KR101647153B1 - Aqueous pressure-sensitive adhesive composition, method for preparing thereof, pressure-sensitive adhesive sheet and wall paper comprising the same - Google Patents

Abstract

The present invention relates to an aqueous pressure-sensitive adhesive composition, a method for producing the same, and a pressure-sensitive adhesive sheet and wallpaper containing the same. The water-based pressure-sensitive adhesive composition of the present invention comprises a water-dispersible acrylic copolymer having flame retardance and flame retardancy, a tackifier, a flame retardant and a curing agent, Or more, and excellent flame retardancy and flame retardancy can be exhibited. In addition, the water-based pressure-sensitive adhesive composition of the present invention can efficiently prevent contamination of the indoor environment before and after the operation without the emission of contaminants due to the presence of the organic solvent.

Description

[0001] The present invention relates to an aqueous pressure-sensitive adhesive composition, a method for producing the same, a pressure-sensitive adhesive composition comprising the same,

The present invention relates to an aqueous pressure-sensitive adhesive composition, a method for producing the same, a pressure-sensitive adhesive sheet and wallpaper containing the same.

Heretofore, oil-based adhesives have been generally used for various decorative materials such as interior / exterior materials for buildings, flooring materials, advertisement materials, and vehicle / airborne interior materials. However, the oil-based pressure-sensitive adhesives are very likely to contaminate the indoor environment before and after the operation due to the undissolved residual organic solvent. Accordingly, the pressure-sensitive adhesive may adversely affect the health of workers and consumers due to air pollution and the like.

Due to such a problem, in recent years, there has been an increasing demand for water-based or water-dispersed pressure-sensitive adhesives that do not include organic solvents, and a lot of research and development has been made on such water-based pressure-sensitive adhesives both domestically and externally.

Korean Patent Publication No. 1996-41303 discloses an aqueous pressure-sensitive adhesive composition prepared by adding monomers or polymers of polyhydric alcohols to an aqueous acrylic emulsion. Korean Patent Publication No. 1997-0042907 discloses a pressure-sensitive adhesive composition comprising a low molecular weight polyacrylic acid and a high molecular weight polyacrylic acid Based on the total weight of the pressure-sensitive adhesive composition. Further, Japanese Patent Laid-Open No. 2005-146271 discloses an aqueous dispersion which is an emulsion polymer of a (meth) acrylic acid alkyl ester, a polymerizable unsaturated carboxylic acid and a monomer copolymerizable therewith; And an aqueous emulsion of a tackifier resin, and the amount of the non-volatile component is limited in viscosity, agglomerate occurrence rate and non-volatile component.

However, the pressure-sensitive adhesive composition disclosed in the above literature has adhesive properties similar to conventional oil-based pressure-sensitive adhesives, but has a problem that flame retardancy and flame retardancy are greatly reduced. In other words, in recent years, in order to prevent the combustion of products and the emission of toxic gases due to fire, flame retardancy and flame retardancy of the above-mentioned building interior / exterior materials and floor materials are highly required, and legal regulations therefor are also strengthened. Accordingly, although the flame-proofing process is mainly performed on the above-mentioned material itself, a flame-retarding process of a certain level or more is also required for a pressure-sensitive adhesive to be used together with a material in order to obtain more excellent flame retardancy and flame retardancy. Accordingly, in the case of a conventional oil-based pressure-sensitive adhesive, flame-retarding treatment is generally carried out.

Therefore, in the case of an aqueous pressure-sensitive adhesive, it is also necessary to impart a certain degree of flame retardancy together with basic adhesive properties. To this end, a method of adding flame-retardant inorganic particles to the composition can be considered. However, in the case of the above method, satisfactory flame retardancy can not be ensured due to low dispersibility of the inorganic particles, and there is a problem that the adhesion force is significantly lowered by the addition of the inorganic particles. In order to solve the problem of dispersibility of the inorganic particles, organic solvents may be used as a dispersion medium in some technologies. However, the same contamination problems as in the case of using a conventional oil-based pressure-sensitive adhesive may occur.

As such, an environmentally friendly water-based pressure-sensitive adhesive having excellent flame retardancy and flame retardancy while having the same or higher adhesive properties as existing oil-based pressure-sensitive adhesives has not been developed to date.

