KR101725855B1 - Curable resin composition - Google Patents

Abstract

A curable resin composition showing high initial adhesion and adhesion durability is provided. (A) an oligomer having no epoxy group and having a dienic or hydrogenated diene skeleton, (B) a homopolymer of (meth) acrylate having a glass transition temperature of -100 to 60 ° C, (C) a radical polymerization initiator, (D) a reducing agent. The curable resin composition according to the present invention can be used as an adhesive composition and can be used in a touch panel laminate.

Description

Curable resin composition < RTI ID = 0.0 >

The present invention relates to a curable resin composition. More particularly, the present invention relates to an adhesive composition comprising a curable resin composition.

A touch panel mounted on a display body such as an LCD (liquid crystal display) includes a resistive film, a capacitance type, an electromagnetic induction type, and an optical type. There is a case where a bright plate for improving the design of the appearance of the touch panel or an icon sheet for specifying the touch position is joined to the surface of the touch panel. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded on the transparent electrode.

Conventionally, an adhesive is used for joining the screen and the touch panel, joining the icon sheet and the touch panel, and joining the transparent substrate and the transparent plate. There has been a problem that the adhesive is insufficient in the technique using such an adhesive.

Thus, Patent Document 1 proposes a photocurable adhesive composition for bonding a touch panel comprising (A) a (meth) acrylate oligomer having polyisoprene, polybutadiene or polyurethane skeleton and (B) a softening component.

In Patent Document 2, 100 parts by weight (100 parts by weight) of a (meth) acrylic monomer mainly composed of isobornyl (meth) acrylate is used for the purpose of providing excellent workability and long-term reliability, And 25 to 100 parts by weight of a prepolymer having polybutadiene as a main chain and having at least one (meth) acrylic group on both ends or side chains of the main chain thereof, and a photopolymerization initiator.

Further, if the bonding surface is subjected to printing processing, there is a problem that the portion of the printing processing is difficult to be adhered by the light energy line and the adhesiveness is deteriorated due to the influence of the uncured portions. Thus, Patent Document 3 proposes a curable composition containing (meth) acrylic acid ester, a radical polymerization initiator, epoxidized polyisoprene, and a curing accelerator.

Patent Document 1: International Publication No. 2010/027041 Patent Document 2: Japanese Patent Application Laid-Open No. 64-85209 Patent Document 3: International Publication No. 2004/076558

Patent Document 1 discloses a thermosetting resin composition comprising a phenoxyethyl (meth) acrylate, a phenoxypolyethylene glycol (meth) acrylate, a 2-hydroxy-3-phenoxypropyl (meth) acrylate, a cyclohexyl Cyclic (meth) acrylates such as (meth) acrylate monomers selected from adduct (meth) acrylate, methoxy triethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate are used.

In Patent Document 2, since it is a high-elasticity resin based on rigid skeletal monomers such as isobonyl (meth) acrylate and dicyclopentenyl (meth) acrylate, it can not withstand the expansion and contraction of the adherend in a high temperature reliability test, There is a possibility of occurrence.

The curable composition mainly composed of the epoxidized polyisoprene described in Patent Document 3 can not be said to have sufficient moisture and heat resistance.

In applications such as joining of a screen and a touch panel, joining of an icon sheet and a touch panel, joining of a transparent substrate and a transparent plate, and the like, the touch panel is flexible enough to follow the deformation of the adherend in a warm- Is considered to be preferable.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for joining a transparent plate and a transparent plate, The problems of the prior art that it is difficult to impart sufficient initial adhesion and wet heat resistance in case of bonding the optical functional material to the display body or the problem of the prior art that the adhesive surface is peeled off or the glass of the display body is broken Based on the weight of the curable resin composition.

That is, the present invention is, in one aspect, a curable resin composition containing the following components (A) to (C).

(A) an oligomer having no epoxy group and having a dienic or hydrogenated dienic skeleton

(B) homopolymer (meth) acrylate having a glass transition temperature of -100 to 60 ° C

(C) a radical polymerization initiator

(D) Reducing agent

In one embodiment of the curable resin composition according to the present invention, the component (B) is a compound represented by the general formula (1).

General formula (1) ZOR ₁

Wherein Z represents a (meth) acryloyl group, and R ₁ represents an alkyl group having 9 to 20 carbon atoms.

