KR20210085638A - Laminate and image display apparatus comprising same - Google Patents

Abstract

The present invention relates to a laminate and an image display device including the same. The laminate includes a protective substrate, an adhesive layer, and a primer layer. Excellent adhesion between the primer layer and the adhesive layer can be maintained even at high temperatures.

Description

A laminate and an image display device including the same {LAMINATE AND IMAGE DISPLAY APPARATUS COMPRISING SAME}

The present invention relates to a laminate and an image display device including the same.

A polarizing plate has been used in a structure in which a protective film is laminated using an adhesive on one or both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as PVA)-based resin dyed with a dichroic dye or iodine. Conventionally, a triacetyl cellulose (hereinafter referred to as TAC)-based film has been mainly used as a polarizing plate protective film.

Since the TAC has a high moisture permeability, it can be applied to a water-based adhesive, but there is a problem that it is easily deformed in a high temperature or high humidity environment, so it is difficult to apply it to a recent display requiring high moisture resistance and high durability. Thus, methods for protecting a polarizing plate using a low moisture permeable substrate have been proposed.

As a representative low moisture permeability base material applied thereto, polyethylene polypropylene polybutene, polyfluoroethylene chlorinated polyethylene chlorinated propylene, ethylenically unsaturated carboxylic acid copolymer, cycloolefin resin, norbornene-based cyclic polyolefin resin, etc. can be heard The substrate is used in a stretched state to increase rigidity or to impart a phase difference. In this case, compared to an unstretched state, the adhesion to other materials is significantly reduced, and various methods for improving this have been proposed.

For example, in the process, the surface of the substrate is subjected to surface treatment by corona discharge treatment, etc., or a chlorinated polyolefin resin, polyurethane resin, etc. having good adhesion to the polyolefin resin, an acrylic resin, a chlorinated polyethylene resin, a thermoplastic resin such as a chlorprene rubber, an adhesive or By mixing with a coating agent, the method of improving the adhesiveness to an olefin resin base material, and paintability is known.

However, the surface treatment by corona discharge or the like achieves a certain effect, but the introduction of special maintenance is inevitable, and the practical limitations are large and the versatility is insufficient. In addition, although the method of mixing or grafting a thermoplastic resin with an adhesive agent or a coating agent to a certain extent can expect the improvement of adhesiveness, it is the present situation that sufficient adhesiveness is not obtained.

On the other hand, a technique for improving adhesion by using a primer on the surface of a substrate has been developed, and a technique using a primer such as polyurethane or polyester has been generally used.

The primer expresses adhesive force by imparting partial erosion (solubility) with the adhesive layer. However, due to the heat generated during the manufacturing process, the temperature of the surface of the substrate rises and excessive erosion of the primer layer occurs, resulting in rather reduced adhesion.

Since it is difficult to control the heat generated during the process, development of an adhesive capable of maintaining adhesion to the primer layer even at high temperatures is required.

JP Application No. 2013-032153

The present invention relates to a laminate and an image display device including the same.

The present invention provides a protective substrate; an adhesive layer provided on one surface of the protective substrate; and a primer layer provided between the protective substrate and the adhesive layer, wherein the adhesive layer includes a cured product of an active energy ray-curable composition, and the active energy ray-curable composition contains a hydroxyl group-containing acrylic monomer 100 parts by weight of the total composition It provides a laminate that contains 18 parts by weight or less as a basis.

Further, the present invention provides an image display device including the above-described laminate.

The laminate of the present invention may maintain excellent adhesion between the primer layer and the adhesive layer even at a high temperature.

1 shows the structure of the laminate of the present invention.

Hereinafter, the present specification will be described in more detail.

The laminate of the present invention has the effect that the adhesive force between the adhesive layer and the primer layer can be maintained excellently even at high temperatures. The laminate may be applied to an optical film, and examples of the optical film include a polarizing plate, an antireflection film, a retardation film, and a prism lens sheet. In addition, the laminate can be applied to an image display device such as a liquid crystal display.

The present invention is a protective substrate 101; an adhesive layer 103 provided on one surface of the protective substrate; and a primer layer 102 provided between the protective substrate 101 and the adhesive layer 103, wherein the adhesive layer includes a cured product of an active energy ray-curable composition, and the active energy ray-curable composition includes a hydroxyl group It provides a laminate comprising 18 parts by weight or less of the containing acrylic monomer based on 100 parts by weight of the total composition. The symbols in parentheses indicate the symbols of each layer of the laminate structure of FIG. 1 .

The laminate may maintain excellent adhesion between the primer layer and the adhesive layer even at a high temperature. Specifically, the temperature of the base material may increase due to heat generated by a device when manufacturing the laminate, or heat according to usage when the laminate is applied to an image display device or the like. At this time, the adhesive layer and the primer layer are dissolved to each other too much, there is a case where the adhesive strength is reduced.

The present inventors have found that by controlling the content of the hydroxyl group-containing acrylic monomer included in the active energy ray-curable composition, the adhesive strength is maintained by maintaining appropriate erosion properties over a wide process temperature, and thus completed the present invention. The hydroxyl group-containing acrylic monomer has excellent erosion properties to the primer layer, and may exhibit sufficient adhesion.

Specifically, the active energy ray-curable composition contains 18 parts by weight or less of the hydroxyl group-containing acrylic monomer based on 100 parts by weight of the total composition, preferably 1 part by weight or more and 18 parts by weight or less, more preferably 5 parts by weight or more and 15 parts by weight or more. or less, or 10 parts by weight or more and 15 parts by weight or less.

