JP6454268B2 - Curable resin composition - Google Patents

Description

The present invention relates to a curable resin composition.

There are a resistive film type, a capacitance type, an electromagnetic induction type, an optical type and the like as a touch panel mounted on a display body such as an LCD (liquid crystal display). There is a case where a decorative board for improving the appearance design and an icon sheet for designating a touch position are pasted on the surface of these touch panels. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.

Conventionally, an adhesive is used for bonding a decorative plate and a touch panel, bonding an icon sheet and a touch panel, and bonding a transparent substrate and a transparent plate. Patent Document 1 discloses (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene or polyurethane as a skeleton, (B) a softening component, and (C1) phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, (Meth) selected from 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate A photocurable resin composition containing an acrylate monomer is described. However, the present invention has been found to be suitable for bonding with a touch panel, bonding with an icon sheet and a touch panel, and bonding between a transparent substrate and a transparent plate by applying an alkoxysilane compound. Patent Document 1 does not describe the alkoxysilane compound of the present invention.

In recent years, glass for display bodies such as LCDs has become thinner. When the glass becomes thinner, the LCD is easily deformed by external stress. When a display body such as LCD using thin glass and an optical functional material such as an acrylic plate or polycarbonate plate are bonded together, the difference in linear expansion between glass and acrylic or plastic molding material such as acrylic plate or polycarbonate Due to the strain at the time of molding, relaxation of molding strain and moisture absorption / drying occur in the heat resistance test and moisture resistance test, and surface accuracy changes such as dimensional change and warpage occur.

When trying to suppress this deformation with a conventional adhesive (for example, Patent Document 2), there are problems that the adhesive surface is peeled off, the LCD is cracked, or the LCD becomes uneven in display. Patent Document 2 describes a cured resin containing urethane (meth) acrylate, polybutadiene (meth) acrylate, and isoprene (meth) acrylate as components. There is no description in patent document 2 about the composition of this invention.

As a conventional adhesive, there is a UV curable resin as in Patent Document 3. Since Patent Document 3 is a highly elastic resin based on a rigid skeletal monomer such as isobornyl (meth) acrylate, it cannot withstand the expansion and contraction of the adherend in a high temperature reliability test, causing peeling. There was a possibility. The present invention has found a design that can withstand the expansion and contraction of the adherend in a high-temperature reliability test by using (C) phenoxy polyethylene glycol (meth) acrylate having an EO chain. In the present invention, it is not necessary to use a monomer having a rigid skeleton such as isobornyl (meth) acrylate.

When the bonded surface is printed, there is a problem that the printed portion is difficult to bond with light energy rays, and the adhesiveness is lowered due to the influence of the uncured portion.

  For applications such as bonding of decorative plates and touch panels, bonding of icon sheets and touch panels, bonding of transparent substrates and transparent plates, etc., the degree to which the adherend can be deformed in a heated atmosphere assuming the usage environment It is desirable to have the flexibility.

  On the other hand, since it has the flexibility that can follow the deformation of the adherend in a heated atmosphere assuming the use environment, it is also clear that there are problems such as coloring after discoloration, discoloration, and strength reduction after humidity resistance test. It has become. As a solution to the above problem, Patent Document 4 contains at least one oligomer selected from the group consisting of a polyisoprene (meth) acrylate oligomer, a polybutadiene (meth) acrylate oligomer, and a polyurethane (meth) acrylate oligomer, and a hindered amine. A photocurable adhesive composition is described. The composition of the present invention is not described in Patent Document 4.

In applications such as laminating a decorative plate and a touch panel, laminating an icon sheet and a touch panel, laminating a transparent substrate and a transparent plate, etc., for example, a photocurable dam composition along the outer periphery of a predefined area. Applying to the surface of the transparent substrate, contacting the dam composition and the photocurable fill composition, exposing the dam composition and the fill composition to actinic radiation, photocuring, and light Providing a cured adhesive, whereby the photocured fill composition and the dam composition are bonded to a transparent substrate, resulting in a display bonded to the transparent substrate. Among them, the boundary between the dam composition and the fill composition greatly affects the optical characteristics of the display.

Patent document 5 is mentioned as a method of performing the said process. Patent Document 5 discloses a step of applying a photocurable dam composition to the surface of a transparent substrate along the outer periphery of the predetermined region in an application for bonding a liquid crystal display, and the dam composition and the photocurable property. A method comprising contacting a fill composition; and exposing the dam composition and the fill composition to actinic radiation to photo-cure to provide a photo-cured adhesive. There is no description in patent document 5 about the composition of this invention.

International Publication No. 2010/027041 Japanese Patent Laid-Open No. 2004-77887 JP-A 64-85209 JP 2012-46658 A International Publication No. 2009/064705

  The present invention provides, for example, sufficient adhesion when a decorative plate or icon sheet used for a display body such as a touch panel is bonded, when a transparent substrate and a transparent substrate are bonded, or when a printed part is bonded. The problem of the prior art that it is difficult to impart the properties, the problem of the prior art that the display surface and the optical functional material are bonded, the adhesive surface is peeled off, or the glass of the display is broken, heat resistance, A curable resin composition that solves the problems of the prior art, such as discoloration and strength reduction after a moisture resistance test, and the problems of the prior art of reduced display optical characteristics when the curable resin composition is used as a dam composition and a fill composition. I will provide a.