In another embodiment of the curable resin composition according to the present invention, 30 to 98 parts by mass of the component (A) and 2 to 70 parts by mass of the component (B) are contained in a total amount of 100 parts by mass of the components (A) and (B).

In another embodiment of the curable resin composition according to the present invention, a silane coupling agent is further contained as component (E).

In another embodiment of the curable resin composition according to the present invention, the diene-based or hydrogenated diene skeleton of the component (A) is selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene and hydrogenated polyisoprene Lt; / RTI > skeleton.

In another embodiment of the curable resin composition according to the present invention, the oligomer having a diene-based or hydrogenated diene skeleton of the component (A) has a molecular weight of 500 to 70000.

In another embodiment of the curable resin composition according to the present invention, (C) the radical polymerization initiator is an organic peroxide.

In another embodiment of the curable resin composition according to the present invention, (D) the reducing agent is one or more of thiourea derivatives,? -Diketone chelates and? -Keto esters.

In another embodiment of the curable resin composition according to the present invention, the first curable resin composition is a two-part curable resin composition comprising at least (C) a radical polymerization initiator and the second agent at least containing (D) a reducing agent.

In another embodiment of the curable resin composition according to the present invention, the total amount of the component (A) and the component (B) accounts for 80 to 99 mass% of the curable resin composition and the total amount of the components (A) and (B) is 10 to 50 parts by mass and the amount of component (C) is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B) (A) and (B) are used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B) ) Is 0.01 to 10 parts by mass based on 100 parts by mass in total.

In another aspect, the present invention is an adhesive composition comprising the curable resin composition according to the present invention.

Another aspect of the present invention is a cured product of the adhesive composition according to the present invention.

In another aspect, the present invention is a composite in which an adherend is covered or bonded by a cured product according to the present invention.

In one embodiment of the composite according to the present invention, the adherend is at least one selected from the group consisting of triacetylcellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass and metal.

In another aspect, the present invention is a touch panel laminate obtained by bonding an adherend with an adhesive composition according to the present invention.

In another aspect, the present invention is a display using the touch panel laminate according to the present invention.

The curable resin composition of the present invention exhibits high initial adhesion and wet heat resistance.

The component (A) in the present invention is an oligomer having a diene-based or hydrogenated diene skeleton without an epoxy group.

The oligomer of the component (A) preferably has no epoxy group in view of its effectiveness.

In the present invention, the backbone skeleton of the oligomer is a diene-based or hydrogenated diene-based skeleton. As the diene-based or hydrogenated diene-based skeleton, at least one skeleton selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene and hydrogenated polyisoprene is preferable. Of these, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable in view of high adhesion durability, and polybutadiene is more preferable.

The oligomer preferably has at least one (meth) acryloyl group in the terminal or side chain of the main chain skeleton. Among them, those having a (meth) acryloyl group at both ends of the main chain skeleton are preferable.

The molecular weight of the oligomer is preferably from 500 to 70000, more preferably from 1000 to 60000, and most preferably from 1000 to 55000. If the molecular weight is 500 or more, the hardness of the cured product obtained by curing the curable resin composition of the present invention is high, so that the adhesive layer can be easily formed. When the molecular weight is less than 70,000, the viscosity of the obtained curable resin composition is small, so that workability in mixing and the like in the production process and workability in practical use are improved.

The molecular weight of the oligomer refers to the number average molecular weight calculated as the average molecular weight per molecule. In the examples of the present invention, the number average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography) was used.

As the oligomer of the component (A), "UC-203" (trade name of an isocyanuric anhydride adduct of an isoprene polymer and an ester oligomer of 2-hydroxyethyl methacrylate) "LIR-50" (isoprene oligomer) manufactured by Kuraray Co., , LBR-50, LBR-307 (butadiene oligomer) manufactured by Kuraray Co., Ltd., TEAI-1000 (terminal acrylic modified hydrogenated 1,2-polybutadiene oligomer) manufactured by Nippon Soda Co., 2000 " (terminal methacryl-modified 1,2-polybutadiene oligomer). Among the oligomers of the component (A), at least one of the maleic anhydride adduct of isoprene polymer and the esterified oligomer of 2-hydroxyethyl (meth) acrylate, isoprene oligomer and 1,2-polybutadiene oligomer is preferable And an esterified maleic anhydride of an isoprene polymer and an esterified oligomer of 2-hydroxyethyl (meth) acrylate and / or a 1,2-polybutadiene oligomer are more preferable, and a maleic anhydride adduct of an isoprene polymer and a 2- Most preferred are esterified oligomers of hydroxyethyl (meth) acrylate. The oligomers of component (A) may be used alone or in combination of two or more.