An object of the present invention is to provide an aqueous pressure-sensitive adhesive composition, a method for producing the same, and a pressure-sensitive adhesive sheet and wallpaper including the above.

The present invention provides, as means for solving the above problems, a water-dispersible acrylic copolymer; And at least one curing agent selected from the group consisting of melamine and oxazoline.

As another means for solving the above-mentioned problems, the present invention provides a process for producing a polyester resin composition, which comprises: (meth) acrylic acid ester monomer; a,? -unsaturated carboxylic acid containing monomers; And a step of copolymerizing the flame retardant component-containing monomer to prepare a water-dispersible acrylic copolymer. The present invention also provides a process for producing an aqueous pressure-sensitive adhesive composition according to the present invention.

The present invention provides, as yet another means for solving the above problems, a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing a cured product of the aqueous pressure-sensitive adhesive composition according to the present invention.

Another aspect of the present invention provides a wallpaper comprising a pressure-sensitive adhesive layer containing a cured product of the aqueous pressure-sensitive adhesive composition according to the present invention.

The present invention includes a water-dispersible acrylic copolymer having flame retardancy, a tackifier, a flame retardant, and a curing agent. Accordingly, the composition of the present invention can have excellent flame retardancy and flame retardancy, as well as adhesive properties and anti-aging properties equal to or higher than those of conventional pressure-sensitive adhesives, through synergistic effects caused by each of the above components or combinations thereof. Further, the water-based pressure-sensitive adhesive of the present invention has an advantage of preventing contamination of the indoor environment after the operation and after the operation due to no emission of pollutants due to the inclusion of the organic solvent.

1 and 2 are sectional views of a pressure-sensitive adhesive sheet according to an example of the present invention.
Figs. 3, 4 and 5 are views showing cross-sections of wallpaper according to an example of the present invention. Fig.

The present invention relates to a water-dispersible acrylic copolymer; And at least one curing agent selected from the group consisting of melamine and oxazoline. INDUSTRIAL APPLICABILITY The pressure-sensitive adhesive composition of the present invention is an aqueous type that does not contain an organic solvent, and it is possible to secure a pressure-sensitive adhesive property equal to or higher than that of the oil-based pressure-sensitive adhesive, without releasing contaminants harmful to the human body. Further, the pressure-sensitive adhesive composition of the present invention has an advantage of having excellent flame retardancy and flame retardancy.

Hereinafter, the pressure-sensitive adhesive composition of the present invention will be specifically described.

The water-based pressure-sensitive adhesive composition of the present invention includes a water-dispersible acrylic copolymer having flame retardance and flame retardancy. In the present invention, the water-dispersible acrylic copolymer can maintain the basic physical properties of the pressure-sensitive adhesive such as adhesion with an adherend. In addition, the water-dispersed acrylic copolymer may play a role of imparting flame retardancy and flame retardancy by forming a film for preventing flame transition by the curing system of the functional group contained at the initial temperature of fire (about 300 ° C).

In the present invention, the water-dispersible acrylic copolymer as described above preferably has a solid content of 50% to 70%. If the solid content is less than 50%, the stability of the emulsion is increased, but the cost may be lowered due to an increase in cost. If the solid content is more than 70%, the stability of the emulsion may be deteriorated. In addition, the acrylic copolymer preferably has a viscosity of 2000 cps to 5000 cps. If the viscosity is less than 2000 cps, the flame retardant may be precipitated. If the viscosity is more than 5000 cps, the processability of the composition may be lowered or precipitation may occur due to agglomeration.

The dispersion of the acrylic copolymer in the present invention, a weight-average molecular weight is preferably (M _w Weight average molecular weight) is 200,000 to 200 all men. If the weight-average molecular weight is less than 200,000, the durability of the pressure-sensitive adhesive may be deteriorated. If the weight-average molecular weight exceeds 200,000, the pressure-sensitive adhesive property may deteriorate. In the present invention, it is preferable that the water-dispersed acrylic copolymer has a particle diameter of 100 nm to 500 nm. If the particle diameter is less than 100 nm, the viscosity of the water-dispersible acrylic copolymer may decrease and the adhesive property after drying may deteriorate. If the particle diameter exceeds 500 nm, the cohesive force of the particles after drying tends to deteriorate, .

