical initiator is not particularly limited as long as it is a compound that generates a radical by heating, and examples thereof include organic peroxides and azo compounds, and organic peroxides are preferable.

  The organic peroxide may be an organic compound containing a peroxy group (—O—O—). For example, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxycarbonates Etc.

  Specific examples of organic peroxides include diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide; 1,1,3,3-tetramethylbutyl hydro Peroxide, cumene hydroperoxide (for example, Kayakumen H manufactured by Kayaku Akzo Co., Ltd.), hydroperoxides such as t-butyl hydroperoxide; t-hexylperoxy 2-ethylhexanoate, dicumyl peroxide, 2,5- Dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2 , 5-Di (t-butylperoxy) hexyne-3 Dialkyl peroxides; 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane Peroxyketals such as 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate T-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di -T-butylperoxyhexahydroterephthalate, t-amylperoxy 3,5 , 5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-hexylperoxybenzoate, peroxyesters such as t-amylperoxybenzoate; di-2-ethylhexylperoxydicarbonate, diisopropylperoxydi Examples thereof include peroxycarbonates such as carbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy 2-ethylhexyl carbonate, and 1,6-bis (t-butylperoxycarbonyloxy) hexane. Such organic peroxides are commercially available from reagent suppliers and can be easily obtained.

  Examples of the azo compound include azobisisobutyronitrile (AIBN, V-60 (manufactured by Wako Pure Chemical Industries, Ltd.)), 2,2′-azobis (2-methylisobutyronitrile) (V-59 (Wako Pure). Yakuhin Kogyo Co., Ltd.)), 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 (Wako Pure Chemical Industries, Ltd.)), dimethyl-2,2′-azobis (isobutyrate) ( V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70 (manufactured by Wako Pure Chemical Industries, Ltd.)) and the like. It is done.

  The thermal radical polymerization initiator is preferably an organic peroxide from the viewpoint of stability and harmfulness. In addition, from the viewpoint of the balance between the stability of the composition and the curing temperature, the organic peroxide has a one-hour half-life decomposition temperature of 50 to 110 ° C., which is an index of deactivation of the organic peroxide. preferable.

In the composition, the content of the thermal radical polymerization initiator is preferably 0.01 to 15 parts by mass, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin. More preferably, it is 1-5 mass parts. When the content of the thermal radical initiator is within the above range, the outgas of the initiator decomposition product generated by heating can be suppressed, and the acrylic groups in the composition can be efficiently reacted and polymerized, and the elasticity of the cured resin layer The rate can be efficiently adjusted to more than 10 ⁵ Pa.

<< Thermal cationic initiator >>
The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates cations by heating. BF ⁴⁻ , PF ⁶⁻ , SbF ⁶⁻ , or (BX ₄ ) ⁻ (where X is at least 2 A sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, and an iodonium salt, each having a counter anion (which represents a phenyl group substituted with two or more fluorine or trifluoromethyl groups).

The sulfonium salts include triphenylsulfonium tetrafluoroboron, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoroarsenide, and diphenyl (4-phenylthiophenyl). Examples include sulfonium arsenic hexafluoride.
Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
Quaternary ammonium salts are dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate , Dimethylphenyl (4-methylbenzyl) ammonium hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methyl Phenyldibenzylammonium, methylphenyldibenzylammonium hexafluoroantimonate Hexafluorophosphate, methylphenyldibenzylammonium trakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N , N-dimethyl-N-benzylanilinium hexafluoride antimony, N, N-diethyl-N-benzylanilinium tetrafluoride, N, N-dimethyl-N-benzylpyridinium antimony hexafluoride, N, N- Examples include diethyl-N-benzylpyridinium trifluoromethanesulfonic acid.

  Commercially available products of thermal cationic polymerization initiators include CXC-1612, CXC-1738 (all manufactured by King Industries), Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI- B4 (both manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

  In the composition, the content of the thermal cationic polymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass in total of the partially (meth) acrylated epoxy resin and the epoxy resin. More preferably, it is 10 mass parts, More preferably, it is 1-5 mass parts.

<Additional ingredients>
The composition can contain further components as long as the effects of the present invention are not impaired. Additional components include plasticizers and other components.

<< Plasticizer >>
The plasticizer is a component that can impart flexibility to the cured product of the composition. Therefore, when a composition contains a plasticizer, there exists a tendency which can reduce shrinkage | contraction after hardening and can prevent the curvature of a laminated body.