The component (B) in the present invention is a (meth) acrylate having a homopolymer glass transition temperature of -100 ° C to 60 ° C. (B) is preferably acyclic (meth) acrylate. The acyclic (meth) acrylate refers to a (meth) acrylate having no alicyclic group or aromatic group and is typically a linear or branched (meth) acrylate. (Meth) acrylate having a homopolymer glass transition temperature of -80 캜 to -40 캜 is more preferable. (Meth) acrylate (homopolymer glass transition temperature of acrylate: -58 占 폚), lauryl (meth) acrylate (methacrylate) having a homopolymer glass transition temperature of -100 占 폚 to 60 占 폚, (Homopolymer glass transition temperature of acrylate: -30 ° C, homopolymer glass transition temperature of methacrylate: -65 ° C), 2-ethylhexyl (meth) acrylate (homopolymer glass transition temperature of acrylate: -85 Butyl (meth) acrylate (homopolymer glass transition temperature of methacrylate: 20 ° C), i-butyl (meth) acrylate (meth) acrylate Acrylate (homopolymer glass transition temperature of acrylate: 20 占 폚), t-butyl (meth) acrylate (glass transition temperature of homopolymer of methacrylate: 20 占 폚), methoxyethyl Glass transition temperature: -50 (Homopolymer glass transition temperature: 25 占 폚), 2-ethylhexyl glycol di (meth) acrylate, dicyclopentenyloxyethyl (Homopolymer glass transition temperature of acrylate: 7 占 폚, homopolymer glass transition temperature of methacrylate: 55 占 폚), 2-hydroxypropyl (meth) acrylate (Glass transition temperature: -7 占 폚, glass transition temperature of homopolymer of methacrylate: 26 占 폚), 2-hydroxybutyl (meth) acrylate (homopolymer glass transition temperature of acrylate: -38 占 폚) . These (meth) acrylates may be used alone or in combination of two or more. Among them, at least one selected from the group consisting of isostearyl (meth) acrylate, lauryl (meth) acrylate and 2-hydroxyethyl (meth) acrylate is preferable, and lauryl (meth) Or isostearyl (meth) acrylate are more preferable.

Glass transition refers to a change in a substance such as glass, which is liquid at high temperature, to an amorphous solid, rapidly increasing its viscosity in a certain temperature range as the temperature is lowered, and losing fluidity almost instantaneously. Examples of the method of measuring the glass transition temperature include thermogravimetry, differential scanning calorimetry, differential thermal measurement, and dynamic viscoelasticity measurement. In the present invention, it was measured by dynamic viscoelasticity measurement.

The glass transition temperature of a homopolymer of (meth) acrylate is described in JBrandrup, EHImmergut, Polymer Handbook, 2nd Ed., J. Wiley, New York 1975, Photocuring Technology Data Book (Technonetbooks) .

Of these components (B), the compound of the general formula (1) is preferable in view of high adhesiveness.

General formula (1) ZOR ₁

Wherein Z represents a (meth) acryloyl group, and R ₁ represents an alkyl group having 9 to 20 carbon atoms.

The compound of the general formula (1) further improves the flexibility of the cured product and further improves the adhesion to polyethylene terephthalate or the like. Examples of the compound represented by the general formula (1) include a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, (Meth) acrylic acid esters having a straight-chain or branched alkyl group having 9 to 20 carbon atoms such as decyl, nonadecyl, eodecyl, stearyl and isostearyl groups. R ₁ is preferably an alkyl group having from 10 to 19 carbon atoms, more preferably an alkyl group having from 11 to 18 carbon atoms, and most preferably a lauryl group and / or isostearyl group. These (meth) acrylates may be used alone or in combination of two or more.

(C) is a radical polymerization initiator. As the radical polymerization initiator, an organic peroxide is preferable. Examples of the organic peroxide include cumene hydroperoxide, paramethane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. . Of these, cumene hydroperoxide is preferable in view of reactivity.

Component (D) is a reducing agent. The reducing agent accelerates the decomposition of the radical polymerization initiator and accelerates the curing of the curable resin composition.