The water-dispersible acrylic copolymer that can be used in the present invention is not particularly limited as long as it satisfies the above-mentioned physical properties. For example, in the present invention, (meth) acrylic acid ester monomer, a,? -Unsaturated carboxylic acid containing monomer; And a polymer of a monomer mixture containing a flame retardant component-containing monomer can be used.

In the present invention, the (meth) acrylic acid ester monomer may serve as an adhesive property, and a (meth) acrylic acid alkyl ester monomer containing an alkyl group having 1 to 13 carbon atoms may be used. (Meth) acrylate, n-octyl (meth) acrylate, butyl (meth) acrylate, t-butyl ) Acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate and i-propyl (meth) acrylate. At this time, when the alkyl group contained in the (meth) acrylic acid ester monomer has a long chain of 10 to 13 carbon atoms, there is a fear that the initial cohesive force is good but the cohesive force is lowered. Therefore, in the case of such a monomer, it may be preferable to use it in combination with a (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 to 8 carbon atoms.

In the present invention, the (meth) acrylic acid ester monomer is preferably contained in an amount of 30 to 50 parts by weight, and more preferably 40 to 48 parts by weight in the water-dispersible acrylic copolymer of the present invention. If the content is less than 30 parts by weight, the adhesive property may be deteriorated. If the content is more than 50 parts by weight, the heat resistance may be deteriorated.

As used herein, "parts by weight" means "parts by weight".

In the present invention, the a, -unsaturated carboxylic acid-containing monomer serves as a crosslinking point for increasing cohesion and curing and may be at least one member selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride and crotonic acid have.

In the present invention, it is preferable that the a, -unsaturated carboxylic acid-containing monomer is contained in the water-dispersible acrylic copolymer of the present invention in an amount of 0.5 to 10 parts by weight. When the content is less than 0.5 parts by weight, cohesive strength, heat resistance and adhesion to an adherend may be deteriorated. If the content is more than 10 parts by weight, the adhesive strength and water resistance may be lowered and aging may occur depending on the temperature.

In the present invention, the flame-retardant component-containing monomer serves to impart flame retardancy and flame retardancy, and may be a vinyl-based monomer or an acrylic monomer substituted with a flame-retardant substituent. Examples of the flame retardant substituent include halogen-based compounds such as a brominated flame retardant and a chlorinated flame retardant; And alkyl benzyl substituted with an alkyl group having 1 to 5 carbon atoms. However, the types of flame retardant substituents and monomers mentioned above are merely an embodiment of the present invention, and conventional flame retardant substituents and monomers can be suitably selected and used depending on the applications in addition to the above components.

That is, the flame-retardant component-containing monomer of the present invention is not particularly limited as long as it contains the flame-retardant substituent as described above, and specifically includes halogenated styrene such as monobromostyrene, dibromostyrene, tribromostyrene and tetrabromostyrene And an alkylbenzyl acrylate monomer substituted with an alkyl group.

In the present invention, it is preferable that the flame retardant component-containing monomer is contained in an amount of 0.01 to 10 parts by weight in the water-dispersed acrylic copolymer of the present invention. When the content is less than 0.01 part by weight, it may be difficult to ensure flame retardancy and flame retardancy. If the content is more than 10 parts by weight, the adhesive strength and polymerization rate may be lowered, thereby deteriorating the adhesive property of the pressure-sensitive adhesive.

In the present invention, the water-dispersed acrylic copolymer may further include trimethylolpropane triacrylate monomer.

The trimethylolpropane triacrylate monomer improves the adhesive property through the role of a crosslinking agent in the water-dispersed acrylic copolymer and improves the flame retardancy and flame retardancy of the water-based pressure-sensitive adhesive composition.

In the present invention, it is preferable that the trimethylolpropane triacrylate monomer is contained in an amount of 0.01 part by weight to 1 part by weight in the water-dispersed acrylic copolymer of the present invention. If the content is less than 0.01 part by weight, the adhesive properties such as durability may be deteriorated. If the content is more than 1 part by weight, the adhesive strength may be lowered.

The water-dispersible acrylic copolymer of the present invention containing such a monomer component may be contained in an amount of 20 to 70 parts by weight in the pressure-sensitive adhesive composition of the present invention. If the content is less than 20 parts by weight, the adhesive property may be deteriorated. If the content is more than 70 parts by weight, the content of the tackifier and the flame retardant may be relatively decreased and flame retardancy and flame retardancy may be lowered.

