KR20190013760A - Curable resin composition - Google Patents

Abstract

The present invention relates to a curable composition which simultaneously secures the adhesion between an inorganic substrate and an organic substrate, which comprises a (meth) acrylic oligomer having a molecular weight of 5,000 or more (component A), a (meth) acrylic monomer (component B), a photo radical polymerization initiator, (Component C) selected from the group consisting of a polymerization initiator and a viscosity of 150 mPa 占 퐏 or less.

Description

Curable resin composition

The present invention relates to a curable resin composition.

BACKGROUND ART [0002] Ink-jet printing using an ink-jet ink is widely known as a method of forming a desired pattern on a substrate at a low cost or forming a very thin resin layer (thin film). As such inkjet ink, Patent Document 1 proposes a photocurable inkjet ink containing a monofunctional polymerizable monomer having hydroxyl, a bifunctional (meth) acrylate and a photopolymerization initiator.

In recent years, as an adhesive for attaching a display element or member such as a cover lens and a TFT (thin film diode) including a front face plate, a panel, a color filter and the like to a display device such as a display, (Meth) acrylate oligomer having at least two (meth) acryloyl groups in one molecule, a (meth) acrylate having a hydroxyl group, a non-radical polymerizable flexible component, and a photo radical polymerization initiator By weight of an ultraviolet curable adhesive composition.

Japanese Patent Application Laid-Open No. 2008-63556 Japanese Patent Application Laid-Open No. 2014-118508

In recent years, as a method for bonding members for an image display apparatus, a method of applying a thinly applied inkjet ink followed by bonding has been developed, and a corresponding adhesive is required. However, what can be applied by inkjet is a very low viscosity of 150 mPa 占 퐏 or less. In the combination disclosed in the example of Patent Document 2, it is difficult to simultaneously secure the adhesive force between an inorganic substrate such as glass and an organic substrate such as a film did.

It is an object of the present invention to provide a light and thermosetting resin composition that solves the above problems and has excellent adhesion between substrates even when an inorganic substrate and an organic substrate are bonded.

The present inventors have found that a composition containing a (meth) acrylic oligomer having a molecular weight of 5,000 or more (component A), a (meth) acrylic monomer (component B) and a light and / or thermal radical polymerization initiator (component C) Or less, and the present invention has been accomplished on the basis of these findings.

The present invention has the following configuration.

(1) at least one radical polymerization initiator selected from the group consisting of a (meth) acrylic oligomer having a molecular weight of 5,000 or more (component A), a (meth) acrylic monomer (component B), and a photo radical polymerization initiator and a thermal radical polymerization initiator Component C) and has a viscosity of 150 mPa s or less.

[2] The curable resin composition of [1], wherein the component B comprises a (meth) acrylic monomer having 10 mPa s or less.

[3] The curable resin composition according to [1] or [2], wherein the component B comprises an alicyclic (meth) acrylic monomer, a hydroxyl group-containing (meth) acryl monomer and a C ₆ to C ₃₀ alkyl (meth) .

[4] The curable resin composition according to any one of [1] to [3], wherein the amount of Component A is 30 parts by weight or less based on 100 parts by weight of the total of Component A and Component B.

[5] The curable resin composition according to any one of [1] to [4], which is an adhesive.

[6] The curable resin composition according to any one of [1] to [4], which is used for at least one method selected from the group consisting of spin coater, die coater, dispenser, inkjet coating, screen printing and gravure printing.

According to the present invention, even when an inorganic substrate and an organic substrate are bonded to each other, a light and thermosetting resin composition excellent in adhesion between substrates can be provided.

 [Definition of Terms]

The term "(meth) acrylate" has the meaning of at least one of acrylate and methacrylate.

The "(meth) acryloyl group" has at least one of an acryloyl group and a methacryloyl group.

The term "(meth) acrylic" has the meaning of at least one of acrylic and methacrylic.

[Curable resin composition]

(Meth) acrylic monomer (component B) having a molecular weight of 5,000 or more and a photoradical polymerization initiator and a thermal radical polymerization initiator (Component C) and has a viscosity of 150 mPa 占 퐏 or less.

((Meth) acryl oligomer having a molecular weight of 5,000 or more (component A))

The (meth) acrylic oligomer having a molecular weight of 5,000 or more (component A) has at least one (meth) acryloyl group in the molecule. The molecular weight of the (meth) acrylate oligomer is preferably from 5,000 to 100,000, more preferably from 10,000 to 70,000, and particularly preferably from 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 calibration curve of standard polystyrene.