As the reducing agent (D), one or more of thiourea derivatives,? -Diketone chelates and? -Keto esters are preferable. Examples of thiourea derivatives include acetyl-2-thiourea, benzoyl thiourea, N, N-diphenyl thiourea, N, N-diethyl thiourea, N, N-dibutyl thiourea and tetramethyl thiourea. have. Among them, from the point of view of the effect, acetyl-2-thiourea, benzoyl thiourea, N, N-diphenyl thiourea, N, N-diethyl thiourea, N, N-dibutyl thiourea and tetramethyl thiourea , And acetyl-2-thiourea is more preferable. Examples of? -diketone chelates include vanadyl acetylacetonate, cobalt acetylacetonate, and copper acetylacetonate. Examples of? -keto esters include vanadyl naphthenate, vanadyl stearate, copper naphthenate, and cobalt octylate. One or more of these may be used. Of these, β-diketone chelate is preferable in view of reactivity, and vanadyl acetylacetonate is more preferable.

In the present invention, a silane coupling agent may be contained as the component (E) for the purpose of improving adhesion to glass. Examples of the silane coupling agent include? -Chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane,? - (meth) acryloxy Propyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Aminopropyltri Aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane,? - . Of these, γ-glycidoxypropyltrimethoxysilane and / or γ- (meth) acryloxypropyltrimethoxysilane are preferable from the viewpoint of adhesiveness to glass and the like, and γ-glycidoxypropyltrimethoxysilane Is more preferable.

The present invention contains the above components (A) to (D) as essential components. It becomes possible to cure at room temperature by the components (A) to (D).

The curable resin composition of the present invention preferably contains 30 to 98 parts by mass of the component (A) and 2 to 70 parts by mass of the component (B) in a total of 100 parts by mass of the components (A) and (B) It is more preferable to contain the component (A) in an amount of 40 to 95 parts by mass and the component (B) in an amount of 5 to 60 parts by mass and the component (A) in an amount of 50 to 90 parts by mass and the component (B) in an amount of 10 to 50 parts by mass .

In a preferred embodiment, the total mass of the component (A) and the component (B) accounts for 80 to 99% by mass, and typically 90 to 98% by mass in the curable resin composition of the present invention.

When the amount of the component (C) used is from 0.1 to 7 parts by mass based on 100 parts by mass of the total of the components (A) and (B), the adhesiveness of the curable resin composition to an adherend is particularly high, , And more preferably 0.5 to 5 parts by mass.

When the amount of the component (D) to be used is 0.01 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B), the adhesiveness of the curable resin composition to the adherend is particularly high, , And more preferably from 0.1 to 5 parts by mass.

The amount of the component (E) to be used is preferably 0.01 to 10 parts by mass, more preferably 1 to 5 parts by mass per 100 parts by mass of the total of the components (A) and (B).

It is also possible to divide the curable resin composition of the present invention into (C) a first agent containing a radical polymerization initiator and (D) a second agent containing a reducing agent. Other components are appropriately contained in the two agents. The first agent and the second agent may be cured at room temperature by contacting and curing immediately before use. In the case of the curable resin composition of Formulation 2, the amount of the radical polymerization initiator (C) and the amount of the reducing agent (D) is an amount of the above-mentioned mass portion.

In the curable resin composition of the present invention, various paraffins can be used to accelerate curing of the portion in contact with air.

The curable resin composition of the present invention may contain (meth) acrylate other than the component (A) and the component (B) for the purpose of further improving the adhesion to each adherend.

A commercially available antioxidant containing a polymerization inhibitor may be used for the purpose of maintaining storage stability.

Other than these, elastomers, various paraffins, plasticizers, fillers, coloring agents, rust inhibitors and the like can be used as desired.

The curable resin composition of the present invention can be used as an adhesive composition. In the present invention, an adherend may be bonded or coated with a cured product of an adhesive composition to prepare a composite. The various materials of the adherend are preferably at least one selected from the group consisting of polyolefins such as cycloolefin polymer, polyesters such as triacetylcellulose, fluoropolymer and polyethylene terephthalate, polycarbonate, glass and metal, At least one selected from the group consisting of polyolefin and glass is more preferable.

The adherend adhered with the curable resin composition of the present invention can be reworked (reused) after full curing. The rework method is not particularly limited, but it is possible to disassociate adherends by applying a load of 0.01 to 100 N between adhered one or two adherends to reuse the adherend after disassembly.

Example

Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto.

(Experimental Example)

Experiments were conducted at 23 ° C unless otherwise noted. Curable resin compositions having the compositions shown in Tables 1 to 4 were prepared and evaluated. The results are shown in Tables 1 to 4.