  The present invention provides a curable resin composition used when, for example, a decorative plate or an icon sheet used for a display body such as a touch panel is bonded. The present invention provides, for example, a curable resin composition that solves the problem of the prior art that a portion that is not directly exposed to light such as ultraviolet rays (for example, a printed ground portion) cannot be cured.

  The present invention provides a curable resin composition for bonding a decorative board or icon sheet used for a display body such as a touch panel, for bonding a transparent substrate and a transparent substrate, or for bonding a printed portion. Provided is a curable resin composition that also serves as a dam agent for the purpose of preventing protrusion. The present invention provides a curable resin composition having an effect that a boundary between a dam agent and a filling agent filling the surface is not visible. By eliminating the boundary between the dam agent and the fill agent, it is possible to suppress the optical unevenness of the display body.

That is, according to the present invention, the following is provided.
(1) A curable resin composition containing the following (A) to (F).
(A) 100 parts by mass of a polymer having a (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton (B) having no (meth) acryloyl group, and a diene-based or 30 to 600 parts by mass of a polymer having a hydrogenated diene-based skeleton (C) (meth) acrylate having an aromatic ring (D) photopolymerization initiator (E) antioxidant (F) general formula alkoxysilane compounds general formula represented by _{(1) (1) (RO} ) n Si [(CH 2) m CH 3] 4-n
(Wherein, R represents CH ₂ or _{C 2 H 5, n = 2~3} , an m = 0 to 12)
Moreover, a preferable aspect is as follows.
(2) The diene-based or hydrogenated diene-based skeleton of the component (A) is one or more skeletons selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. The curable resin composition.
(3) The diene-based or hydrogenated diene-based skeleton of the component (B) is one or more skeletons selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. The curable resin composition.
(4) The curable resin composition wherein the molecular weight of the component (A) is 500 to 70000.
(5) This curable resin composition whose molecular weight of (B) component is 500-70000.
(6) The curable resin composition, wherein the component (E) is a phenol / sulfur antioxidant.
(7) The curable resin composition, wherein the component (E) is an antioxidant having a phenol group and sulfur in the same molecule.
(8) The curable resin composition in which the component (E) is a combination of an antioxidant having a phenol group and an antioxidant having sulfur.
(9) Furthermore, as component (G), (meth) acrylate having a hydroxyl group in the molecule, (meth) acrylate having a carboxyl group, (meth) acrylate having a nitrogen atom in the molecule, (meth) acrylic acid, and The curable resin composition comprising one or more compounds selected from the group consisting of (meth) acrylic acid derivatives having a nitrogen atom in the molecule.
(10) When the curable resin composition is used as a dam agent and a fill agent, the 400 nm transmittance difference between the dam agent and the fill agent is 5% or less, the refractive index difference is 0.01% or less, and the Haze difference is 0.2. % Of the curable resin composition.
(11) The curable resin composition capable of curing a light non-transmissive portion having a width of 1 mm or more by irradiation with ultraviolet rays of 1000 mJ / cm ² or more.
(12) The curable resin composition having a cure shrinkage of 2.0% or less.
(13) An adhesive composition comprising the curable resin composition.
(14) A cured product of the adhesive composition.
(15) A composite in which an adherend is coated or bonded with the cured body.
(16) A composite in which the adherend is at least one selected from the group consisting of triacetylcellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal.
(17) A touch panel laminate in which an adherend is bonded with the adhesive composition.
(18) A liquid crystal panel laminate in which adherends are bonded together using the adhesive composition.
(19) A display using the touch panel laminate.
(20) A display using the liquid crystal panel laminate.

The present invention can provide, for example, a curable resin composition that is small in coloration or discoloration due to heat and a decrease in strength after a moisture resistance test.

One embodiment of the present invention is a novel curable resin composition. This curable resin composition contains (A)-(F) component demonstrated below, for example. The component (A) is a polymer having a (meth) acryloyl group and a diene-based or hydrogenated diene-based skeleton.

In one embodiment of the present invention, the main chain skeleton of the polymer is a diene-based or hydrogenated diene-based skeleton. The diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Among these, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polyisoprene is more preferable in terms of high adhesion durability.

The polymer preferably has one or more (meth) acryloyl groups at the terminal or side chain of the main chain skeleton. Among these, those having (meth) acryloyl groups at both ends of the main chain skeleton are preferable.

The molecular weight of the polymer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If the molecular weight is within this range, the cured product of the present invention has a high hardness, so that it is easy to form an adhesive layer, and the viscosity of the curable resin composition is small, so in workability and practical use in mixing in the manufacturing process. Workability is improved. The molecular weight of the polymer may be, for example, 500, 1000, 2000, 3000, 5000, 10000, 20000, 30000, 40000, 50000, 55000, 60000, or 70000, and any two values thereof. It may be within the range.