The hydroxyl group-containing acrylic monomer is a compound that contains a hydroxyl group (hydroxyl group) in its structure and also contains a polymerizable unsaturated double bond such as a (meth)acryloyl group and a vinyl group, and more preferably contains a hydroxyl group A (meth)acrylic monomer is used. As a specific example of the said hydroxyl-group containing monomer, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxy Hydroxyalkyl (meth)acrylics, such as hexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate and (4-hydroxymethylcyclohexyl)-methyl acrylate. Among the above-mentioned hydroxyl group-containing monomers, from the viewpoint of durability, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferable, and 4-hydroxybutyl (meth)acrylate is particularly preferable. Do.

The hydroxyl group-containing acrylic monomer has an excellent erosion property to the polyester or polyurethane component constituting the primer layer, compared to the acrylic monomer having other functional groups, and thus has a function to implement sufficient adhesion. If the content is too large, excessive erosion Since the primer layer is damaged, there is a problem in that the surface of the substrate is exposed and adhesive strength is reduced. In the present invention, by controlling the content of the acrylate having a hydroxyl group to be low, it was intended to prevent excessive adhesion of the primer layer and the adhesive layer.

The above-described hydroxyl group-containing acrylic monomer may be referred to as a “highly erosion acrylic monomer”, and an acrylic monomer having low erosion among acrylic monomers that may be additionally included may be referred to as a “low erosion acrylic monomer”.

The active energy ray-curable composition may further include a low-erosion acrylic monomer in addition to the hydroxyl group-containing acrylic monomer. The low-erosion acrylic monomer refers to a component having a lower erosion property to the primer layer than the hydroxyl group-containing acrylic monomer. By adjusting the content ratio of the "high erosion acrylic monomer" and the "low erosion acrylic monomer", the erosion of the adhesive layer to the primer layer can be more easily controlled.

Specifically, the content ratio of the hydroxyl group-containing acrylic monomer to the low-erosion acrylic monomer may be 1:1 to 1:10, preferably 1:2 to 1:8, more preferably 1:2 to 1:6. .

Examples of the low-erosion acrylic monomer include dipropylene glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, tetraethylene glue and cold diacrylate, and dipropylene glycol diacrylate is preferable in terms of adhesion and non-erosion.

The content of the low-erosion acrylic monomer may be 40 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the total composition.

Other materials that may be included in the active energy ray-curable composition will be described later.

adhesive layer

The adhesive layer serves to bond the protective substrate and the other optical member to each other.

An optical member such as a protective film for a process may be additionally provided on the opposite surface of the adhesive layer opposite to the primer layer.

The adhesive layer includes a cured product of an active energy ray-curable composition. That is, the adhesive layer may be formed by applying an active energy ray-curable composition on the primer layer and then curing.

As active energy rays for curing the active energy ray-curable resin composition, ultraviolet rays, near ultraviolet rays, infrared rays, X rays, γ rays, electron rays, proton rays, neutron rays, etc. can be used, but in general from the viewpoint of curing speed, price, and productivity Ultraviolet rays or electron beams are used. Here, when using an ultraviolet-ray as an active energy ray, let a photoinitiator be an essential component in an active-energy-ray-curable composition. Moreover, you may add a photosensitizer further if necessary.

When irradiating the electron beam, it has an acceleration voltage of 1000 keV or less, preferably 100-300 keV using a scanning or curtain electron beam accelerator, and when irradiating with ultraviolet rays, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, It is preferable to irradiate ultraviolet rays having an energy of 100 to 2000 mJ/cm 2 in a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, using a carbon arc, a metal halide lamp, or UV-LED. Moreover, when hardening, you may carry out in an inert gas environment.

The method for applying the active energy ray-curable composition is not particularly limited, and various means such as a method of directly dropping an adhesive, a roll coating method, a spraying method, and an immersion method can be employed.

The active energy ray-curable composition of the present invention may further include a monomer containing a polar functional group such as a carboxyl group, an amino group and an amide group in addition to the hydroxyl group-containing acrylic monomer.

The said carboxyl group containing monomer is a compound which contains a carboxyl group in the structure, and also contains polymerizable unsaturated double bonds, such as a (meth)acryloyl group and a vinyl group. Specific examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Among the carboxyl group-containing monomers, acrylic acid is preferable from the viewpoints of copolymerizability, price, and adhesive properties (adhesive strength, etc.).

The said amino-group containing monomer is a compound which contains an amino group in the structure, and also contains polymerizable unsaturated double bonds, such as a (meth)acryloyl group and a vinyl group. Specific examples of the amino group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate.

The said amide group containing monomer is a compound which contains an amide group in the structure, and also contains polymerizable unsaturated double bonds, such as a (meth)acryloyl group and a vinyl group. Specific examples of the amide group-containing monomer include (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropylacrylamide, N-methyl (meth) Acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide-based monomers such as acrylamide, aminoethyl (meth)acrylamide, mercaptomethyl (meth)acrylamide, and mercaptoethyl (meth)acrylamide; N-acryloyl heterocyclic monomers, such as N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, and N-(meth)acryloylpyrrolidine; and N-vinyl group-containing lactam monomers such as N-vinyl-pyrrolidone and N-vinyl-ε-caprolactam. The amide group-containing monomer is preferable from the viewpoint of satisfying durability, and among the amide group-containing monomers, an N-vinyl group-containing lactam-based monomer is particularly preferable.