The aqueous pressure-sensitive adhesive composition of the present invention may further include a tackifier. In the present invention, the tackifier can complement the adhesive property of the water-dispersible acrylic copolymer and further improve the flame retardancy and flame retardancy of the pressure-sensitive adhesive composition. In particular, when the pressure-sensitive adhesive composition of the present invention includes a flame retardant to be described later, the tackifier can perform a role of evoking flame through a flame retarding mechanism together with the flame retardant.

In the present invention, the tackifier may be preferably a tackifier resin substituted with a flame-retardant substituent.

In the present invention, the specific kind of the tackifier resin can be used without limitation as long as it can complement the adhesive property of the water-dispersible acrylic copolymer. For example, in the present invention, rosin resin, hydrogenated rosin resin, An additive terpene resin, a terpene phenol resin, a phenol resin, and a hydrocarbon resin.

The hydrocarbon resin preferably has a carbon number of 5 to 9, and more specifically, an aliphatic (C ₅ ), aromatic (C ₉ ), copolymer system of the aliphatic and aromatic hydrocarbon resin, and a hydrogenated aromatic hydrocarbon Resins and the like.

Examples of the flame retardant substituent that can be substituted for the tackifier resin in the present invention include phosphorus flame retardants, halogen flame retardants, organic flame retardants, and inorganic flame retardants.

Examples of the phosphorus-based flame retardant in the present invention include Phosphorus-Nitrogen intumescent FR (Reogard® 1000, Great Lakes), Triaryl phosphate Isopropylated, Cresyldiphenyl But are not limited to, cresyl diphenyl phosphate, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triaryl phosphate butylated, (Diphenyl phosphate), bisphenol A bis- (diphenyl phosphate), ammonium polyphosphate, phosphorus polyol, and the like. And at least one selected from the group consisting of

In the present invention, examples of the halogen-based flame retardant include monobromostyrene, dibromostyrene, tribromostyrene, tetrabromostyrene, poly (dibromostyrene) There can be mentioned poly (dibromostyrene), dibromostyrene copolymer, dibromostyrene copolymer, brominated polystryene, tetrabromophthalate ester composition, tetrabromophthalic anhydride, tetrabromophthalate diol A tetrabromophthalate diol composition, a tetrabromophthalate diol composition, a tetrabromophthalate diol composition, a tetrabromophthalate ester, a tetrabromobenzoate ester, a tetrabromobenzoate ester composition, , Hexabromocyclo Hexabromocyclododecane, tetrabromobisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A (2,3-dibromopropyl ether) (Tetrabromobisphenol A bis (allyl ether)), a phenoxy-terminated carbonate oligomer of Tetrabromobisphenol of tetrabromobisphenol A, decabromodiphenylethane, decabromodiphenyl The present invention relates to a process for producing a bis (diphenylphosphino) ethane, comprising the steps of: decabromodiphenyl oxide, 2,4,6-tribromophenol, tribromophenyl allyl ether, bis (tribromophenoxy) (tribromophenoxy) ethane, chlorinated paraffin, and chlorinated polyolefin.

Examples of the organic flame retardant in the present invention include alkylbenzyl acryl monomers substituted with an alkyl group having 1 to 5 carbon atoms.

Examples of the inorganic flame retardant in the present invention include at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, antimony trioxide, antimony pentoxide, calcium carbonate and zinc borate.

The tackifier containing the above components may be included in the pressure-sensitive adhesive composition of the present invention in an amount of 3 to 30 parts by weight. If the content is less than 3 parts by weight, the effect of increasing the adhesive strength may be insufficient. If the content is more than 30 parts by weight, the tackifier may act as a low molecular weight substance and the adhesive force may be lowered.

The aqueous pressure-sensitive adhesive composition of the present invention may further include a flame retardant. In the present invention, the flame retardant exhibits a synergistic effect (synergistic effect) together with the water-dispersed acrylic copolymer and / or the tackifier, so that the flame retardancy and flame retardancy of the tackifier can be further improved.