In one embodiment of the present invention, the molecular weight refers to a number average molecular weight calculated as an average molecular weight per molecule. In the Example of this invention, the number average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography) was used. Specifically, the average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using tetrahydrofuran as a solvent under the following conditions, using a GPC system (SC-8010 manufactured by Tosoh Corporation). .

Flow rate: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corp. 6.0 mm ID × 4.0 cm 1 and “TSK-GELMULTIPOREHXL-M” 7.8 mm ID × 30.0 cm (16,000 theoretical plates) manufactured by Tosoh Corp. 2, 3 in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid feeding pressure: 39 kg / cm ²
Detector: RI detector

As the polymer of the component (A), an esterified polymer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate (see the following formula (1) for the structure, “UC-” manufactured by Kuraray Co., Ltd. 203 ")," TEAI-1000 "manufactured by Nippon Soda Co., Ltd. (hydrogenated 1,2-polybutadiene polymer modified with terminal acrylic)," TE-2000 "manufactured by Nippon Soda Co., Ltd., 1,2-polybutadiene polymer modified with terminal acrylic Thing) etc. are mentioned. Among these, an esterified polymer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate is preferable.

The component (B) is a polymer having no (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton.

In one embodiment of the present invention, the main chain skeleton of the polymer is a diene-based or hydrogenated diene-based skeleton. The diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Among these, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polybutadiene is more preferable in terms of high adhesion durability.

The molecular weight of the polymer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If the molecular weight is within this range, the hardness of the cured body is high, so that it is easy to form an adhesive layer, and the viscosity of the curable resin composition is small, so that the workability in mixing in the manufacturing process and the workability in practical applications are high. Become good. The molecular weight of the polymer may be, for example, 500, 1000, 2000, 3000, 5000, 10000, 20000, 30000, 40000, 50000, 55000, 60000, or 70000, and any two values thereof. It may be within the range.

As the polymer of the component (B), Kuraray "LIR-30" "LIR-50" (isoprene polymer), Kuraray "LBR-307" "LBR-305" (butadiene polymer), Toyobo Co., Ltd. “Byron” manufactured (amorphous polyester resin) and the like can be mentioned. Among these, at least one selected from the group consisting of isoprene polymer, 1,2-polybutadiene polymer, and 1,4-polybutadiene polymer is preferable, and 1,2-polybutadiene polymer and 1,4-polybutadiene are preferable. One or more selected from the group consisting of polymers is more preferred.

The amount of the component (B) used is such that the adhesiveness to the adherend of the curable resin composition is particularly high and the curability is good, with respect to 100 parts by mass of the component (A). 30-600 mass parts is preferable, 40-500 mass parts is more preferable, and 50-450 mass parts is the most preferable. The amount of component (B) used may be 401 parts by mass or more. The amount used may be, for example, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, or 600. , Any two of them may be within the range of values.

The component (C) is a (meth) acrylate having an aromatic ring. The aromatic ring may have a substituent such as an alkyl group such as a nonyl group. Among the component (C), alkylene oxide chain - (RO) n-(R is an alkylene group) is preferable phenoxy polyalkylene glycol (meth) acrylates having, EO (ethylene oxide) chain _{- (CH 2 CH 2 O)} n Phenoxypolyethylene glycol (meth) acrylate having — is more preferable. Here, n is preferably 4 or more. Among phenoxypolyethylene glycol (meth) acrylates, nonylphenoxypolyethylene glycol (meth) acrylate is preferable. The (C) component alkylene oxide chain-(RO) n- (R is an alkylene group) is preferably n = 10 or less, more preferably n = 8 or less. These (meth) acrylates can be used alone or in combination of two or more.

The amount of the component (C) used is such that the adhesion to the adherend of the curable resin composition is particularly high and the curability is good, with respect to 100 parts by mass of the component (A). 10-300 mass parts is preferable, 20-200 mass parts is more preferable, and 25-120 mass parts is the most preferable. The amount of component (C) used may be 101 parts by mass or more. The amount used may be, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, or 300. It may be within a range of two values.

The component (D) is a photopolymerization initiator. (D) As a component, 1 or more types in the group which consists of an alkylphenone type photoinitiator and an acyl phosphine oxide type photoinitiator is preferable. Examples of the alkylphenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and the like. Examples of the acylphosphine oxide photoinitiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. One or more of these can be used.

The amount of component (D) used is such that the adhesion of the curable resin composition to the adherend is particularly high and the curability is good, so that component (A), component (B) and ( C) 0.01-50 mass parts is preferable with respect to a total of 100 mass parts of components, 0.1-30 mass parts is more preferable, and 0.5-10 mass parts is the most preferable. In addition, this usage-amount may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, or 50, for example. It may be within the range of values.

(E) A component is antioxidant. As the component (E), a phenol / sulfur antioxidant is preferable. A phenolic / sulfur antioxidant is an antioxidant having a phenol group and sulfur. Examples of the phenol / sulfur antioxidant include an antioxidant having a phenol group and sulfur in the same molecule. Examples of the phenol-based / sulfur-based antioxidant include those in which an antioxidant having a phenol group and an antioxidant having sulfur are used in combination. As sulfur, sulfide is preferable.