The active energy ray-curable composition of the present invention may further include an aromatic ring-containing (meth)acrylate. The said aromatic ring containing (meth)acrylate is a compound containing an aromatic ring structure in the structure, and also containing a (meth)acryloyl group. As an aromatic ring, a benzene ring, a naphthalene ring, or a biphenyl ring is mentioned. An aromatic ring containing (meth)acrylate can satisfy durability and can improve the display nonuniformity by whitening of a peripheral part. As a specific example of aromatic ring containing (meth)acrylate, For example, benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, ethylene oxide-modified cresol (meth)acrylate, phenol ethylene Oxide-modified (meth) acrylate, 2-hydroxy-3-phenoxy propyl (meth) acrylate, methoxy benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, cresyl (meth) acrylate, What has a benzene ring, such as polystyryl (meth)acrylate; Naphthalenes such as hydroxyethylated β-naphthol acrylate, 2-naphthoethyl (meth) acrylate, 2-naphthoxyethyl acrylate, and 2-(4-methoxy-1-naphthoxy) ethyl (meth) acrylate having a ring; What has a biphenyl ring, such as biphenyl (meth)acrylate, is mentioned. In particular, as the aromatic ring-containing (meth)acrylate, from the viewpoint of adhesive properties and durability, benzyl (meth)acrylate and phenoxyethyl (meth)acrylate are preferable, and in particular, phenoxyethyl (meth)acrylate is desirable.

The active energy ray-curable composition may include a polyfunctional (meth)acrylate monomer having a glass transition temperature (Tg) of 150° C. or higher of the homopolymer. The polyfunctional (meth)acrylate monomer forms a second cross-linked structure through curing by irradiation with radiation and makes the adhesive more hard during curing, thereby improving the problem of durability degradation and at the same time improving the desired storage modulus ( G') can be obtained. In addition, it is a component for easy coating by diluting the active energy ray-curable composition to adjust the viscosity. That is, the multifunctional (meth)acrylate monomer serves to improve the workability of the active energy ray-curable composition by imparting durability to the cured adhesive layer, maintaining viscoelasticity, and controlling the viscosity.

As a polyfunctional (meth)acrylate monomer having a glass transition temperature (Tg) of 150° C. or higher of the homopolymer, for example, dimethyloltricyclodecane diacrylate (Tg: 214° C.), (trishydroxyethyl Socyanurate) triacrylate (Tg: 225° C.), [2-[1,1-dimethyl-2[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5yl ]methyl acrylate (Tg: 180°C), 9,9-bis[4-(2-acrylooxyethoxy)phenylfluorene (Tg: 179°C) and (trishydroxyethylisocyanurate)triacrylic The rate (Tg: 275° C.) may be exemplified, but is not limited thereto.

The active energy ray-curable composition of the present invention may further include a modifying monomer. The modifying monomer may be a vinyl-based monomer such as vinyl acetate or vinyl propionate; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate; glycol-based (meth)acrylates such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxy polypropylene glycol (meth) acrylate; (meth)acrylate monomers, such as tetrahydrofurfuryl (meth)acrylate, a fluorine (meth)acrylate, silicone (meth)acrylate, and 2-methoxyethyl acrylate, etc. can also be used. Moreover, isoprene, butadiene, isobutylene, vinyl ether, etc. are mentioned.

The active energy ray-curable composition of the present invention may further include a silane-based monomer containing a silicon atom. Examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8 -Vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyl Triethoxysilane, 10-acryloyloxydecyl triethoxysilane, etc. are mentioned.

In addition, as other monomers, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth) ) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (meth)acryloyl groups such as esters of (meth)acrylic acid and polyhydric alcohols such as meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, A polyfunctional monomer having two or more unsaturated double bonds such as a vinyl group, or a (meth)acryloyl group, an unsaturated double bond such as a vinyl group as the same functional group as the monomer component in the skeleton such as polyester, epoxy, urethane Polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, etc. added more than one can also be used.

The active energy ray-curable composition of the present invention may include a (meth)acrylic polymer formed from the above-described acrylic monomer. At this time, those having a weight average molecular weight (Mw) of 500,000 to 3,000,000 are preferably used. When durability, especially heat resistance is considered, it is more preferable that it is 1 million - 2.5 million, and, as for a weight average molecular weight (Mw), 1.1 million - 2 million are still more preferable. When the weight average molecular weight (Mw) is smaller than 500,000, it is not preferable from the viewpoint of heat resistance. Moreover, when a weight average molecular weight (Mw) becomes larger than 3 million, there exists a tendency for an adhesive bond layer to become hard easily, and it will become easy to generate|occur|produce peeling. In addition, a weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography), and is calculated|required from the value computed by polystyrene conversion.

The active energy ray-curable composition of the present invention may include a polyester-based urethane acrylate oligomer. In this case, even when the total glass transition temperature (Tg) of the composition falls, it has excellent heat resistance and water resistance by imparting retardation by a polyester group. In addition, since it has excellent adhesion to other members, it has an advantage of excellent adhesion to the film without a separate treatment such as corona treatment. In particular, the polyester-based urethane acrylate oligomer has an excellent adhesion to the non-pretreated protective film compared to other oligomers such as epoxy-based urethane acrylate oligomer. When the above-described active energy ray-curable composition is applied to a protective substrate, the bonding surface of the protective film with the adhesive is eroded by the ester group having an acid value, so that the composition has a physical structure that can easily penetrate the protective film surface. . That is, it is possible to increase the adhesion by simultaneously implementing the physical and chemical effects of the ester group.