The flame retardant that can be used in the present invention includes at least one selected from the group consisting of a phosphorus-based flame retardant, a halogen-based flame retardant, an organic flame retardant, and an inorganic flame retardant. Specific examples thereof are as exemplified in the tackifier. Among the flame retardants of the present invention, the phosphorus-based flame retardant, in particular, is converted into polyphosphoric acid by heating at the time of combustion. The polyphosphoric acid film formed thereby acts as a protective film, and the carbon film formed by the dehydration action blocks oxygen The flame retarding effect can be exhibited. Further, in the case of the halogen-based flame retardant, the flame-retarding effect can be exhibited by stabilizing the radical reaction during the combustion reaction and blocking oxygen by the halogenated combustion gas.

The particle size of the flame retardant present in the form of powder in the present invention may preferably be 500 nm to 1 탆. If the particle diameter is less than 500 nm, the flame retardant may flocculate in the medium. If the particle diameter is more than 1 m, the flame retardant may precipitate and the uniform physical properties may not be obtained, and the adhesive property of the pressure-sensitive adhesive may be deteriorated.

The flame retardant of the present invention containing the above-mentioned components may be contained in an amount of 10 to 50 parts by weight in the pressure-sensitive adhesive composition of the present invention. If the content is less than 10 parts by weight, the desired flame retardancy and flame retardancy may not be secured. If the content is more than 50 parts by weight, the pressure-sensitive adhesive property of the pressure-sensitive adhesive composition may be deteriorated.

The aqueous pressure-sensitive adhesive composition of the present invention also includes a curing agent. In the present invention, the curing agent can perform a role of imparting flame retardancy by forming a coating for preventing flame transition by operating the curing system together with the water-dispersed acrylic copolymer at an initial fire temperature of 300 ° C or higher.

Examples of the curing agent usable in the present invention include at least one selected from the group consisting of melamine and oxazoline.

The curing agent of the present invention may be contained in an amount of 0.01 to 5 parts by weight in the pressure-sensitive adhesive composition of the present invention. When the content is less than 0.01 part by weight, the heat resistance is lowered and the curing rate is lowered. When the content is more than 5 parts by weight, the crosslinking density is too high, and the adhesive strength is lowered.

The present invention also relates to a process for producing (meth) acrylic acid ester monomers by emulsion polymerization; a,? -unsaturated carboxylic acid containing monomers; And a step of copolymerizing the flame retardant component-containing monomer to prepare a water-dispersible acrylic copolymer. The present invention also relates to a method for producing an aqueous pressure-sensitive adhesive composition according to the present invention.

The manufacturing method of the present invention may further include a step of mixing the tackifier and the flame retardant to the prepared water-dispersed acrylic copolymer after the step of preparing the copolymer.

Further, the manufacturing method of the present invention may further comprise, following the mixing step, a step of mixing a curing agent in a mixture of the water-dispersed acrylic copolymer, the tackifier and the flame retardant.

Hereinafter, each step of the production method of the present invention will be described in detail.

The production method of the present invention includes a step of producing an aqueous dispersion acrylic copolymer contained in a pressure-sensitive adhesive composition using an emulsion polymerization method. Emulsion polymerization is a kind of radical polymerization, and is a method of performing polymerization in an emulsion composed of water, a monomer, a surfactant, and the like. In the present invention, in the emulsion polymerization as described above, the (meth) acrylic ester monomer, the a,? -Unsaturated carboxylic acid-containing monomer and the flame retardant-containing monomer are used as the monomer to be polymerized. Further, trimethylolpropane triacrylate may be further used as a comonomer in emulsion polymerization. Such emulsion polymerization is usually carried out in the presence of a pH buffer substance, an initiator, an oxidation-reduction catalyst, a molecular weight regulator, an emulsifier and / or ionized water.

The type of the pH buffer material used in the emulsion polymerization of the production method of the present invention is not particularly limited, and examples thereof include at least one selected from the group consisting of sodium bicarbonate, sodium acetate and potassium bicarbonate. The pH buffer material may be used in an amount of 0.01 part by weight to 1 part by weight in the emulsion polymerization of the present invention. If the amount is less than 0.01 part by weight, it may be difficult to control the molecular weight. If the amount is more than 1 part by weight, problems such as deterioration in polymerization degree and / or formation of agglomerated particles may occur.

The kind of the initiator used in the emulsion polymerization of the production method of the present invention is not particularly limited, and examples thereof include at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate. The initiator may preferably be used in an amount of 0.05 to 5 parts by weight based on the emulsion polymerization of the present invention. If the amount is less than 0.05 part by weight, the degree of polymerization may be lowered. If the amount is more than 5 parts by weight, the molecular weight may be lowered.