Examples of the antioxidant having a phenol group and sulfur in the same molecule include 4,6-bis (octylthiomethyl) -O-cresol, 4,6-bis (dodecylthiomethyl) -O-cresol, 4,6- Bis (alkylthiomethyl) -O-cresol, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, dioctadecyl 3, Examples thereof include 3′-thiodipropionate and didodecyl 3,3′-thiodipropionate.

When the antioxidant having a phenol group and the antioxidant having sulfur are used in combination, the phenolic antioxidant is not particularly limited as long as it is an antioxidant having a phenol group in the molecule, and the following formula (2) An antioxidant having the following structure is preferred.

When the antioxidant having a phenol group and the antioxidant having sulfur are used in combination, BHT (dibutylhydroxytoluene), pentaerythritol tetrakis [3- (3,5-di-t-butyl) are used as the phenolic antioxidant. -4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N-hexane-1,6-diylbis [3- (3,5-di -T-butyl-4-hydroxyphenylpropionamide), benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 3,3 ', 3 " , 5,5 ', 5 "-hexa-t-butyl-a, a', a"-(mesitylene-2,4,6-triyl) tri-p-cresol, ethyl Bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tris ( 2,4-di-t-butylphenyl) phosphite and the like.

When the antioxidant having a phenol group and the antioxidant having sulfur are used in combination, the sulfur-based antioxidant is not particularly limited as long as it is an antioxidant having sulfur in the molecule, and the following formula (3) An antioxidant having the following structure is preferred. When the antioxidant having a phenol group and the antioxidant having sulfur are used in combination, the mass ratio is preferably an antioxidant having a phenol group: an antioxidant having sulfur = 1 to 10:10 to 1, preferably 1. ˜5: 5-1 is more preferred, and 1: 1 is most preferred.

Examples of the skeleton having an antioxidant function include a skeleton having a hydrocarbon group, a skeleton having a carbonyl group, a skeleton having a ketone group, and a skeleton having an ether group. Of these, alkylpropionate groups are preferred.

Examples of sulfur-based antioxidants include ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, distearyl-3,3. Examples include '-thiodipropionate and dioctyl-3,3'-thiodipropionate.

The amount of component (E) used is the sum of component (A), component (B) and component (C) in that the color and discoloration of the curable resin composition due to heat is small and the decrease in strength after the moisture resistance test is small. 0.01-30 mass parts is preferable with respect to 100 mass parts, 0.05-20 mass parts is more preferable, and 0.1-10 mass parts is the most preferable. In addition, this usage-amount may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, or 30, for example. It may be within the range.

The component (F) is an alkoxysilane compound represented by the general formula (1).
Formula _{(1) (RO) n Si} [(CH 2) m CH 3] 4-n
Here, R is CH ₂ or _{C 2 H 5, n = 2~3} , an m = 0 to 12.
R is preferably CH _{2 and} preferably m = 5 to 10.

As the alkoxysilane compound of component (F), methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, etc. Is mentioned. Among these, one or more members selected from the group consisting of hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane are preferable.

In one embodiment of the present invention, the component (F) is different from, for example, a silane coupling agent known to improve adhesion to a substrate or the like. The component (F) in one embodiment of the present invention has an effect that does not affect the optical characteristics of the display when, for example, a decorative board or an icon sheet used for a display body such as a touch panel is attached.

The amount of component (F) used is preferably 0.01 to 30 parts by mass, and 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of component (A), component (B) and component (C). More preferred is 1 to 10 parts by mass. In addition, this usage-amount may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 20, or 30, for example, and is in the range of any two of these. It may be.

Furthermore, the curable resin composition of one Embodiment of this invention has (meth) acrylate which has a hydroxyl group in a molecule | numerator, (meth) acrylate which has a carboxyl group, and a nitrogen atom in a molecule | numerator as (G) component ( It is preferable to contain one or more compounds selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and (meth) acrylic acid derivatives having a nitrogen atom in the molecule. By containing the component (G), the adhesion to the adherend can be improved. When the component (G) is a (meth) acrylate, the (meth) acrylate is preferably a (meth) acrylate other than the component (A) or the component (C).

The (meth) acrylate having a hydroxyl group as the component (G) is not particularly limited as long as it has a hydroxyl group in the molecule. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, isocyanuric acid EO (EO stands for ethylene oxide), modified diacrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, ECH (ECH is an abbreviation for ethylene chlorohydrin) modified allyl (meth) acrylate, butanediol mono (meth) acrylate, caprolactone (meth) Acry Over DOO, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate. Among these, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl ( One or more selected from the group consisting of (meth) acrylates are preferred.

The (meth) acrylate having a carboxyl group as the component (G) is not particularly limited as long as it has a carboxyl group in the molecule. For example, EO-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) Acrylate, ω-carboxy-polycaprolactone mono (meth) acrylate and the like.