By controlling the acid value of the polyester-based urethane acrylate oligomer, it is possible to further improve the adhesion of the active energy ray-curable composition to the base film. Specifically, the polyester-based urethane acrylate oligomer has an acid value of 90 mgKOH/g to 180 mgKOH/g, preferably an acid value of 95 mgKOH/g to 175 mgKOH/g, more `preferably an acid value of 100 mgKOH/g to 170 mgKOH/g. When the above range is satisfied, the active energy ray-curable composition effectively erodes (etches) the base film, thereby ensuring excellent adhesion to the base film. In addition, when the range is less than the above range, the degree of etching the protective film is small, so the adhesive strength is lowered, and when it exceeds the range, there is a problem of excessive etching of the base film, so it is preferable to adjust the range of the acid value to the range .

The acid value is to measure the equivalent of KOH required to neutralize the acid component (carboxyl group of the polyhydric acid) of the polyhydric acid or its ester contained in 1 kg of the sample, and the same amount of KOH as the acid content in 1 kg of the sample is measured. It means the amount corresponding to the equivalent weight. The said acid value can be calculated|required by the following method.

First, in order to measure the acid value of the synthesized acrylate oligomer, a 0.1 N potassium hydroxide solution to be used for titration is prepared. Put 5.9 g of 95 wt% reagent grade potassium hydroxide in a 1 L flask, and then add a small amount of water to dissolve it completely. Methanol is added here and mixed so that the total volume is 1 L.

To obtain the correction factor of the prepared titrant, 10 mL of 35 wt% HCl solution is placed in a beaker, and 2-3 drops of phenolphthalein indicator are added. Here, the 0.1 N potassium hydroxide titration solution prepared above is added until it turns pale red, and then the volume used is calculated. Among the values obtained by repeating this experiment three times, the average value A (mL) is obtained by averaging the remaining three values excluding the maximum and minimum values, and then the correction factor f is obtained using the following formula.

f = 5.611 / A

Take about 1 g of the sample, measure the mass (M) accurately, and then dissolve it in 42.8 g (50 mL) of toluene. Add 2-3 drops of 1 wt% phenolphthalein indicator and titrate with 0.1 N potassium hydroxide solution while stirring. At this time, measure the consumed amount (B) in mL, and then calculate the acid value using the following formula.

Acid Value = 5.611 x N x f x B / M

where N: concentration of potassium hydroxide standard solution,

f: Calibration of potassium hydroxide solution

factor, B: consumption of potassium hydroxide solution (mL),

M : mass of sample (g)

The method for obtaining the acid value is an example of an acid/base titration method in which a carboxyl group of a polyhydric acid or an ester thereof is titrated with KOH as a base, and known methods for analyzing an unreacted acid component or an ester component thereof may also be used. For example, in the case of an ester component of a polyhydric acid, the acid value may be obtained by analyzing the unreacted ester component in 1 kg of the sample using gas chromatography analysis, etc., and then calculating the amount of KOH corresponding thereto.

The polyester-based urethane acrylate oligomer is a component that controls the physical properties (eg, hardness, adhesion, flexibility, etc.) of a cured resin by forming a cross-linked structure with a (meth)acrylate-based reactive monomer, and is used in an active energy ray-curable composition. When applied, it can improve moldability, elasticity and adhesion.

The urethane acrylate oligomer has a chemical structure having acrylate groups at both ends in the structure of the oligomer. Specifically, the urethane acrylate oligomer is a polyester-based polyol compound; isocyanate-based compounds; And it may be formed from a composition comprising an acrylate-based compound.

The polyester-based urethane acrylate oligomer may be synthesized through the following synthesis process. That is, a polyester-based polyol compound (P) having an ester group (R1) is reacted with a diisocyanate-based compound (I) to first synthesize an isocyanate group at the terminal, and then an acrylate-based compound having a hydroxyl group (A) ) can be reacted with isocyanate to prepare a final polyester-based urethane acrylate oligomer. Alternatively, it may be a polymer (co-polymer) synthesized by the following reaction scheme, but may be in the form of a simple mixed mixture.

Due to the polyester-based polyol compound, the oligomer includes a polyester chemical structure in the main chain, and as a result, when it has the same degree of curing, it has better step absorption compared to an oligomer that does not contain a polyester chemical structure, and the curing reaction It may be advantageous for securing reliability due to high efficiency.

The isocyanate compound is specifically selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI) and combinations thereof may contain one. Specifically, the isocyanate compound may include isophorone diisocyanate (IPDI), and in this case, the oligomer contains a chemical structure of a cycloalkylene structure in the main chain, and as a result, does not contain this chemical structure An advantage can be obtained in securing the reliability of high temperature and high humidity compared to the case.

The acrylate-based compound is a compound for providing acrylate groups to both ends of the oligomer, and may include an acrylate compound having a hydroxyl group. Specifically, the acrylate-based compound may include one selected from the group consisting of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA), and combinations thereof. .

The number average molecular weight of the polyester-based urethane acrylate oligomer may be 1,000 to 50,000, preferably 1,000 to 35,000, and more preferably 1,000 to 20,000. When the number average molecular weight of the urethane acrylate oligomer is less than 1000, the abrasion resistance, adhesion, and chemical resistance of the cured adhesive layer may be reduced. When the number average molecular weight of the urethane acrylate oligomer exceeds 50,000, pencil hardness, abrasion resistance, adhesion and chemical resistance of the cured adhesive layer may be reduced.