In the emulsion polymerization of the production method of the present invention, an oxidation-reduction catalyst may be used. Specific examples thereof include t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, Rongalite (sodium formaldehyde sulfoxylate dehydrate) At least one selected from the group consisting of sodium metabisulfite, sodium persulfate, ammonium persulfate, sodium thiosulfate, hydrogen peroxide and L-ascorbic acid. In the present invention, at least one catalyst among the above catalysts may be used, and preferably at least two of the above catalysts may be selected and used so as to form a redox combination. The redox catalyst may be used in an amount of 0.01 to 1 part by weight based on the emulsion polymerization of the present invention. If the amount is less than 0.01 part by weight, it may be difficult to control the reaction time and to remove unreacted materials. If the amount is more than 1 part by weight, there is a possibility of causing a problem of contamination of the polymer.

Examples of the molecular weight regulator which can be used in the emulsion polymerization of the production process of the present invention include at least one selected from the group consisting of thioglycolic acid ester compounds, n-dodecyl mercaptan and lower alcohols (e.g., methanol, ethanol and butanol) . It is preferable that the molecular weight modifier is used in an amount of 0.005 part by weight to 1 part by weight in the emulsion polymerization of the present invention. When the amount is less than 0.005 parts by weight, it is difficult to control the molecular weight, and when the amount is more than 1 part by weight, the heat resistance may be deteriorated.

In the emulsion polymerization of the production process of the present invention, an emulsifier may also be used. At this time, two or more kinds selected from the group consisting of polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, carboxylic acid salt and sulfonic acid salt are used May be preferred. The emulsifier may be used in an amount of 1 to 5 parts by weight based on the emulsion polymerization of the present invention. If the amount is less than 1 part by weight, the water dispersibility may deteriorate. If the amount is more than 5 parts by weight, the water resistance may deteriorate.

Deionized water may also be added to the emulsion polymerization of the process of the present invention, and the deionized water may be used in an amount of 30 to 50 parts by weight based on the emulsion polymerization of the present invention. If the amount is less than 30 parts by weight, there is a problem of deterioration of the reaction step and formation of precipitates due to viscosity, and if it exceeds 50 parts by weight, there is a fear that drying of the post-processing phase becomes difficult.

Each of the above-mentioned components is only one specific example that can be used in the emulsion polymerization of the present invention. In the present invention, the additives used in conventional emulsion polymerization may be used without limitation, depending on the desired copolymer.

In the present invention, the polymerization reaction is carried out using a mixture of the above-mentioned respective components appropriately selected and mixed. The conditions at this time are not particularly limited. An example of such emulsion polymerization conditions is as follows. First, the deionized water and the pH buffer material are put into the reactor, the temperature is raised to about 65 ° C to 75 ° C, and the temperature is maintained for 20 to 30 minutes. Then, an initiator and an aqueous solution of an emulsifier are added to the reactor, heated to about 75 ° C to 85 ° C, and a part of a mixture obtained by pre-emulsifying the monomer to be polymerized and deionized water with an emulsifier aqueous solution is added to form a seed. Then, after about 5 to 30 minutes have elapsed, the remaining pre-emulsion mixture and initiator aqueous solution are slowly added dropwise over a period of about 20 minutes to 300 minutes. Thereafter, the mixture was aged for about 1 hour, cooled to about 50 ° C to 60 ° C, and subjected to redox reaction again for about 30 minutes to 200 minutes, followed by cooling. Thus, the water-dispersed acrylic copolymer can do. In the present invention, it is preferable to control the residual monomer content to be less than 300 ppm after the emulsion polymerization as described above. If the content of the residual monomer is 300 ppm or more, the adhesive property of the whole composition may be deteriorated.