Examples of the (meth) acrylate having a nitrogen atom in the molecule of the component (G) include imide (meth) acrylate, amino (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, dimethylaminoethyl (meth) ) Acrylate, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, and hydroxyethyl (meth) acrylamide. (G) As a (meth) acrylic acid derivative which has a nitrogen atom in the molecule | numerator of a component, (meth) acryloyl morpholine etc. are mentioned, for example. (G) component is a point which the adhesiveness to a to-be-adhered body improves, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl One or more compounds selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and (meth) acryloylmorpholine are more preferable.

The amount of component (G) used is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of component (A), component (B) and component (C). More preferred. The amount used may be, for example, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, or 20, and is within the range of any two of them. May be.

The curable resin composition of one embodiment of the present invention contains the components (A) to (F) and, if necessary, the component (G). 0% or less. Curing shrinkage is calculated by the volume specific gravity method. Due to the small curing shrinkage rate, for example, when a decorative board or icon sheet used for a display body such as a touch panel is attached, it is possible to suppress peeling due to external factors such as stress, heat, and humidity.

The curable resin composition of one embodiment of the present invention contains the components (A) to (F), and if necessary, the curable resin composition also includes the component (G). When used as a composition and a fill composition, the 400 nm transmittance difference between the dam composition and the fill composition is 5% or less, the refractive index difference is 0.01% or less, and the Haze difference is 0.2% or less. be able to. Thereby, for example, when a decorative board or an icon sheet used for a display body such as a touch panel is bonded, a curable resin composition that does not affect the optical characteristics of the display can be prepared.

The curable resin composition according to an embodiment of the present invention includes the components (A) to (F) and, if necessary, the component (G) to be cured with light or ultraviolet rays. Is possible. The curable resin composition of one embodiment of the present invention contains the components (A) to (F) and, if necessary, the component (G), for example, a display body such as a touch panel. When a decorative board and an icon sheet used in the above are pasted together, particularly a portion (such as a printed ground portion) that is not directly exposed to light such as ultraviolet rays can be cured. The curable resin composition of one embodiment of the present invention can harden a printed base portion with a width of 1 mm or more, for example, with ultraviolet rays of 1000 mJ / cm ² or more.

The curable resin composition of one embodiment of the present invention is (meta) other than (A) component, (C) component, and (G) component, particularly for the purpose of further improving the adhesion to each adherend. Acrylates can be included.

In addition to these, elastomers, various paraffins, plasticizers, fillers, colorants, rust inhibitors and the like can be used as desired.

The curable resin composition of one embodiment of the present invention can be used as an adhesive composition. According to one embodiment of the present invention, a composite can be produced by bonding or covering an adherend with a cured body of an adhesive composition. The various materials of the adherend are preferably at least one selected from the group consisting of polyesters such as triacetyl cellulose, fluoropolymers, polyethylene terephthalate, polycarbonates, polyolefins such as cycloolefin polymers, glass, and metals. And at least one selected from the group consisting of glass is more preferred.

Furthermore, when the curable resin composition of one embodiment of the present invention is used as an adhesive composition and a composite is produced by bonding or covering an adherend, the present invention is used for the purpose of preventing the adhesive composition from sticking out. The curable resin composition of one embodiment of the invention can also serve as a dam agent. The curable resin composition of one embodiment of the present invention can also serve as a filling agent that fills the adherend surface. The curable resin composition of one embodiment of the present invention can be used as a dam agent and a fill agent. In the curable resin composition of one embodiment of the present invention, the 400 nm transmittance difference between the dam agent and the fill agent is 5% or less, the refractive index difference is 0.01 or less, and the Haze difference is 0.2% or less. Therefore, the boundary line can be eliminated.

The adherend adhered with the curable resin composition of one embodiment of the present invention can be reworked (reused) after being completely cured. The rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the bonded one or two adherends, and the adherend after disassembly is performed. The body can be reused. In this specification, “polymerized product” includes a compound having a monomer unit. The degree of polymerization of the polymer may be, for example, 2, 10, 100, 200, 300, or 400 or more, and may be in the range of any two values thereof. In this specification, “or” is used when “at least one or more” of the items listed in the text can be adopted. In this specification, when “in the range of two values” is specified, the range includes the two values themselves. In the present specification, “A to B” means A or more and B or less.

Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto. Unless otherwise stated, experiments were conducted at 23 ° C.

(Experimental example 1)
Curable resin compositions having the compositions shown in Tables 1 and 2 were prepared and evaluated. The results are shown in Tables 1-2. The following compounds were selected as each component in the curable resin composition described in the experimental examples.