The number of functional groups of the polyester-based urethane acrylate oligomer may be 1 to 10. Considering the photocuring rate and water resistance, the urethane acrylate may have 1 to 8 functional groups, preferably 2 to 6 functional groups. In this case, the urethane acrylate oligomer having a specific number of functional groups may be a concept including other urethane acrylate oligomers substantially performing the role of the urethane acrylate oligomer having the specific number of functional groups. For example, in a urethane acrylate oligomer having a 10-functional group, when one functional group among the functional groups has substantially no activity, the urethane acrylate oligomer having a 10-functional group may be included in the urethane acrylate oligomer having a 9 functional group. .

The polyester-based urethane acrylate oligomer may have a viscosity at 25° C. of 1,000 cPs or more and 50,000 cPs or less, preferably 2,000 cPs or more and 50,000 cPs or less, and more preferably 2,500 cPs or more and 50,000 cPs or less. In the above-mentioned viscosity and molecular weight range, when the cured product is manufactured, the molding processability is excellent, and the elasticity and adhesiveness are excellent.

The active energy ray-curable composition may include a photoinitiator. As the photoinitiator, a conventionally known photoinitiator may be used without particular limitation. Specific examples thereof include onium salts such as aromatic diazonium salts, aromatic iodonium salts and aromatic sulfonium salts, and iron-allene complexes. These may be used individually or in combination of 2 or more types.

Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

Examples of the aromatic iodonium salt include diphenyliodoniumtetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4 -Nonylphenyl) iodonium hexafluorophosphate, etc. are mentioned.

Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenyl) Thio) phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4,4'-bis [diphenylsulfonio] diphenyl sulfide bis hexafluoro Rhophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy) ) Phenylsulfonio] diphenyl sulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p) -Toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4 -(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p -toluyl)sulfonio-diphenylsulfide tetrakis(pentafluorophenyl)borate, the phosphate of diphenyl[4-(phenylthio)phenyl]sulfonium, etc. are mentioned.

Examples of the iron-allene complex include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, and xylene-cyclopentadiene. and nyliron(II)-tris(trifluoromethylsulfonyl)methanide.

The photoinitiator may use a commercially available product, for example, CPI-100P, 101A, 200K, 210S (above, San Apro Co., Ltd. product), Kayarad (registered trademark) PCI-220, PCI-620 (above, Nihon Kayaku Co., Ltd.), UVI-6990 (above, Union Carbide (Yunionka-Bide)), Adekaoptomer (registered trademark) SP-150, SP-170 (above, ADEKA Co., Ltd.), CI-5102, CIT-1370, 1682, CIP-1866S, 2048S, 2064S (above, manufactured by Nippon Soda Co., Ltd.), DPI-101, 102, 103, 105, MPI-103, 105, BBI-101, 102, 103, 105, TPS-101, 102, 103, 105, MDS-103,105, DTS-102, 103 (above, Midori Chemical Co., Ltd.), PI-2074 (Rhodia Japan) ) Co., Ltd. products) and the like.

The type of the photoinitiator is not particularly limited, and a conventionally known photoinitiator can be preferably used. A photoinitiator may be used individually or in combination of 2 or more types.

The photoinitiator is specifically hydrogen peroxide, an inorganic peroxide such as potassium persulfate or ammonium persulfate, t-butyl hydroperoxide, t-dibutyl peroxide, cumene hydroperoxide, acetyl peroxide, organic such as benzoyl peroxide and lauroyl peroxide Peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride and azobiscyanovaler Azo compounds such as acids, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, 2,3-dialkyldione compounds, disulfide compounds, fluorine and loamine compounds, aromatic sulfoniums, lopin dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. More specifically, acetophenone, 3-methylacetophenone, benzyldimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-[4 acetophenones such as -(methylthio)phenyl]-2-morpholinopropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenones including benzophenone, 4-chlorobenzophenone, and 4,4'-diaminobenzophenone; benzoin ethers such as benzoin propyl ether and benzoin ethyl ether; thioxanthone such as 4-isopropylthioxanthone; 1-hydroxycyclohexylphenyl ketone, xanthone, fluorenone, camphorquinone, benzaldehyde, anthraquinone, etc. are mentioned.

The photoinitiator may use a commercially available product, for example, IRGACURE (registered trademark) 184, 819, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR (registered trademark) TPO , Darocure (registered trademark) 1173 (above, BASF Japan Co., Ltd. product), Esacure (registered trademark) KIP150, TZT (above, DKSH Japan Co., Ltd. product), KAYACURE (registered trademark) BMS, DMBI (above, Nippon Kayaku Co., Ltd. product) etc. are mentioned.

In addition, the photoinitiator is an amine such as ethylamine, triethanolamine and dimethylaniline, polyamine, a ferric salt compound, ammonia, triethylaluminum, triethylboron, an organometallic compound such as diethylzinc, sodium sulfite, hydrogen sulfite You may use together appropriate reducing agents, such as sodium, cobalt naphthenate, a sulfinic acid, and a mercaptan.

The active energy ray-curable composition may include a photosensitizer. There is no restriction|limiting in particular in the kind of photosensitizer, A conventionally well-known photosensitizer can be used preferably. A photosensitizer may be used individually or in combination of 2 or more types.