In the production process of the present invention, a step of adding and mixing a tackifier and a flame retardant to the water-dispersed acrylic copolymer followed by water dispersion may be further performed. At this time, it is preferable that the components are mixed by a physical dispersion method using a conventional mixing means such as a homomixer, a homodisper, a planetary mixer, a high speed mixer, a dynomill, a triple roll mill or a sand mill. In the present invention, an emulsifier and / or a dispersant may be added in an amount of 0.01 to 5 parts by weight in the aqueous pressure-sensitive adhesive composition in order to improve the dispersibility of the tackifier and / or the flame retardant and to maintain a stable dispersion state. Examples of the emulsifier that can be used in this case include at least one selected from the group consisting of polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, carboxylic acid salt and sulfonic acid salt. Examples of the dispersant include fatty amine acetate a fatty acid alcohol ester, a fatty acid ester, a fatty acid acetate, an acetylenicglycol compound, an acetylenic diol compound, a fatty acid alcohol ester, a metal soap, a polar acidic ester of long chain alcohols, Polyether-modified polysiloxane, and the like, but is not limited thereto.

The production method of the present invention may further include a step of adding a hardener to the mixture followed by mixing, following the mixing step of the tackifier and the flame retardant.

At this time, it may be preferable to mix the curing agent before the coating of the mixture with the adhesive sheet. The curing agent is a substance for promoting the curing of the pressure-sensitive adhesive composition. The pre-curing of the pressure-sensitive adhesive composition can be prevented by mixing and stirring the pressure-sensitive adhesive composition before coating with the pressure-sensitive adhesive sheet.

The present invention also relates to a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing a cured product of the aqueous pressure-sensitive adhesive composition according to the present invention described above.

1 is a sectional view of a pressure-sensitive adhesive sheet 10 according to one example of the present invention. The pressure-sensitive adhesive sheet 10 of the present invention comprises a pressure-sensitive adhesive layer 11 comprising a sheet-like cured product of the pressure-sensitive adhesive composition of the present invention, as shown in Fig.

The method for curing the aqueous pressure-sensitive adhesive composition in the present invention to produce the pressure-sensitive adhesive layer is not particularly limited. In the present invention, for example, a pressure-sensitive adhesive layer can be produced by applying the pressure-sensitive adhesive composition or a coating liquid prepared by using the pressure-sensitive adhesive composition to an appropriate processing base material by a conventional means such as a bar coater and then curing. In the present invention, the curing process is preferably performed after sufficiently removing the bubble-inducing component such as volatile components or reaction residues contained in the pressure-sensitive adhesive composition or coating solution. Accordingly, the crosslinking density or the molecular weight of the pressure-sensitive adhesive is too low to lower the elastic modulus, and bubbles existing in the pressure-sensitive adhesive interface at high temperature are increased to form a scattering body therein.

The method of curing the pressure-sensitive adhesive composition or coating liquid is not particularly limited. For example, the coating layer may be cured by appropriately heating, drying or aging.

In the pressure-sensitive adhesive sheet of the present invention, the thickness of the pressure-sensitive adhesive layer may be from 20 탆 to 100 탆. In the present invention, by controlling the thickness of the pressure-sensitive adhesive layer in the above-mentioned range, excellent adhesive property, flame retardancy and flame retardancy can be exhibited even when the wallpaper is formed thin.

The pressure-sensitive adhesive sheet of the present invention may further comprise a release film formed on one side or both sides of the pressure-sensitive adhesive layer, if necessary.

2, the pressure-sensitive adhesive sheet 20 of the present invention comprises a release film (not shown) formed on both surfaces of the pressure-sensitive adhesive layer 11 21). ≪ / RTI >

The specific type of the release film used in the present invention is not particularly limited, and for example, those conventionally used in this field can be used. In the present invention, as the release film, for example, a polyester film (e.g., a PET film), a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, , An ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film may be used.

In the present invention, a suitable release process may be performed on one or both sides of the release film. In this case, examples of the release agent used in the release process include an alkyd type, a silicone type, a fluorine type, an unsaturated ester type, a polyolefin type, Among them, it is preferable to use an alkyd type, silicone type or fluorine type releasing agent from the viewpoint of heat resistance, but the present invention is not limited thereto.

In the pressure-sensitive adhesive sheet of the present invention, the thickness of the release film is not particularly limited and may be suitably selected according to the application to which it is applied. In the present invention, for example, the thickness of the release film may be about 20 탆 to 80 탆, preferably about 30 탆 to 70 탆.

The present invention also relates to a wallpaper comprising a pressure-sensitive adhesive layer containing a cured product of the above-mentioned aqueous pressure-sensitive adhesive composition according to the present invention.