The (meth) acrylate oligomer is not particularly limited and includes (meth) acrylate oligomers having a polyurethane skeleton, (meth) acrylate oligomers having a polyisoprene skeleton, and (meth) acrylates having a polybutadiene skeleton And oligomers. The term " oligomer " These (meth) acrylate oligomers may be used alone or in combination of two or more.

≪ (Meth) acrylate oligomer having polyurethane skeleton >

The (meth) acrylate oligomer having a polyurethane skeleton may be at least one selected from the group consisting of aliphatic (excluding rubber and hydrogenated rubber to be described later), polybutadiene and polyisoprene, (Meth) acrylate oligomers such as a hydrogenated rubber type, polyether type, polycarbonate type, polyester type, or a combination thereof, each of which is at least one selected from the group consisting of polybutadiene and hydrogenated polyisoprene. UA10000B (molecular weight: 25,000), UN7700 (manufactured by Negami Kogyo Co., Ltd., molecular weight: 20,000), and polyvinyl chloride (component A) having a polyurethane skeleton (component A) UN-9000H (manufactured by Negami Chemical Industry Co., Ltd., molecular weight: 5,000) and EB230 (manufactured by Daicel Scientific Co., Ltd., molecular weight: 5,000) .

The urethane (meth) acrylate can be produced, for example, by reacting an organic diisocyanate with a hydroxyl group-containing (meth) acrylate compound by the method as described in Japanese Patent Application Laid-Open No. 2008-260898.

<< Organic diisocyanate >>

The organic diisocyanate is not particularly limited as long as it is a compound having at least two isocyanato groups, and aromatic, aliphatic or alicyclic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate , Polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, nor Polyisocyanates such as boranedediisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate and naphthalene diisocyanate, And a terminal isocyanate group-containing urethane prepolymer prepared by reacting a polyisocyanate with a polyol.

&Lt; Hydroxyl group-containing (meth) acrylate compound &gt;

The hydroxyl group-containing (meth) acrylate compound is not particularly limited as long as it is a (meth) acrylate compound having at least one hydroxyl group in the molecule. Specific examples of such hydroxyl group-containing (meth) acrylate compounds include, in addition to those described later in Component B, phosphorus atoms such as 2-hydroxyethyl (meth) acryloyl phosphate, (Meth) acrylate compound having a hydroxyl group or more; And (meth) acrylate compounds having two or more hydroxyl groups in the molecule such as glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

<(Meth) acrylate oligomer having polyisoprene as a backbone and (meth) acrylate oligomer having polybutadiene as a backbone>

The (meth) acrylate oligomer having a polyisoprene skeleton and the (meth) acrylate oligomer having a polybutadiene skeleton may be hydrogenated. Commercially available (meth) acrylate oligomers having polybutadiene skeleton and (meth) acrylate oligomers having polyisoprene as a backbone can be used. Examples of commercially available (meth) acrylate oligomers having a polyisoprene skeleton include UC-1 (manufactured by Kuraray Co., Ltd., molecular weight: 25,000) and UC-203 (Kuraray Co., Ltd., molecular weight: 35,000). In the present specification, the (meth) acrylate oligomer having a polyisoprene skeleton and the (meth) acrylate oligomer having a polybutadiene skeleton are assumed to have no urethane bond.

The (meth) acrylate oligomer is preferably a (meth) acrylate oligomer having a polyurethane skeleton and may be a polyether urethane (meth) acrylate oligomer, a polyester urethane (meth) acrylate oligomer, an aliphatic urethane (Meth) acrylate oligomer, rubber-based urethane (meth) acrylate oligomer, and hydrogenated rubber-based urethane (meth) acrylate oligomer. One or more (meth) acrylate oligomers may be used in combination.

((Meth) acrylic monomer (component B))

The (meth) acrylic monomer (component B) is not particularly limited as long as it is a monomer resin having at least one (meth) acryloyl group in the molecule, but is preferably at least one selected from the group consisting of monofunctional (meth) acrylate monomers Do. The viscosity of the component B is not particularly limited, but is preferably 10 mPa s or less, and more preferably 8 mPa s or less. If such a component B has a viscosity, the viscosity of the composition tends to be lowered efficiently.

&Lt; 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 examples thereof include alicyclic (meth) acrylate, Alkyl (meth) acrylate, and aromatic (meth) acrylate.