As a specific example of the said photosensitizer, For example, pyrene; benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and α,α dimethoxy-α-phenylacetophenone; Benzophenones such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone derivative; thioxanthone derivatives such as 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; acridone derivatives such as N-methylacridone and N-butylacridone; In addition, (alpha), (alpha)- diethoxy acetophenone, benzyl, fluorenone, xanthone, a uranyl compound, a halogen compound, etc. are mentioned.

A compound may be used for the said photosensitizer, and a commercial item may be used for it. As an example of a commercial item, For example, Kayacur (trademark) DMBI, BDMK, BP-100, BMBI, DETX-S, EPA (above, Nippon Kayaku Co., Ltd. product), Anthracure (trademark) UVS-1331, UVS are, for example, -1221 (above, Kawasaki Kasei Kogyo Co., Ltd. product), Uvecryl P102, 103, 104, 105 (above, UCB company product), TPO, etc. are mentioned.

The amount of at least one of the photoinitiator and the photosensitizer (when the photoinitiator and the photosensitizer are used together, the amount of the total amount used) is based on the total weight of the remaining components except for the photoinitiator and the photosensitizer in the active energy ray-curable composition. Preferably it is 0.1 weight part or more and 7 weight part or less, More preferably, it is 0.2 weight part or more and 3.5 weight part, 0.2 weight part or more and 2.5 weight part or less. Since it is excellent in curing efficiency by ultraviolet irradiation in the said range, the fall of adhesiveness and durability by bleed-out can be suppressed.

The active energy ray-curable composition may include a silane coupling agent.

The type of the silane coupling agent is not particularly limited, for example, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycy Doxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxy Silane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-amino Propylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl -3-Aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The said active energy ray-curable composition may contain additives other than the said component as needed in the grade which does not significantly reduce the effect of this invention.

The additives include, for example, other polymerizable components other than the above, ultraviolet absorbers, antioxidants, heat stabilizers, inorganic fillers, softeners, antioxidants, antioxidants, stabilizers, tackifying resins, modified resins (polyol resins, phenolic resins, acrylics) resins, polyester resins, polyolefin resins, etc.), leveling agents, defoamers, plasticizers, dyes, pigments (colored pigments, extenders, etc.), treatment agents, sunscreens, optical brighteners, dispersants, light stabilizers, antistatic agents, lubricants, etc. can be heard

The content of the additive is preferably 0.01 parts by weight or more and 20 parts by weight or less, more preferably 0.02 parts by weight or more and 10 parts by weight or less, and 0.05 parts by weight or more, based on 100 parts by weight of the total active energy ray-curable composition excluding the additive. It is more preferable that it is below weight part. By making content of an additive into the said range, the effect of the adhesive agent of this invention can fully be exhibited.

The thickness of the adhesive layer may be adjusted within a range exhibiting adhesive force, and specifically, may be greater than 0 μm and less than or equal to 20 μm.

primer layer

The primer layer may include a urethane resin or an acrylic resin, preferably a urethane resin. In addition, it may include a polyester resin.

Examples of the urethane resin include those obtained by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender. By using a polyol having a sulfonic acid group or a metal salt of a sulfonic acid group in a part of the polyol, a sulfonic acid group in the urethane resin is used. can be introduced In this case, it is advantageous to include an acid value to have sufficient curing density and hardness.

As the polyol having a sulfonic acid group, for example, a polyester polyol obtained by reacting a dicarboxylic acid having a sulfonic acid group or a metal salt of a sulfonic acid group or a salt thereof with a low molecular weight polyol, 2-butene-1,4-diol, etc. and polyols having a sulfonic acid group obtained by sulfonating a polyol having an unsaturated group of

Examples of the dicarboxylic acid having a sulfonic acid group include 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and dialkyl esters thereof. can be heard Moreover, those in which the sulfonic acid group which these compounds have is a metal salt can be used. Among these, 5-sodium sulfoisophthalate and 5-sodium dimethyl sulfoisophthalate are preferable because long-term storage stability can be maintained and more excellent water resistance and solvent resistance can be provided.

In addition, it is preferable to use the polyol having a sulfonic acid group in an amount of 50 to 90% by mass based on the total mass of the urethane resin, since good water dispersibility can be imparted.

peel properties

In general, the adhesive layer has excessive erosion to the primer layer at a high temperature, so that the high temperature adhesive strength is reduced. However, the adhesive layer of the present invention has a characteristic that the erosion property to the primer layer is appropriately adjusted at a high temperature, and the adhesive force to the primer layer is low even at a high temperature.

Specifically, the laminate is characterized in that excellent adhesion between the adhesive layer and the primer layer is maintained even at a high temperature.

An adhesive force retention ratio (high temperature adhesive force/low temperature adhesive force) between the adhesive layer and the primer layer of the laminate may be 40% or more.

The high-temperature adhesive strength is the peel force when the laminate is heat treated at 50° C. for 20 seconds, and then the substrate is peeled off at a peeling rate of 30 m/min and a peel angle of 90 degrees in an environment of 25° C.

The low-temperature adhesive strength is the peeling force when the substrate is peeled at a peeling rate of 30 m/min and a peeling angle of 90 degrees in an environment of 25°C.

In addition, after the laminate was heat-treated at 50° C. for 20 seconds, the high-temperature adhesive strength when the substrate was peeled at a peel rate of 30 m/min and a peel angle of 90 degrees in an environment of 25° C. was 200 gf/20 mm or more, 250 gf/20mm or more, more preferably 300 gf/20mm or more.

protective film

The protective substrate may be a polyolefin-based substrate or an acrylic substrate. Specifically, a polyethylene terephthalate (PET, polyethylene terephthalate) film, a cycloolefin polymer (COP, cycloolefin polymer) film, an acrylic film, etc. may be used. Among them, in consideration of optical properties, durability, economical efficiency, etc., it is particularly preferable to use a polyethylene terephthalate or triacetyl cellulose-based film.

image display device

The present invention provides an image display device including the above-described laminate.