  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; phosphoric esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester; (hydrogenated) polyisoprene, hydroxyl-containing (hydrogenated) polyisoprene , (Hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polybutadiene, polybutene, and other rubber polymers; thermoplastic elastomers; petroleum resins; alicyclic saturated hydrocarbon resins; terpene resins, terpenes Terpene resins such as phenolic resins, modified terpene resins, hydrogenated terpene resins; rosin resins such as rosin phenol; rosin esters such as disproportionated rosin ester resins, polymerized rosin ester resins, hydrogenated rosin ester resins Resins and the like; xylene resins and the like; acrylic polymers and acrylic copolymers. The plasticizer is preferably a rosin ester resin and particularly preferably a hydrogenated rosin ester resin.

  The content of the plasticizer is preferably 300 parts by mass or less, more preferably 10 to 250 parts by mass, with respect to 100 parts by mass in total of the (meth) acrylic resin and the epoxy resin. Part is more preferable, and 30 to 90 parts by mass is particularly preferable.

<< Other ingredients >>
The composition is within the range not impairing the effects of the invention, and further, other known additives such as coupling agents, polymerization inhibitors, adhesion promoters, antioxidants, antifoaming agents, pigments, fillers, One or more other components selected from the group consisting of a chain transfer agent, a light stabilizer, a surface tension adjusting agent, a leveling agent, an ultraviolet absorber, and an antifoaming agent can be included.

  In the composition, the total content of other components is preferably 0.01 to 15 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin and the epoxy resin. More preferably, it is 1 to 5 parts by mass.

<Viscosity of composition>
The viscosity of the composition is not particularly limited, but is preferably 500 to 30,000 mPa · s, and more preferably 1,000 to 20,000 mPa · s. If it is this range, since it is possible to apply | coat with a thin film thickness on a base material, it is preferable. The viscosity is a value measured with a cone plate viscometer at 25 ° C. under atmospheric pressure.

<Method for preparing composition>
A composition can be obtained by the manufacturing method including the process of mixing each component. The mixing method is not particularly limited, and various metals, plastic containers, stirring blades, a stirrer, and the like can be used.

(Method of applying)
The method for applying the composition to the substrate 1 is not particularly limited, and examples thereof include one or more methods selected from the group consisting of a spin coater, a die coater, a dispenser, inkjet printing, screen printing, and gravure printing.

  The thickness of the curable resin composition layer formed by applying the composition is not particularly limited, and can be, for example, 10 to 500 μm, and preferably 30 to 350 μm.

[Step (B)]
Step (B) is a step of irradiating the curable resin composition layer with energy rays to form a cured resin layer having an elastic modulus of 10 ² Pa to 10 ⁵ Pa.

  When the base material 1 is a base material that transmits energy rays, the curable resin composition layer may be formed by irradiating the curable resin composition layer with energy rays from the base material 1 side. The cured resin layer may be formed by irradiating energy rays from the layer side. When the base material 1 is a base material that does not transmit energy rays, the curable resin composition layer is irradiated with energy rays from the curable resin composition layer side to form a cured resin layer. The base material 1 may not transmit light (not transmit visible light), but may transmit energy rays (for example, ultraviolet rays), and may transmit light (transmit visible light). (For example, ultraviolet rays) may not be transmitted.

The energy light is not particularly limited, and active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams can be used. The energy ray is preferably ultraviolet light.
As the ultraviolet light source, a light source that emits ultraviolet light (UV) can be used. Examples of the ultraviolet light source include a metal halide lamp, a high-pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a halogen lamp, a pulse xenon lamp, and an LED. Although the peak wavelength of LED is not specifically limited, 365 nm, 405 nm, 375 nm, 385 nm, and 395 nm are mentioned. Light emitted from a light source other than the LED may be adjusted to light of a specific wavelength by passing through an optical filter.

It is preferable to irradiate the energy rays so that the integrated light quantity of the energy rays is 200 to 10,000 mJ / cm ² . Integrated light quantity is more preferably from 500~10,000mJ / cm ^2, more preferably in the range of 1,000~8,000mJ / cm ^2, and even a 1,000~6,000mJ / cm ² Particularly preferred.

The cured product of the curable resin in the cured resin layer in the step (B) has an elastic modulus of 10 ² Pa to 10 ⁵ Pa. When the elastic modulus is less than 10 ² Pa, the composition has high fluidity, and in the step (C), the composition may protrude greatly out of the base material due to the pressure at the time of bonding, which may cause device contamination. There is. When the elastic modulus exceeds 10 ⁵ Pa, the composition becomes too hard, and in the step (C), it does not adhere well to the surface of the substrate 2 at the time of bonding, and the adhesive strength after thermosetting may be lowered. There is sex. Modulus is preferably ^{5 × 10 2 Pa~7 × 10 4} , 7 × 10 2 Pa~3 × 10 4 is more preferable.
The elastic modulus can be measured using a rheometer.