The alkyl (meth) acrylate is not particularly limited and includes, for example, n-butyl (meth) acrylate, i-butyl (meth) acrylate, Acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate. The alkyl (meth) acrylate is preferably a C ₆ to C ₃₀ alkyl (meth) acryl monomer. From the viewpoint of imparting flexibility to the cured product, lowering the viscosity of the composition more efficiently, and reducing the odor of the composition, alkyl (meth) acrylate is preferably a C ₆ to C ₃₀ alkyl (meth) acrylate . C ₆ To C ₃₀ alkyl is linear or branched, it is in a more superior adhesion point of view, preferred are branched. The carbon number of C ₆ to C ₃₀ alkyl is preferably 6 to 20, more preferably 8 to 16.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxy-substituted alkyl (meth) acrylates such as acrylate; (Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone- (Meth) acrylate other than hydroxy-substituted alkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate.

Examples of the alicyclic (meth) acrylate include dicyclopentenyloxyethyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl .

Component B includes alicyclic (meth) acrylate, hydroxyl group-containing (meth) acrylate and C ₆ to C ₃₀ alkyl (meth) acrylate from the viewpoint of better adhesion to both the inorganic substrate and the organic substrate .

(At least one radical polymerization initiator (component C) selected from the group consisting of a photo radical polymerization initiator and a thermal radical polymerization initiator)

The composition includes at least one radical polymerization initiator selected from the group consisting of a photo radical polymerization initiator and a thermal radical polymerization initiator in order to promote curing. One kind of radical polymerization initiator or two or more kinds thereof may be used in combination. When the composition comprises a photo-radical polymerization initiator, the composition is a photo-curable resin composition which is cured with an energy ray. When the composition contains a thermal radical polymerization initiator, the composition is a thermosetting resin composition which is thermally cured. The composition is a light and / or thermosetting resin composition which is cured with energy rays and / or heat, so that the composition contains a photo radical polymerization initiator and a thermal radical polymerization initiator.

&Lt; Photo radical polymerization initiator >

The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals upon irradiation with light. The photoradical polymerization initiator may be at least one selected from the group consisting of benzophenone, diacetyl, benzyl, benzoin, omega -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy- , p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzo Hydroxy-2-methyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Carbonyl group photopolymerization initiators such as methylpropane-1-one, methylbenzoylformate, 2,2-diethoxyacetophenone and 4-N, N'-dimethylacetophenone; A sulfide-based photopolymerization initiator such as diphenyl disulfide and dibenzyl disulfide; Quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; An azo type photopolymerization initiator such as azobisisobutyronitrile and 2,2'-azobispropane, and an ultraviolet ray initiator such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (4-methyl-benzyl) -l- (4-morpholinophenyl) -butan-l-one, bis (2,4,6- trimethylbenzoyl) -phenylphosphinic acid Silane, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

The photoradical polymerization initiator is preferably a carbonyl group photopolymerization initiator and particularly preferably 1-hydroxy-cyclohexyl-phenyl-ketone from the viewpoint that the rate of curing increases and the coloration after photocuring is reduced.

One kind of photo radical polymerization initiator or two or more kinds of photo radical polymerization initiators may be used in combination.

<Thermal radical polymerization initiator>

The thermal radical polymerization initiator is not particularly limited as long as it is a compound capable of generating a radical by heating, and examples thereof include organic peroxides and azo compounds, and organic peroxides are preferred.

The organic peroxide may be any organic compound containing a peroxy group (-OO-), for example, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxycetals, peroxy esters, Carbonates, and the like.

Specific examples of the organic peroxide include diacyl peroxides such as di lauroyl peroxide, dibenzoyl peroxide and bis-3,5,5-trimethylhexanoyl peroxide; Hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide (for example, Kayakumen H from Kayacqua Corporation), t-butyl hydroperoxide; t-butylperoxy 2-ethylhexanoate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- ) Dialkyl peroxides such as benzene, t-butylcumyl peroxide, di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Di-t-butylperoxycyclohexyl) propane, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxycyclohexyl Peroxyketalization; Butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t- Butyl peroxypivalate, 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-amyl peroxybenzoate; Di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexylcarbonate, 1,6-bis and peroxycarbonates such as bis (t-butylperoxycarbonyloxy) hexane.

Examples of the azo compound include azo compounds such as azobisisobutyronitrile, 2,2'-azobis (2-methylisobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) 2'-azobis (isobutyrate), and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).