The laminate may further include a display panel.

The display panel may be a liquid crystal panel, a plasma panel, and an organic light emitting panel. Accordingly, the image display device may be a liquid crystal display device (LCD), a plasma display device (PDP), and an organic light emitting display device (OLED). More specifically, the image display device may be a liquid crystal display device including a liquid crystal panel and polarizing plates respectively provided on both surfaces of the liquid crystal panel.

In this case, the type of the liquid crystal panel included in the liquid crystal display is not particularly limited. For example, it is not limited to the type, TN (twisted nematic) type, STN (super twisted nematic) type, F (ferroelectic) type or PD (polymer dispersed) type panels such as passive matrix type; an active matrix type panel such as a two terminal type or a three terminal type; All known panels such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel may be applied. In addition, other components constituting the liquid crystal display device, for example, the types of upper and lower substrates (eg, color filter substrates or array substrates), etc. are not particularly limited, and configurations known in this field are not limited. can be employed

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

<Production of active energy ray-curable composition for adhesive layer>

An active energy ray-curable composition according to the composition of Table 1 was prepared.

Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Preparation 5 Preparation 6 (A) 4-HBA 15 12 0 20 0 5 2-HEA 0 0 10 0 0 0 (B) DPGDA 42 46 42 38 42 52 ACMO 0 0 0 0 15 0 M370 20 16 20 20 20 20 (C) BNU5347 8 8 8 8 8 8 (D) KBM403 15 15 15 15 15 15 (E) I250 1.5 1.5 1.5 1.5 1.5 1.5 (F) TPO 2 2 2 2 2 2. DETX 1.3 1.3 1.3 1.3 1.3 1.3 (A): hydroxyl group-containing acrylic monomer

4-HBA: 4-hydroxybutyl acrylate
2-HEA: 4-hydroxyethyl acrylate

(B): other acrylic monomers
DPGDA: dipropylene glycol diacrylate
ACMO: N-acryloylmorpholine
M370: tris (2-hydroxyethyl) isocyanurate triacrylate

(C): Urethane acrylate oligomer
BNU5347 (manufactured by BNTM)

(D): Silane coupling agent
KBM403: (3-glycidoxypropyl) trimethoxysilane

(E): photoinitiator
I250: (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate

(F): photosensitizer
TPO: 2,4-diethylthioxanthone diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide
DETX: 2,4-diethylthioxanthone

<Preparation of Primer Composition 1>

A primer composition of a polyurethane component was prepared. A primer composition 1 was prepared by mixing 20 pt of a polyurethane-based resin (composed of an isocyanate compound of IPDI and a diol compound of 1,6-hexanediol, caproctamdiol, terephthalic acid, and isophthalic acid) and 5 pt of an oxazoline compound as a crosslinking agent. .

<Preparation of Primer Composition 2>

A primer composition of a polyester component was prepared. A primer composition 2 was prepared by mixing 20 pt of a polyester-based resin (A-645GH: Takamatsu oil; solid content of 30 wt %) and 5 pt of an isocyanate compound of IPDI as a crosslinking agent.

<Example 1: Preparation of laminate>

A primer layer was formed by applying and drying the primer composition 1 or 2 on the acrylic film. Thereafter, the active energy ray-curable composition of Preparation Example 1 is applied to the surface of the primer layer, a polyvinyl alcohol-based polarizer is laminated, and then the UV light of ^{1,000 mJ/cm 2 is irradiated using a metal halide lamp to cure it.} , an adhesive layer was formed to prepare a laminate.

<Example 2: Preparation of laminate>

A laminate was prepared in the same manner as in Example 1, except that the active energy ray-curable composition of Preparation Example 2 was used instead of the active energy ray-curable composition of Preparation Example 1.

<Example 3: Preparation of laminate>

A laminate was prepared in the same manner as in Example 1, except that the active energy ray-curable composition of Preparation Example 3 was used instead of the active energy ray-curable composition of Preparation Example 1.

<Comparative Example 1: Preparation of laminate>

A laminate was prepared in the same manner as in Example 1, except that the active energy ray-curable composition of Preparation Example 4 was used instead of the active energy ray-curable composition of Preparation Example 1.

<Comparative Example 2: Preparation of laminate>

A laminate was prepared in the same manner as in Example 1, except that the active energy ray-curable composition of Preparation Example 5 was used instead of the active energy ray-curable composition of Preparation Example 1.

<Comparative Example 3: Preparation of laminate>

A laminate was prepared in the same manner as in Example 1, except that the active energy ray-curable composition of Preparation Example 6 was used instead of the active energy ray-curable composition of Preparation Example 1.

<Experimental example: adhesion test>

For the laminates of Examples and Comparative Examples, laminates were prepared while changing heat treatment conditions before curing the active energy ray-curable composition. Thereafter, the peeling force when the adhesive layer and the primer layer were peeled from each other were measured and compared.