[Step (C)]
A process (C) is a process of bonding the base material 2 on a cured resin layer and obtaining a bonded body. The substrate 2 can be placed on the substrate 1 on which the cured resin layer is formed so as to be in contact with the cured resin layer, and the substrate 1 and the substrate 2 can be bonded to each other.

  In the method for manufacturing a laminate, the step (C) may include a step of pressure-treating a bonded body including the base material 1 and the base material 2 and a resin layer therebetween. When the manufacturing method of a laminated body contains a pressurization process, the adhesive force of a bonded body improves and the adhesive strength of the laminated body obtained in a process (D) improves more. The pressure treatment can be performed using a rubber roller, a flat plate press device or the like. In addition, in process (C), you may improve the adhesive force of a bonding body using the weight of at least one of the base material 1 and the base material 2. FIG.

[Step (D)]
The step (D) is a step of heating the bonded body to obtain a laminate by setting the elastic modulus of the cured resin layer to more than 10 ⁵ Pa. By the step (D), curing of the cured resin layer between the substrate 1 and the substrate 2 is further promoted, and the substrates are bonded to each other.

  The heating temperature and the heating time are not particularly limited as long as the composition is thermoset and the base material 1 and the base material 2 are bonded to each other. The heating temperature is preferably 70 to 120 ° C, more preferably 80 to 110 ° C. The heating time is preferably 30 minutes to 2 hours, more preferably 50 minutes to 100 minutes.

  A laminated body can be used for adhesion | attachment of the base material 1 and the base material 2 whose at least one of the base material 1 and the base material 2 is a light transmissive member. The use of the laminate includes an image display device such as a liquid crystal. In addition, the laminate can be used for bonding the base material 1 and the base material 2 in which the base material 1 and the base material 2 are both formed with members that do not transmit light or elements and filters that do not transmit light. The use of the laminate includes an image display device such as an organic EL.

In addition, light and thermosetting resin compositions for use in the method for producing a laminate are also objects of the present invention. That is, the composition in which the elastic modulus is 10 ² Pa to 10 ⁵ Pa after being irradiated with energy rays, and then the elastic modulus of the cured resin layer is more than 10 ⁵ Pa by heating is also an object of the present invention. is there. The composition is as described above in the step (A), including preferable ones. The irradiation conditions of energy rays are as described above in the step (B). The heating conditions are as described in the step (D). By using the composition in a method for producing a laminate, it is possible to efficiently produce a laminate in which protrusion of an uncured composition at the time of bonding is reduced and adhesive strength is sufficient.

  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.

(Preparation of light and thermosetting resin composition)
Ingredients other than the thermal radical initiator and thermal cation initiator of the formulation shown in Table 1 and Table 2 are weighed in a container (material SUS), and three-one motor (Shinto Kagaku Co., Ltd.) at 60 to 80 ° C. and atmospheric pressure The product was stirred at 200 rpm for 30 minutes to 1 hour. Then, after confirming that the temperature of the composition has returned to 25 ° C., the thermal radical initiator and the thermal cation initiator are weighed and uniformly mixed at 25 ° C. under atmospheric pressure using a three-one motor. The light and thermosetting resin compositions of Examples 1 to 3 were prepared.

(Measurement of physical properties)
Using the light and thermosetting resin composition, the characteristics were measured as follows.

<Viscosity>
The viscosity of the light and thermosetting resin composition was measured using an E-type viscometer (RE-105U manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. under atmospheric pressure.

<Elastic modulus>
<< Elastic modulus after UV curing >>
A light and thermosetting resin composition is set in a rheometer (manufactured by Anton Paar Co., Ltd .: MCR302), and ultraviolet (UV) is irradiated with 3000 mJ / cm ² with a high-pressure mercury lamp (manufactured by Hamamatsu Photonics Co., Ltd .: LC5). After that, the elastic modulus after UV curing of the light and thermosetting resin composition was measured.
<< Elastic modulus after thermosetting >>
A light and thermosetting resin composition is set in a rheometer (manufactured by Anton Paar Co., Ltd .: MCR302), and ultraviolet (UV) is irradiated with 3000 mJ / cm ² with a high-pressure mercury lamp (manufactured by Hamamatsu Photonics Co., Ltd .: LC5). Then, the light and thermosetting resin composition were further heated at 105 ° C. for 1 hour, and the elastic modulus of the light and thermosetting resin composition after thermosetting was measured.