Commercially available thermal radical polymerization initiators can be used. The thermal radical polymerization initiator is preferably an organic peroxide from the viewpoints of stability and harmfulness, and a peroxyester is particularly preferable. From the viewpoint of the balance between the stability of the composition and the curing temperature, it is preferable that the organic peroxide has a one-hour half-life temperature of 50 to 110 DEG C which is an index of deactivation of the organic peroxide.

One kind or two or more kinds of thermal radical polymerization initiators may be used in combination.

(Additional component)

The composition may further contain components insofar as the effect of the present invention is not impaired. And as an additional component, at least one selected from the group consisting of a plasticizer, a coupling agent, a polymerization inhibitor, an adhesion imparting agent, an antioxidant, a defoaming agent, a pigment, a filler, a chain transfer agent, a light stabilizer, a surface tension adjusting agent, a leveling agent, One or more species can be mentioned. These can use components known to those skilled in the art in the field of ink jet application compositions.

(Viscosity of the composition)

The viscosity of the composition is 150 mPa s or less. Because of such a low-viscosity composition, it is possible to apply the composition on a substrate with a thin film thickness. The viscosity of the composition is preferably 100 mPa s or less, and particularly preferably 80 mPa s or less. The lower limit of the viscosity of the composition is not particularly limited as long as it is a value at which inkjet application is possible, and may be less than a viscosity measurable by a viscometer. Although it is not intended to limit the lower limit of the viscosity of the composition, the viscosity of the composition may be, for example, 1 mPa s or more. The viscosity is a value measured at 25 占 폚 under atmospheric pressure using a cone plate type viscometer.

(Preferred composition)

In the composition, the content of the component A is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less, based on 100 parts by weight of the total of the components A and B. When the content of the component A is in the above range, the viscosity of the composition can be effectively lowered and the adhesive force tends to be more excellent.

In the composition, the content of the photo radical polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the total of the components A and B More preferable. When the content of the photo radical polymerization initiator is within the above range, the curing of the composition can be efficiently proceeded by irradiation with energy rays.

The content of the thermal radical polymerization initiator in the composition is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total of the components A and B More preferable. When the content of the thermal radical polymerization initiator is within the above range, the composition can be efficiently cured by heating.

The total content of other components in the composition is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total of Component A and Component B Particularly preferred.

It is preferable that the composition comprises only the component A and the component B as the curable component. When the curable component is composed only of component A and component B, the composition does not include component A such as epoxy resin and additional curing component other than component B. Here, the curable component means a component which undergoes polymerization and crosslinking by light irradiation and heating.

(Method for producing composition)

The method for preparing the composition can be obtained by a manufacturing method comprising a step of mixing component A, component B, component C and optionally further components. The mixing method is not particularly limited, and various metals, plastic containers, stirring blades, stirrers, and the like can be used.

(Curing method of composition)

When the composition comprises a photo-radical polymerization initiator, the composition may be cured with an energy beam. When the composition comprises a thermal radical polymerization initiator, the composition may be cured by heating. When the composition comprises a photo radical polymerization initiator and a thermal radical polymerization initiator, the composition can be cured with energy rays and / or heat.

<Curing by Energy Line>

The energy ray is not particularly limited, and an active energy ray such as visible ray, ultraviolet ray, X ray, or electron ray can be used. The energy ray is preferably ultraviolet ray. As a light source of ultraviolet rays, a light source capable of emitting ultraviolet rays (UV) can be used. Examples of the ultraviolet light source include metal halide lamps, high pressure mercury lamps, xenon lamps, mercury xenon lamps, halogen lamps, pulse xenon lamps, and LEDs.

The irradiation of the energy ray is preferably carried out such that the accumulated light amount of the energy ray is 500 to 10,000 mJ / cm 2. The accumulated light quantity is preferably 1,000 to 8,000 mJ / cm2, more preferably 1,000 to 6,000 mJ / cm2.

&Lt; Curing by heating >

The heating temperature and heating time are not particularly limited as long as the temperature and time are such that the composition is thermally cured and the substrates adhere to each other. The heating temperature is preferably 70 to 120 占 폚, more preferably 80 to 110 占 폚. The heating time is preferably 10 minutes to 2 hours, more preferably 20 minutes to 100 minutes.