As the respective components in the curable resin composition described in the Experimental Examples, the following compounds were selected.

The following compounds were selected as oligomers having a diene-based or hydrogenated diene skeleton of the component (A).

(Number average molecular weight 2000 in terms of polystyrene by GPC) (A-1) Both ends methacrylic modified 1,2-polybutadiene oligomer ("TE-2000"

(A-2) isoprene oligomer ("LIR-50" manufactured by Kuraray Co., Ltd. (number average molecular weight 54,000 in terms of polystyrene by GPC)

(A-3) An ester of maleic anhydride of an isoprene polymer and an esterified oligomer of 2-hydroxyethyl methacrylate ("UC-203" manufactured by Kuraray Co., Ltd. (number-average molecular weight of 36,000 in terms of polystyrene by GPC)

The following compounds were selected as comparative examples of component (A).

(A-4) Epoxidized polyisoprene "E-IR" (product of Kuraray Co., Ltd., number average molecular weight of 28000 in terms of polystyrene by GPC)

The following compounds were selected as the (meth) acrylates having a homopolymer glass transition temperature of the component (B) of -100 to 60 캜.

(B-1) lauryl methacrylate (" Lite Ester L " manufactured by Kyowa Chemical Industry Co., Ltd.: homopolymer glass transition temperature: -65 캜)

(B-2) 2-hydroxyethyl methacrylate ("Light Ester HO" manufactured by Kyoeisha Chemical Co., Ltd.: homopolymer glass transition temperature: 55 ° C)

(B-3) isostearyl acrylate ("ISTA" manufactured by Osaka Organic Chemical Industry Co., Ltd .: homopolymer glass transition temperature: -58 ° C)

The following compounds were selected as comparative examples of component (B).

(B-4) isobornyl methacrylate (homopolymer glass transition temperature: 120 占 폚)

The following compounds were selected as the radical polymerization initiator of the component (C).

(C-1) cumene hydroperoxide

The following compounds were selected as the reducing agent of component (D).

(D-1) Acetyl-2-thiourea

(D-2) vanadyl acetylacetonate

(D-3) Diethylenetriamine

The following compounds were selected as comparative examples of component (D).

(D-4) aromatic sulfonium salt ("Rhodorsil-2074" manufactured by Rhodia)

The following compounds were selected as the silane coupling agent of component (E).

(E-1)? -Glycidoxypropyltrimethoxysilane

Various physical properties were measured as follows.

[Room Temperature Curing Property (Tensile Adhesive Strength)]

And the temperature was measured at 23 ° C. Regarding the room temperature curing property, the curable resin composition was applied to the surface of SPCC test piece (width 100 mm x length 25 mm x thickness 1.6 mm) so that the thickness was 0.05 mm. Separately, SPCC specimens were bonded to the SPCC test specimens so that the bonding area would be 15 mm long × 25 mm wide. The specimens were cured for 24 hours at 23 ° C. × 50% RH and tensile shear bond strength was measured at a tensile speed of 10 mm / min Respectively. When the adhesive strength was 5 MPa or more, the curing property at room temperature under a light shielding environment was considered to be good. The curable resin composition was prepared by mixing the first agent (A) and the second agent (B) at a ratio of 1: 1 by volume using a static mixer.

[Evaluation of adhesion of polyethylene terephthalate (PET) (peel adhesion strength between polyethylene terephthalate test pieces)]

A test piece (50 mm in width x 10 mm in length x 0.05 mm in thickness) of a biaxially stretched PET film (Rumirror T60, manufactured by Toray) was used as an adhesive composition to form an adhesive layer having a thickness of 30 m and an adhesive area of 40 mm x And 10 mm in width. After curing by room temperature curing, the portions of the test piece bonded with the adhesive composition were peeled off by peeling the two unfiltered film ends, thereby measuring the initial 180 ° peel adhesion strength . The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. The peel adhesion strength (unit: N / cm) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.