As the component (A), a polymer having a (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton, the following compounds were selected.
(A-1) 1,2-polybutadiene polymer (“TE-2000” manufactured by Nippon Soda Co., Ltd., the structure is represented by the following formula (4)) (number average molecular weight 2000 in terms of polystyrene by GPC)
(A-2) Isoprene polymer (“UC-203” manufactured by Kuraray Co., Ltd.) (number average molecular weight of 36,000 in terms of polystyrene by GPC, maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (esterified polymerization of methacrylate) In formula (1), Y is an ethylene group, R is a methyl group)
(A-3) Isoprene polymer ("UC-102" manufactured by Kuraray Co., Ltd.) (number average molecular weight of 17,000 in terms of polystyrene by GPC, maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (esterification polymerization with methacrylate) In formula (1), Y is an ethylene group, R is a methyl group)
The following compounds were selected as the polymer having no (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton as the component (B).
(B-1) Isoprene polymer ("LIR-30" manufactured by Kuraray Co., Ltd.) (number average molecular weight 28000 in terms of polystyrene by GPC)
(B-2) Butadiene polymer (“LBR-307” manufactured by Kuraray Co., Ltd.) (Number average molecular weight 8000 in terms of polystyrene by GPC)
The following compounds were selected as the phenoxy polyethylene glycol (meth) acrylate of component (C).
(C-1) Nonylphenoxypolyethylene glycol acrylate (n = 4) (“M-113” manufactured by Toa Gosei Co., Ltd.)
(C-2) Nonylphenoxy polyethylene glycol acrylate (n = 8) ("FA-318A" manufactured by Hitachi Chemical Co., Ltd.)
The following compounds were selected as the photopolymerization initiator of component (D).
(D-1) 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals)
(D-2) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“Darocur TPO” manufactured by Ciba Specialty Chemicals)
The following compounds were selected as the antioxidant for component (E).
The following compounds were selected as antioxidants having a phenol group and sulfur in the same molecule.
(E-1) 4,6-bis (dodecylthiomethyl) -O-cresol ("Irganox 1726" manufactured by BASF)
The following compounds were selected as phenolic antioxidants.
(E-2) Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain alkyl ester ("Irganox 1135" manufactured by BASF)
The following compounds were selected as sulfur-based antioxidants.
(E-3) didodecyl 3,3′-thiodipropionate (“Inganox PS800FD” manufactured by BASF)
The following compounds were selected as the alkoxysilane compound of component (F).
(F-1) Decyltrimethoxysilane (“KBM-3103” manufactured by Shin-Etsu Silicone)
(F-2) Methyltriethoxysilane (“KBE-13” manufactured by Shin-Etsu Silicone)
As a comparison of the component (F), the following compounds were selected.
(F-3) 3-Glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone)
The following compounds were selected as the component (G).
(G-1) Methacrylic acid (“MAA” manufactured by Mitsubishi Rayon Co., Ltd.)
(G-2) Acryloyl morpholine (“ACMO” manufactured by Kojin Co., Ltd.)
(G-3) 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “light ester“ HO-250 ”, abbreviated as 2-HEMA)

Various physical properties were measured as follows.

[Photocurability]
Measurement was performed at a temperature of 23 ° C. Regarding photocurability, a curable resin composition was applied to a surface of Tempax glass (width 25 mm × length 25 mm × thickness 2 mm) to a thickness of 0.1 mm. Thereafter, using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, UV light having a wavelength of 365 nm was irradiated and cured under the condition of an integrated light quantity of 2000 mJ / cm ² . Thereafter, the tensile shear bond strength was measured.

[Polyethylene terephthalate (PET) adhesiveness evaluation (peel adhesion strength between polyethylene terephthalate test pieces)]
Test pieces (width 50 mm × length 10 mm × thickness 0.05 mm) of biaxially stretched PET films (Lumirror T60, average thickness 190 μm, manufactured by Toray Industries, Inc.) are used as the adhesive composition. Then, the adhesive layer was bonded with a thickness of 30 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Evaluation of glass adhesion (tensile bond strength between heat-resistant glass specimens)]
Heat-resistant glass test pieces (width 25 mm × length 25 mm × thickness 2.0 mm) were used, and a Teflon (registered trademark) tape having a thickness of 80 μm × width 11.5 mm × length 25 mm was used as a spacer. It was used as an adhesive composition and adhered (adhesion area 3.125 cm ² ). The light irradiation conditions followed the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on both sides of the test piece, and a galvanized steel sheet (width 100 mm × length 25 mm × A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered. After the curing, using the test piece bonded with the adhesive composition, the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Cycloolefin polymer (COP) adhesion evaluation (peel adhesion strength between cycloolefin polymer specimens)]
Bonding test pieces (width 50 mm x length 10 mm x thickness 0.04 mm) of COP films (ZEONOR, average thickness 40 μm, manufactured by Nippon Zeon Co., Ltd.) using the curable resin composition as an adhesive composition The layers were bonded with a thickness of 10 μm and a bonding area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two non-adhered film end portions of the test piece bonded with an adhesive, the film-adhered portions are peeled off, and the initial 180 ° peel adhesion strength Was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Evaluation of triacetyl cellulose adhesion (peel adhesion strength between triacetyl cellulose test pieces)]
Using test pieces (width 50 mm × length 10 mm × thickness 0.04 mm) of triacetyl cellulose (TAC) films (average thickness 40 μm, manufactured by Fuji Film Co., Ltd.), and curable resin composition as an adhesive composition. Then, the adhesive layer was bonded with a thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. The initial 180 ° peel strength was measured by pulling the two film ends that were not in close contact with the test piece that was adhered with the adhesive composition, thereby peeling the portions where the films were in close contact with each other. . After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Fluoropolymer adhesion evaluation (peel adhesion strength between fluoropolymer specimens)]
Pvdf (Polyvinylidene fluoride) film (average thickness 40 μm, “DX film” manufactured by Denki Kagaku Kogyo Co., Ltd.) test pieces (width 50 mm × length 10 mm × thickness 0.04 mm) are bonded to each other with a curable resin composition as an adhesive. Using as a composition, the adhesive layer was bonded with a thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. The initial 180 ° peel strength was measured by pulling the two film ends that were not in close contact with the test piece that was adhered with the adhesive composition, thereby peeling the portions where the films were in close contact with each other. . After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Polycarbonate adhesion evaluation (tensile bond strength between polycarbonate specimens)]
Polycarbonate (“Panlite” manufactured by Teijin Limited) specimens (width 25 mm × length 25 mm × thickness 2.0 mm) and Teflon (registered trademark) tape of thickness 80 μm × width 12.5 mm × length 25 mm as spacers The curable resin composition was used as an adhesive composition and adhered (adhesion area: 3.125 cm ² ). The light irradiation conditions followed the method described in [Photocurability]. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Curing shrinkage]
The specific gravity bottle was filled with the curable resin composition, the mass in the air and the mass in pure water were measured, and the liquid specific gravity was calculated. Furthermore, the curable resin composition is cured by the method described in [Photocurability] to produce a cured product having a width of 25 mm × length of 25 mm × thickness of 2 mm, and the mass in the air and the mass in pure water are measured. It measured and computed hardened | cured material specific gravity. The cure shrinkage was calculated from the ratio of liquid specific gravity and cured product specific gravity. Curing shrinkage rate = ((cured product specific gravity−liquid specific gravity) / cured product specific gravity) × 100 (%)