(Use of composition)

The composition can be used as an adhesive for bonding a composition and a substrate for forming a cured product on a substrate, and can be preferably used as an adhesive. In addition, since the composition is low in viscosity and can be applied with a thin film thickness on a substrate, it is preferable that the composition is selected from the group consisting of a spin coater, a die coater, a dispenser, an inkjet application (inkjet printing), a screen printing and a gravure printing Can be used as a composition for at least one method, and preferably as a composition for inkjet application. Therefore, it is more preferable that the composition is used as an adhesive for bonding substrates by inkjet application. Hereinafter, a method for producing a laminate obtained by bonding the substrates using the composition will be described below.

&Lt; Method for producing laminate >

The method for producing the laminate includes the following steps (A), (B) and (C).

(A) a step of applying a curable resin composition to the substrate 1 to form a curable resin composition layer,

(B) bonding the substrate 2 to the cured resin layer to obtain a bonded body, and

(C) A step of heating the bonded body and / or irradiating the energy ray to obtain a laminated body.

<Laminate>

In the laminate, the substrate 1 and the substrate 2 are adhered via a cured product of the curable resin composition.

Examples of the substrate 1 and the substrate 2 include an inorganic substrate, an organic substrate, and a substrate made of a mixture of inorganic and organic. The inorganic substrate may include at least one selected from the group consisting of glass, metal, and ceramic. The organic substrate may be plastic. The substrate 1 and the substrate 2 may be the same substrates or different substrates. The laminate may include an additional base material in addition to the base material 1 and the base material 2, and the method of bonding the base material is not particularly limited.

The substrate 1 and the substrate 2 may be a light-transmitting member or a member that does not transmit light. The light transmitting member may have light transmittance according to the purpose of the laminate. For example, when the laminate is an image display device, the light transmitting member may have visible light transmittance to the extent that the image formed on the display member is visible. Examples of the light-transmitting member include plate materials and sheet materials such as glass, (meth) acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyester and cycloolefin polymer. These may be subjected to a hard coating treatment, an antireflection treatment, an antiglare treatment, an antifouling treatment, a fogging treatment, a polarization treatment, a wavelength cut treatment, or the like on one surface or both surfaces. Further, the light-transmitting member may be provided with a light-shielding layer. Examples of such a light-transmitting member include an icon sheet and a bright sheet.

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. Examples of the member that does not transmit light include plate-like materials such as alumina and the like, sheet materials such as alumina, metal sheets such as stainless steel subjected to insulation treatment such as surface oxidation, thermosetting resins, . Specific examples of the member that does not transmit such 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 already formed with a color filter.

For example, a laminate that is a variety of image display devices can be manufactured by using one of the substrate 1 and the substrate 2 as a display body and the other as a light-transmissive member or a member that does not transmit light. Specific embodiments are as follows.

(1) A liquid crystal display device can be manufactured by using one of the substrate 1 and 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 protective panel or a substrate with a protective panel can be manufactured by using one of the substrate 1 and the substrate 2 as a protective panel and the other as an image display device or various substrates. Further, one of the substrate 1 and the substrate 2 may be a protective panel, and the other may be a light-transmitting member.

(5) A touch panel can be manufactured by using one of the substrate 1 and the substrate 2 as a light-transmitting substrate having a transparent electrode and the other as a light-transmitting member. Further, one of the substrate 1 and the substrate 2 may be a touch panel and the other may be a light-transmitting member.

Therefore, in the method of producing a laminate, one of the substrate 1 and the substrate 2 may be a liquid crystal display panel, an organic EL display panel, a protective panel or a touch panel, and the other may be a light transmitting member or a member which does not transmit light .

The combination of the substrate 1 and the substrate 2 is preferably a combination in which one of them is an inorganic material and the other is an organic material, and the substrate is a glass, a polyimide or a combination thereof, on which a color filter is laminated And a substrate in which a device such as an EL and a protective film are stacked in this order on a substrate of glass, polyimide or a combination thereof is more preferable. Here, it is preferable that the optical and thermosetting resin composition is applied on a substrate on which a color filter is laminated.

&Lt; Process (A) >

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

<< How to apply >>

The method of applying the composition to the substrate 1 is not particularly limited and one or more methods selected from the group consisting of spin coater, die coater, dispenser, inkjet printing, screen printing and gravure printing can be mentioned, Do. The thickness of the curable resin composition layer formed by applying the composition is not particularly limited and may be, for example, 10 to 500 탆, preferably 30 to 350 탆.