When the primer layer has an appropriate erosion property, high adhesion is exhibited, but when the primer layer is over-eroded, the peeling force is lowered, thereby exhibiting low adhesion.

heat treatment conditions Primer layer composition Primer layer not included Primer composition 1 Primer composition 2 Example 1 unprocessed 300 gf/20mm 560 gf/20mm 90 gf/20mm Treatment at 50°C for 20 seconds 300 gf/20mm 340 gf/20mm unmeasured Treatment at 50°C for 30 seconds 250 gf/20mm 260 gf/20mm unmeasured Example 2 unprocessed 280 gf/20mm 580 gf/20mm 80 gf/20mm Treatment at 50°C for 20 seconds 290 gf/20mm 350 gf/20mm unmeasured Treatment at 50°C for 30 seconds 260 gf/20mm 300 gf/20mm unmeasured Example 3 unprocessed 250 gf/20mm 540 gf/20mm 80 gf/20mm Treatment at 50°C for 20 seconds 250 gf/20mm 460 gf/20mm unmeasured Treatment at 50°C for 30 seconds 220 gf/20mm 330 gf/20mm unmeasured Comparative Example 1 unprocessed 300 gf/20mm 560 gf/20mm 70 gf/20mm Treatment at 50°C for 20 seconds 100 gf/20mm 150 gf/20mm unmeasured Treatment at 50°C for 30 seconds 80 gf/20mm 80 gf/20mm unmeasured Comparative Example 2 unprocessed 50 gf/20mm 100 gf/20mm 70 gf/20mm Treatment at 50°C for 20 seconds 80 gf/20mm 100 gf/20mm unmeasured Treatment at 50°C for 30 seconds 80 gf/20mm 100 gf/20mm unmeasured Comparative Example 3 unprocessed 50 gf/20mm 80 gf/20mm 50 gf/20mm Treatment at 50°C for 20 seconds 80 gf/20mm 90 gf/20mm unmeasured Treatment at 50°C for 30 seconds 80 gf/20mm 90 gf/20mm unmeasured

From the above results, when the primer layer is not included, the adhesion of the acrylic substrate is significantly lowered, and thus it can be confirmed that the introduction of the primer layer is necessary.

On the other hand, since the laminates of Examples 1 to 3 contained a small amount of acrylate having a hydroxyl group having excellent erosion property to the primer layer, the erosion property to the primer layer was controlled even after heat treatment, and the adhesion was maintained excellently.

On the other hand, in the laminate of Comparative Example 1, it was confirmed that the adhesive strength was significantly reduced because the primer layer was excessively eroded during heat treatment.

The adhesive layer of the laminate of Comparative Example 2 contains ACMO instead of an acrylate having a hydroxyl group, and ACMO has a higher solubility parameter than 4-HBA, but has low erosion to the primer layer, so it was confirmed that the adhesive force was significantly lowered.

On the other hand, since the adhesive layer of the laminate of Comparative Example 3 contains a small amount of the acrylate having a hydroxyl group, and has poor erosion to the primer layer, it can be confirmed that the acrylate having a hydroxyl group must be included in a certain amount or more.

Through the above results, it was confirmed that the laminates of Examples 1 to 3, in which the erosion to the primer layer was maintained at a certain level, maintained excellent adhesion even during heat treatment.

Claims (13)

protective substrate;
an adhesive layer provided on one surface of the protective substrate; and
A primer layer provided between the protective substrate and the adhesive layer,
The adhesive layer includes a cured product of an active energy ray-curable composition,
The active energy ray-curable composition is a laminate comprising 18 parts by weight or less of the hydroxyl group-containing acrylic monomer based on 100 parts by weight of the total composition. The method according to claim 1,
A laminate in which the adhesive force retention rate (high temperature adhesion / low temperature adhesion) between the adhesive layer and the primer layer of the laminate is 40% or more:
The high temperature adhesive strength is the peel force when the laminate is heat treated at 50° C. for 20 seconds, and then the substrate is peeled at a peeling rate of 30 m/min and a peeling angle of 90 degrees in an environment of 25° C.,
The low-temperature adhesive force is the peeling force when the substrate is peeled at a peeling rate of 30 m/min and a peeling angle of 90 degrees in an environment of 25° C. under conditions of not heat-treating the substrate. The method according to claim 1,
After the laminate is heat-treated at 50° C. for 20 seconds, the high-temperature adhesive strength when the substrate is peeled at a peel rate of 30 m/min and a peel angle of 90 degrees in an environment of 25° C. is 200 gf/20 mm or more. . The method according to claim 1,
The hydroxyl group-containing acrylic monomer is a laminate of 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate. The method according to claim 1,
The active energy ray-curable composition is a laminate that further comprises a low-erosion acrylic monomer. 6. The method of claim 5,
The content ratio of the hydroxyl group-containing acrylic monomer to the low erosion acrylic monomer is 1:1 to 1:10 in a laminate. The method according to claim 1,
The active energy ray-curable composition further comprises a polyfunctional (meth)acrylate monomer having a glass transition temperature (Tg) of 150° C. or higher of the homopolymer. The method according to claim 1,
The active energy ray-curable composition is a laminate further comprising a polyester-based urethane acrylate oligomer. The method according to claim 1,
The active energy ray-curable composition is a laminate comprising a silane coupling agent. The method according to claim 1,
The thickness of the adhesive layer is more than 0㎛ 20㎛ the laminate. The method according to claim 1,
The primer layer is a laminate comprising a urethane resin or an acrylic resin. The method according to claim 1,
The protective substrate may be a polyolefin-based substrate or an acrylic substrate. An image display device comprising the laminate according to any one of claims 1 to 12.

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