[Heat and heat resistance evaluation (tensile bond strength between heat resistant glass specimens after exposure to high temperature and humidity)]
Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm), curable resin composition as adhesive composition, adhesive layer thickness 100 μm, adhesive area 1.0 mm ² Glued and cured. The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. The tensile shear bond strength was measured using the test piece after exposure. The appearance of the bonded part was visually observed to determine whether it was yellowed. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Heat and heat resistance evaluation (yellowing degree)]
Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm), curable resin composition as adhesive composition, adhesive layer thickness 100 μm, adhesive area 1.0 mm ² Glued and cured. The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. After the exposure, the Δb value of the test piece adhered with the adhesive composition was measured with a color measuring device (“UV-VISABLE SPECTROPOHOTOMETER” manufactured by SHIMADZU) to obtain the yellowing degree.

[Moisture and heat resistance evaluation (transmittance)]
Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm), curable resin composition as adhesive composition, adhesive layer thickness 100 μm, adhesive area 1.0 mm ² Glued and cured. The light irradiation conditions followed the method described in [Photocurability]. After curing, the initial transmittance (transmittance initial) was measured. After curing, the test piece adhered with the adhesive composition was exposed to an environment of 95 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. After exposure, a haze meter (manufactured by Suga Test Instruments Co., Ltd.) was used, and the transmittance (transmittance after 95 hours at 95 ° C.) was measured according to JIS K736.

(Experimental example 2)
Evaluation was performed using the fill agent of the experimental example shown in Table 3 and the dam agent of the experimental example shown in Table 3. The results are shown in Table 3.

[Boundary observation (difference in transmittance)]
On the Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm), using the curable resin composition (fill agent) shown in Table 3 as an adhesive composition, the thickness of the coating layer is 200 μm, It was applied as a coating area 1.0 mm ^2. Furthermore, using the curable resin composition (dam agent) shown in Table 3 as an adhesive composition from above, it was applied with a coating layer thickness of 100 μm and a coating area of 1.0 mm ² , and another Tempax (registered) (Trademark) Glass was laminated, adhered and cured. The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was used in an instant multi-side light system (“instant multi-side light system” manufactured by Otsuka Electronics Co., Ltd.) in two thickness directions (50 μm position of the adhesive composition, The transmittance at 400 nm at a position of 150 μm was measured. The difference between the transmittances at the two points was defined as the transmittance difference.

[Boundary observation (difference in refractive index)]
On the Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm), using the curable resin composition (fill agent) shown in Table 3 as an adhesive composition, the thickness of the coating layer is 200 μm, It was applied as a coating area 1.0 mm ^2. Furthermore, using a curable resin composition (dam agent) as a dam agent as an adhesive composition, a coating layer having a thickness of 100 μm and an application area of 1.0 mm ² is applied, and another Tempax (registered) (Trademark) Glass was laminated, adhered and cured. The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was used (Shimadzu Device Manufacturing Co., Ltd. “KPR-2000”), and the refractive index in two thickness directions (50 μm position and 150 μm position of the adhesive composition). Was measured. The difference in refractive index between the two points was taken as the refractive index difference.