&Lt; Process (B) >

The step (B) is a step of bonding the substrate 2 to the curable resin composition layer to obtain a bonded body. The substrate 1 and the substrate 2 can be bonded by mounting the substrate 2 on the substrate 1 on which the curable resin composition layer is formed so as to be in contact with the curable resin composition layer.

The method for producing the laminate may include the step (B) of pressing the bonded body composed of the substrate 1 and the substrate 2 and the resin layer therebetween. Thereby, the adhesion of the joined body can be improved. The pressurizing treatment can be performed using a rubber roller, a flat press apparatus or the like.

&Lt; Process (C) >

Step (C) is a step of heating the joined body and / or irradiating the energy ray to obtain a laminate. By the step (C), the curable resin composition layer between the substrate 1 and the substrate 2 is cured to bond the substrates together.

The various conditions of the step (C) are curing by energy ray and heating and are as described above. When the substrate 1 is a base material that transmits an energy ray, the curable resin composition layer may be irradiated with an energy ray from the substrate 1 side to form a cured resin layer. Alternatively, the curable resin composition layer may be irradiated with an energy ray, A resin layer may be formed. When the substrate 1 is a substrate 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 be a material that does not transmit light (does not transmit visible light) that transmits an energy ray (for example, ultraviolet light), or a material that transmits light (transmits visible light) For example, ultraviolet light).

The laminate can be used for bonding the substrate 1 and the substrate 2, in which at least one of the substrate 1 and the substrate 2 is a light-transmitting member. The application of the laminate is an image display device such as liquid crystal. Further, the laminate can be used for adhering the substrate 1 and the substrate 2, in which neither the substrate 1 nor the substrate 2 does not transmit light or a device or filter in which light is not transmitted is already formed. The use of the laminate may be an image display device such as an organic EL.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise stated, parts and parts are by weight.

[Preparation of curable resin composition]

Each component other than the thermal radical polymerization initiator among Component A, Component B and Component C was weighed in a vessel (material SUS) according to the compounding ratio shown in the table, and the resultant was weighed at 60 to 80 ° C under atmospheric pressure, At 200 rpm for 30 minutes to 1 hour. After confirming that the temperature of the composition returned to 25 캜, the thermal radical polymerization initiator was weighed and uniformly mixed at 25 캜 under atmospheric pressure using a three-one motor, The optical or thermosetting resin compositions of Examples 1 to 4 were prepared.

[Measurement of physical properties]

Using the curable resin composition, the characteristics were measured as follows.

(Viscosity)

The viscosity of the liquid photo-curable resin composition was measured by using a viscometer (RE105U, manufactured by Daikuzan Kogyo Co., Ltd.) under the atmospheric pressure at 25 占 폚 by selecting an appropriate cone plate and rotational speed.

(Peeling test)

A slide glass was used as an inorganic substrate, and a PI (polyimide) film was used as an organic material. 0.2 g of the curable resin composition described in Tables 1 to 3 was dropped on a slide glass (S1127 manufactured by Matsunami Garasu), and the laminate was bonded to a PI film (capton made by Toray Industries, Ltd., thickness 50 탆) The film was transferred to the substrate 5 times while applying a force of about 1 kg to the roller (SN-print rubber roller No. 1). Thereafter, the curable resin compositions of Examples 1 to 3, 7, 9, and 11, and Comparative Examples 1 and 2 to which the photo radical polymerization initiator was added were exposed to light of 3000 mJ / cm2 by a metal halide lamp (ECS- Cm &lt; 2 &gt; The curable resin compositions of Examples 4 to 6, 8, 10 and 12, and Comparative Examples 3 and 4 to which a thermal radical polymerization initiator was added were cured by heating in an oven (LC113, manufactured by ESPEC) at 100 DEG C for 30 minutes. These test pieces were subjected to a 180 deg. Peel test at a tensile rate of 60 mm / min by a tensile tester (Minervase TG-2kN). And the average value was calculated.

The results are shown in Tables 1 to 3.

(A) (meth) acrylic oligomer

(a-1): UA10000B: polyether-based urethane acrylate oligomer (molecular weight: 25,000, manufactured by KSM)

(a-2): UN7700: polyester-based urethane acrylate oligomer (molecular weight 20,000, manufactured by Negami Kogyo K.K.)

(a-3): EB230: an aliphatic urethane acrylate oligomer (molecular weight 5,000, manufactured by Daicel-Cotech)

(a-4): UV6300B: urethane acrylate oligomer (molecular weight 3,000, manufactured by Nippon Gosei Chemical Industry Co., Ltd.)