[Evaluation of glass adhesion property (Tensile adhesion strength between heat resistant glass test pieces)]

A Teflon (registered trademark) tape having a thickness of 80 m, a width of 12.5 mm and a length of 25 mm was used as a spacer between the heat-resistant glass test pieces (25 mm in width x 25 mm in length x 2.0 mm in thickness) and adhered using the curable resin composition as an adhesive composition (Bonding area: 3.125 cm 2). The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. After the adhesive composition was cured under the above conditions, a zinc-plated steel sheet (100 mm wide × 25 mm long × 2.0 mm thick, manufactured by Engineering Test Service) was applied on both sides of the test piece using an adhesive composition "G-55" manufactured by Denki Kagaku Kogyo Co., Respectively. After curing, the zinc plated steel sheet was chucked using the test piece adhered with the adhesive composition to measure the initial tensile shear bond strength. The tensile shear bond strength (unit: MPa) was measured at a tensile rate of 10 mm / min under a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of Cycloolefin Polymer (COP) Adhesion (Peel Adhesion Strength Between Cycloolefin Polymer Test Specimens)]

A test piece (50 mm in width x 10 mm in length x 0.05 mm in thickness) of a COP film (ZEONOR, manufactured by Zeon Corporation) was bonded to each other with a curing resin composition as an adhesive composition so that the adhesive layer had a thickness of 10 m and an adhesive area of 40 mm x 10 mm . After curing by room temperature curing, the untouched two film ends of the test piece adhered with the adhesive composition were pulled to peel off the portions where the films adhere to each other, and the initial 180 ° peel adhesion strength was measured. The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. The peel adhesion strength (unit: N / cm) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.

[Evaluation of Humidity Durability (Tensile Adhesive Strength Between Heat-Resistant Glass Test Piece after High-Temperature and High-humidity Exposure)]

TEMPAX glass (25 mm in width x 25 mm in length x 2 mm in thickness) was cured by bonding the adhesive layer to an adhesive layer having a thickness of 100 m and an adhesive area of 1.0 mm 2 using the curable resin composition as an adhesive composition. The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. After curing, the test piece adhered with the adhesive composition was exposed to an environment of 85 ° C and 85% relative humidity using a constant temperature and humidity bath for 1000 hours. The tensile shear bond strength was measured using the test piece after exposure. The appearance of the adhesive area was visually observed to determine whether it was yellowing. The degree of yellowing was defined as the value of Δb obtained by a color measuring device ("UV-Visible Spectrophotometer" manufactured by SHIMADZU). The tensile shear bond strength (unit: N / cm) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of Triacetyl Cellulose Adhesion (Peel Adhesion Strength Between Triacetyl Cellulose Test Specimens)]

A test piece (50 mm in width x 10 mm in length x 0.04 mm in thickness) of a triacetyl cellulose (TAC) film (average thickness: 40 m, manufactured by Fuji Film Co., Ltd.) was laminated using a curable resin composition as an adhesive composition, 40 mm long x 10 mm wide. After curing by room temperature curing, the untouched two film ends of the test piece adhered with the adhesive composition were pulled to peel off the portions where the films adhere to each other, and the initial 180 ° peel adhesion strength was measured. The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 50 mm / min under a temperature of 23 캜 and a humidity of 50%.

[Evaluation of fluoropolymer adhesiveness (peel adhesion strength between fluorine film test pieces)]

A test piece (50 mm in width x 10 mm in length x 0.04 mm in thickness) of a PVDF film (average thickness 40 占 퐉, manufactured by Denki Kagaku Kogyo Co., Ltd., "DX film") was laminated using a curable resin composition as an adhesive composition, 40 mm long x 10 mm wide. After curing by room temperature curing, the untouched two film ends of the test piece adhered with the adhesive composition were pulled to peel off the portions where the films adhere to each other, and the initial 180 ° peel adhesion strength was measured. The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 50 mm / min under a temperature of 23 캜 and a humidity of 50%.

[Evaluation of Polycarbonate Adhesion (Tensile Adhesion Strength Between Polycarbonate Test Specimens)]

A Teflon (registered trademark) tape having a thickness of 80 占 퐉, a width of 12.5 mm and a length of 25 mm was used as a spacer between polycarbonate (Panlite, manufactured by Teijin Co., Ltd.) (25 mm width x 25 mm length x 2.0 mm thickness) The composition was bonded using an adhesive composition (bonding area: 3.125 cm 2). The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. The tensile shear bond strength (unit: MPa) was measured at a tensile rate of 10 mm / min under a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Appearance observation (yellowing degree)]

TEMPAX glass (25 mm in width x 25 mm in length x 2 mm in thickness) was adhered and cured by using the curable resin composition as an adhesive composition so that the thickness of the adhesive layer was 100 m and the adhesive area was 1.0 mm < 2 >. The room temperature curing conditions were according to the method described in [room temperature curability (tensile adhesive strength)]. After the curing, the test piece adhered with the adhesive composition was subjected to a yellow color change in the? B value in a color measuring device ("UV-VISIBLE SPECTROPOHOTOMETER" manufactured by SHIMADZU).