[Boundary observation (Haze difference)]
On the Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm), using the curable resin composition (fill agent) shown in Table 3 as an adhesive composition, the thickness of the coating layer is 200 μm, It was applied as a coating area 1.0 mm ^2. Using a curable resin composition (dam agent) shown in Table 3 as an adhesive composition in the same manner, the coating layer was applied with a thickness of 200 μm and an application area of 1.0 mm ² . The light irradiation conditions followed the method described in [Photocurability]. After curing, the Haze value of the test piece bonded with the adhesive composition was measured using a Haze meter (“HZ-2” manufactured by Suga Test Instruments Co., Ltd.), and the Haze difference between the fill agent and the dam agent was calculated.

In the case of the curable resin composition corresponding to the comparative example, it does not have the effect of the present invention. (B) If a component is 30 mass parts or more, surface accuracy changes, such as a dimensional change and curvature, do not occur. When the component (B) is 600 parts by mass or less, the adhesion is improved.

According to this example, there is provided a curable resin composition in which coloring and discoloration due to heat and reduction in strength after a moisture resistance test are reduced while maintaining flexibility. Moreover, if the curable resin composition of a present Example is used, the optical display body or touch sensor bonded together using the curable resin composition will be obtained. The curable resin composition of this example can be used as a dam agent or a fill agent. At this time, since the transmittance difference, refractive index difference, and Haze difference between the dam composition and the fill composition are small, the optical characteristics of the display are not affected.

The curable resin composition of this example may not use a monomer having a rigid skeleton such as isobornyl (meth) acrylate.

The present invention can provide, for example, a curable resin composition that retains flexibility while eliminating coloration or discoloration due to heat and a decrease in strength after a moisture resistance test. In the present invention, since the transmittance difference, refractive index difference, and Haze difference between the dam composition and the fill composition are reduced, it is difficult to see the boundary line between the dam agent and the fill agent, and at the boundary between the dam agent and the fill agent. There is little distortion in the image of the display device.

The curable resin composition of the present invention can be used for an adhesive composition for a touch panel laminate or a liquid crystal panel laminate. The touch panel laminate and the liquid crystal panel laminate of the present invention can be used as a display. The curable resin composition of the present invention can improve curability even when a transparent portion is bonded.

Claims (20)

Curable resin composition containing the following (A)-(F).
(A) 100 parts by mass of a polymer having a (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton (B) having no (meth) acryloyl group, and a diene-based or 30 to 600 parts by mass of a polymer having a hydrogenated diene-based skeleton (C) (meth) acrylate having an aromatic ring (D) photopolymerization initiator (E) antioxidant (F) general formula alkoxysilane compounds general formula represented by _{(1) (1) (RO} ) n Si [(CH 2) m CH 3] 4-n
(Wherein, R represents CH ₃ or _{C 2 H 5, n = 2~3} , an m = 0 to 12) The diene-based or hydrogenated diene-based skeleton of the component (A) is at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Item 2. A curable resin composition according to Item 1. The diene-based or hydrogenated diene-based skeleton of component (B) is one or more skeletons selected from the group consisting of polybutadiene, polyisoprene, hydrogenated polybutadiene, and hydrogenated polyisoprene. Item 3. The curable resin composition according to any one of Items 1 and 2. The number average molecular weight of (A) component is 500-70000, The curable resin composition of any one of Claims 1-3. The number average molecular weight of (B) component is 500-70000, The curable resin composition of any one of Claims 1-4. (E) A component is a phenol type / sulfur type antioxidant, The curable resin composition of any one of Claims 1-5. (E) Component is an antioxidant which has a phenol group and sulfur in the same molecule, The curable resin composition of any one of Claims 1-6. The curable resin composition according to any one of claims 1 to 6, wherein the component (E) is a combination of an antioxidant having a phenol group and an antioxidant having sulfur. Further, as the component (G), (meth) acrylate having a hydroxyl group in the molecule, (meth) acrylate having a carboxyl group, (meth) acrylate having a nitrogen atom in the molecule, (meth) acrylic acid, and in the molecule The curable resin composition according to any one of claims 1 to 8, comprising one or more compounds selected from the group consisting of (meth) acrylic acid derivatives having a nitrogen atom. When the curable resin composition is used as a dam agent and a fill agent, the 400 nm transmittance difference between the dam agent and the fill agent is 5% or less, the refractive index difference is 0.01% or less, and the Haze difference is 0.2% or less. The curable resin composition according to claim 1. The curable resin composition according to claim 1, wherein a light non-transmissive portion having a width of 1 mm or more can be cured by irradiation with ultraviolet rays of 1000 mJ / cm ² or more. The curable resin composition according to claim 1, which has a curing shrinkage rate of 2.0% or less. An adhesive composition comprising the curable resin composition according to any one of claims 1 to 12. A cured product of the adhesive composition according to claim 13. A composite in which an adherend is coated or bonded with the cured body according to claim 14. The composite_body | complex which the to-be-adhered body of Claim 15 is 1 or more types chosen from the group which consists of a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, polyolefin, glass, and a metal. A touch panel laminate in which an adherend is bonded with the adhesive composition according to claim 13. The liquid crystal panel laminated body which bonded together the to-be-adhered body with the adhesive composition of Claim 13. A display using the touch panel laminate according to claim 17. A display using the liquid crystal panel laminate according to claim 18.