(a-5): TE2000: polybutadiene-based urethane acrylate oligomer (molecular weight 3,000, manufactured by Nippon Soda Co., Ltd.)

(B) (meth) acrylic monomer

(b-1): IBOA: isobornyl acrylate (viscosity: 7.7 mPa 揃 s, available from Osaka Kikinaga Kogyo K.K.)

(b-2): 4HBA: 4-hydroxybutyl acrylate (viscosity: 5.5 mPa 占 퐏; Osaka Kikaku Kogyo Co., Ltd.)

(b-3): L-A: lauryl acrylate (viscosity 4.0 mPa 占 퐏, manufactured by Osaka Kikinaga Kogyo K.K.)

(b-4): IOAA: isooctyl acrylate (viscosity: 2 mPa 占 퐏, manufactured by Osaka Kikinaga Kogyo K.K.)

(C) a radical polymerization initiator

(c-1) I-184: 1-Hydroxy-cyclohexyl-phenyl-ketone (photo radical polymerization initiator, BASF)

(c-2) perocta O: t-butylperoxy 2-ethylhexanoate (thermal radical polymerization initiator, manufactured by Nippon Oil Co., Ltd.)

When the inorganic substrate and the organic substrate were bonded using the compositions of Examples 1 to 12, the peel strength was high and the adhesion between the inorganic substrate and the organic substrate was excellent.

In particular, according to the comparison of Examples 1 to 3 and the comparison of Examples 4 to 6, the higher the molecular weight of the oligomer, the higher the peel strength.

According to the comparison between Examples 1 and 4, the comparison between Examples 2 and 5, and the comparison between Examples 3 and 6, the peeling strength was further increased by thermosetting. According to the comparison between Examples 2 and 7, Examples 5 and 8, Examples 3 and 9, and Examples 6 and 10, when the content of Component A was smaller, the peel strength was higher.

According to a comparison between Examples 3 and 11 and Examples 6 and 12, a composition containing a (meth) acrylic monomer in which the component B is a "short alkyl chain and branched" has a "long alkyl chain" (Meth) acrylic monomer, the peel strength was higher.

In Comparative Examples 1 to 4, since the oligomer having a molecular weight of 3,000 was used, the peeling strength was low and the adhesion between the inorganic substrate and the organic substrate was poor.

Since the composition is excellent in adhesion between an inorganic material and an organic material, it can preferably be used as an adhesive for joining substrates for inkjet application, which is highly industrially useful.

Claims (13)

(Component C) selected from the group consisting of a (meth) acrylic oligomer having a molecular weight of 5,000 or more (Component A), a (meth) acrylic monomer (Component B), and a photo radical polymerization initiator and a thermal radical polymerization initiator, , And has a viscosity of 150 mPa s or less. The curable resin composition according to claim 1, wherein the component B comprises (meth) acrylate having 10 mPa 占 퐏 or less. The curable resin composition according to claim 1 or 2, wherein the component B comprises alicyclic (meth) acrylate, hydroxyl group-containing (meth) acrylate and C ₆ to C ₃₀ alkyl (meth) acrylate. The curable resin composition according to Claim 1 or 2, wherein the amount of Component A is 30 parts by weight or less based on 100 parts by weight of the total of Component A and Component B. The curable resin composition according to claim 3, wherein the component A is 30 parts by weight or less based on 100 parts by weight of the total of the component A and the component B. The curable resin composition according to claim 1 or 2, wherein the curable resin composition is an adhesive. The curable resin composition according to claim 3, which is an adhesive. The curable resin composition according to claim 4, which is an adhesive. The curable resin composition according to claim 5, which is an adhesive. The curable resin composition according to claim 1 or 2, wherein the curable resin composition for at least one method selected from the group consisting of spin coater, die coater, dispenser, ink jet application, screen printing and gravure printing. The curable resin composition according to claim 3, wherein the curable resin composition for at least one method selected from the group consisting of spin coater, die coater, dispenser, ink jet application, screen printing and gravure printing. The curable resin composition according to claim 4, wherein the curable resin composition for at least one method selected from the group consisting of spin coater, die coater, dispenser, ink jet application, screen printing and gravure printing. The curable resin composition according to claim 5, wherein the curable resin composition for at least one method selected from the group consisting of spin coater, die coater, dispenser, ink jet application, screen printing and gravure printing.