From the experimental examples, the following can be known. The curable resin composition of the present invention exhibits high adhesiveness. In particular, it exhibits high adhesiveness to polycarbonate, polyolefin and glass. The curable resin composition of the present invention exhibits high adhesiveness. Therefore, when an optical functional material such as an acrylic plate or a polycarbonate plate is adhered to a display body such as a thin glass LCD, the adhesive surface is peeled off, the LCD is broken, Do not display stains. Since the curable resin composition of the present invention has a high resistance to humidity and humidity, it can follow the deformation of the adherend in the warmed atmosphere, and therefore the adherend does not peel off. The curable resin composition of the present invention can impart sufficient adhesiveness even when a printed part is bonded. Experimental Example 10 does not contain a silane coupling agent but has adhesive property.

The comparative example does not have the effect of the present invention. In Examples 14 to 15, since the oligomer having an epoxy group is contained, the adhesiveness is small and the cured product is yellowed. In Experimental Example 20, the homopolymer glass transition temperature was high and the curable resin composition had no flexibility, so the adhesion was small.

The curable resin composition of the present invention can be used in an adhesive composition for a touch panel laminate. The touch panel laminate generally comprises layers of cover material / touch panel sensor / liquid crystal panel. The curable resin composition according to the present invention can be used as an adhesive for bonding a touch panel sensor and a cover material. For example, when a cover material such as an icon sheet or the like for specifying a screen or a touch position is bonded to the surface of a touch panel Can be used as an adhesive agent. It can also be used as an adhesive bonding the touch panel sensor to the liquid crystal panel. In the capacitive touch panel, a transparent electrode is formed on a transparent substrate, and a transparent plate is bonded on the transparent electrode. The curable resin composition of the present invention is also very suitable as an adhesive when a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon. The touch panel laminate of the present invention can be used as a display.

Claims (16)

(A) to (D), wherein the total amount of the component (A) and the component (B) accounts for 80 to 99 mass% of the curable resin composition, Wherein the component (A) is 50 to 90 parts by mass and the component (B) is 10 to 50 parts by mass in the mass part,
(A) an oligomer having no epoxy group and having a dienic or hydrogenated dienic skeleton,
(B) homopolymer (meth) acrylate having a glass transition temperature of -100 to 60 ° C,
(C) a radical polymerization initiator,
(D) Reducing agent. The method according to claim 1,
Wherein the component (B) is a compound represented by the general formula (1):
General formula (1) ZOR ₁
Wherein Z represents a (meth) acryloyl group and R ₁ represents an alkyl group having 9 to 20 carbon atoms. delete The method according to claim 1,
And a silane coupling agent as a component (E). The method according to claim 1,
Wherein the diene-based or hydrogenated diene skeleton of component (A) is at least one skeleton selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene and hydrogenated polyisoprene. The method according to claim 1,
The oligomer having a diene-based or hydrogenated diene skeleton of the component (A) has a number average molecular weight of 500 to 70000. The method according to claim 1,
(C) the radical polymerization initiator is an organic peroxide. The method according to claim 1,
(D) a curing resin composition wherein the reducing agent is at least one selected from the group consisting of thiourea derivatives,? -Diketone chelates and? -Keto esters. The method according to claim 1,
A curable resin composition which is a curable resin composition of two formulations, wherein the first agent comprises at least (C) a radical polymerization initiator and the second agent contains at least (D) a reducing agent. The method according to any one of claims 1, 2, or 4 to 9,
(C) is used in an amount of 0.1 to 7 parts by mass based on 100 parts by mass of the total of the components (A) and (B), and the amount of the component (D) (E) is 0.01 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B) when the component (E) is contained. An adhesive composition comprising the curable resin composition according to any one of claims 1, 2, or 4 to 9. A cured product of the adhesive composition according to claim 11. A composite in which an adherend is covered or bonded by the cured product according to claim 12. The composite according to claim 13, wherein the adherend is at least one selected from the group consisting of triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. A touch panel laminate obtained by bonding an adherend with the adhesive composition according to claim 11. A display using the touch panel laminate according to claim 15.