<Extruding and adhesiveness>
<< Manufacture of laminated body >>
A cellophane tape (manufactured by Nichiban Co., Ltd., 50 mm wide, 0.05 mm thick) was laminated with two sheets of 10 × 20 mm holes and attached to a slide glass (S1126, Matsunami Glass Industrial Co., Ltd.) to provide a bank. The light and thermosetting resin composition was dropped, a release-treated PET film (Toyobo Co., Ltd., Toyobo Ester Film E7002) was applied from above, and glass was further placed between the glass and the glass. Subsequently, UV of 3,000 mJ / cm ² was irradiated with a metal halide lamp (ECS-301, manufactured by Eye Graphics Co., Ltd.). Next, after removing the glass, the release PET film, the bank, and the light and thermosetting resin composition protruding from the bank, the light and thermosetting resin composition of 10 × 20 × 0.1 mm on the slide glass The cured product (cured resin layer) was obtained. Using a rubber roller, a polyethylene terephthalate (PET) film (manufactured by Panac Corporation, product name Lumirror 100T60, thickness 100 μm) was pasted on a cured product of light and a thermosetting resin composition so that air bubbles would not enter. The back surface of the glass was marked with a pen along the periphery of the cured product of the light and thermosetting resin composition. Next, 10 slide glasses were placed on the PET film as a weight, and then heated at 105 ° C. for 1 hour in a hot air dryer, and the glass and PET were passed through a cured product of light and a thermosetting resin composition. A laminate to which the film was adhered was obtained.
<< Evaluation >>
After taking out from a hot air dryer and returning to normal temperature, the slide glass was removed, the distance which uncured light and the thermosetting resin composition protruded from the mark was confirmed, and protrusion was evaluated on the following references | standards.
○: The protrusion is small (the protrusion of less than 1 mm)
×: Large protrusion (over 1 mm or more)
Moreover, adhesiveness was evaluated on the following reference | standard by the presence or absence of peeling of PET film when a PET film was picked up and the test piece was lifted.
○: Adhesive (PET film did not peel off)
X: No adhesion (PET film was peeled off)

  The results are shown in Tables 1 and 2.

(A) (Meth) acrylic resin (a-1): UA10000B: polyether-based polyurethane acrylate oligomer (molecular weight 25,000, manufactured by KS Corporation)
(A-2): FA513AS: Dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd.)
(A-3): LA: lauryl acrylate (a-4): 4HBA: 4-hydroxybutyl acrylate (a-5): SA1002N: tricyclodecane dimethanol diacrylate (manufactured by Mitsubishi Chemical Corporation)
(A-6) Compound A: Bisphenol A type epoxy resin (Epicron-850S [manufactured by Dainippon Ink & Chemicals, Inc.]) 1 produced by the method described in “Synthesis Example” of JP-A-5-295087 Partially methacrylated epoxy resin obtained by using 1,000 parts by mass and 250 parts by mass of methacrylic acid.
(B) Epoxy resin (b-1): EHPE 3150: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Corporation)
(B-2): EXA-830LVP: Bisphenol F type epoxy resin (manufactured by DIC Corporation)
(B-3): CEL2021P: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation)
(B-4): EP-4088L: DCPDM (dicyclopentadiene) type epoxy resin (manufactured by ADEKA Corporation)
(B-5): EP-4080E: Hydrogenated BPA (hydrogenated bisphenol A) type epoxy resin (manufactured by ADEKA Corporation)
(C) Initiator (c-1) Photoradical initiator (c-1-1): TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (c-2) Thermal radical initiator (c- 2-1): Perhexyl O: t-hexyl peroxy 2-ethylhexanoate (manufactured by NOF Corporation)
(C-3) Thermal cation initiator (c-3-1): CXC-1738: Quaternary ammonium hexafluorophosphate (manufactured by King Industries)
(C-4) Photocationic initiator (c-4-1): CPI-210S: Sulphonium salt photocationic initiator (manufactured by San Apro Co., Ltd.)
(D) Plasticizer (d-1): KE-311: Hydrogenated rosin ester (Arakawa Chemical Industries, Ltd.)

Claims (5)

(A) Applying light and a thermosetting resin composition to the substrate 1 to form a curable resin composition layer;
(B) A step of irradiating the curable resin composition layer with energy rays to form a cured resin layer having an elastic modulus of 10 ² Pa to 10 ⁵ Pa, and (C) the substrate 2 on the cured resin layer. A process of obtaining a bonded body,
(D) heating the bonded body, setting the elastic modulus of the cured resin layer to more than 10 ⁵ Pa, and obtaining a laminate;
The manufacturing method of a laminated body containing this.   The production of a laminate according to claim 1, wherein the light and thermosetting resin composition is an acrylate resin composition containing a (meth) acrylic resin or a hybrid resin composition containing a (meth) acrylic resin and an epoxy resin. Method.   The manufacturing method of the laminated body of Claim 2 with which light and a thermosetting resin composition contain 0.1-20 mass parts of photoradical initiators with respect to 100 mass parts of (meth) acrylic resins.   Any 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 transmissive member or a member that does not transmit light. The production method according to claim 1.   The light and thermosetting resin composition for using with the manufacturing method of any one of Claims 1-4.