The specific structure of the wallpaper of the present invention is not particularly limited as long as it is constituted using the aqueous pressure-sensitive adhesive composition according to the present invention.

Figure 3 is a cross-sectional view of a wallpaper constructed in accordance with one example of the present invention.

As shown in Fig. 3, the wallpaper 30 of the present invention comprises a substrate 31; A printing layer (32) formed on the substrate; And a pressure-sensitive adhesive layer (11) formed on the printing layer (32).

The type of the substrate used in the wallpaper of the structure shown in Fig. 3 is not particularly limited, and for example, a transparent or translucent plastic film can be used. Examples of the transparent or translucent plastic film include a polyvinyl chloride film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polyurethane film, an ethylene-vinyl acetate film , An ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film.

In the present invention, the thickness of the substrate is not particularly limited and may be suitably adjusted according to the application to which it is applied.

In addition, in the present invention, the type, formation method, or thickness of the print layer formed on the substrate is not particularly limited, and any of the general means known in the art may be used depending on the application to which the invention is applied.

In the present invention, the wallpaper may further include a primer layer formed between the substrate and the print layer.

Figure 4 is a cross-sectional view of a wallpaper constructed in accordance with another example of the present invention.

As shown in Fig. 4, the wallpaper 40 of the present invention comprises a substrate 31; A primer layer 41 formed on the substrate 31; A printing layer (32) formed on the primer layer (41); And a pressure-sensitive adhesive layer (11) formed on the printing layer (32).

In the present invention, the primer layer can improve the adhesion between the substrate and the print layer, and the kind, formation method, and thickness of the primer layer are not particularly limited, and any of ordinary means known in the art Can be used.

In the present invention, the wallpaper may further include a release film formed on the pressure-sensitive adhesive layer.

5 is a sectional view of a wallpaper constructed according to another example of the present invention.

As shown in Fig. 5, the wallpaper 50 of the present invention comprises a substrate 31; A printing layer (32) formed on the substrate (31); A pressure-sensitive adhesive layer (11) formed on the printing layer (32); And a release film (21) formed on the pressure-sensitive adhesive layer (11).

The specific type of the release film used in the present invention is not particularly limited, and for example, those conventionally used in this field can be used. In the present invention, for example, the same release film as used in the above-mentioned pressure-sensitive adhesive sheet can be used.

In the present invention, a suitable release process may be performed on one or both sides of the release film. In this case, examples of the release agent used in the release process include an alkyd type, a silicone type, a fluorine type, an unsaturated ester type, a polyolefin type, Among them, it is preferable to use an alkyd type, silicone type or fluorine type releasing agent from the viewpoint of heat resistance, but the present invention is not limited thereto.

In the wallpaper of the present invention, the thickness of the release film is not particularly limited and may be suitably selected in accordance with the application to which it is applied. In the present invention, for example, the thickness of the release film may be about 20 탆 to 80 탆, preferably about 30 탆 to 70 탆.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.

Example  One

Water dispersion  Preparation of Acrylic Copolymer (First Step)

15 parts by weight of deionized water and 0.1 part by weight of sodium bicarbonate as a pH buffer substance were poured into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and the mixture was purged with nitrogen gas and heated to 70 캜 and maintained for 30 minutes. Subsequently, 0.05 parts by weight of an aqueous solution of 5% potassium persulfate as an initiator and 0.03 parts by weight of an aqueous solution of an emulsifier (SE-10N, sodium erythorbate) were added and the temperature was raised to 80 占 폚. 10 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of butyl acrylate, 7 parts by weight of methyl acrylate, 1 part by weight of acrylic acid, 0.01 part by weight of trimethylolpropane triacrylate and 0.5 parts by weight of dibromostyrene were added , And 0.01 part by weight of a thioglycolic acid ester compound as a molecular weight regulator. Thereafter, 40 parts by weight of deionized water, 0.5 part by weight of an anionic emulsifier (SE-10N, Sodium Erythorbate), and 0.5 part by weight of a nonionic emulsifier (Aquaron RN-50, manufactured by Daicel Chemical Industries, ) (0.3 parts by weight) was added dropwise to the reactor. The mixture was aged for 10 minutes in this state, and 1 part by weight of the remaining solution of the pre-emulsion solution and 1 part by weight of an aqueous solution of ammonium persulfate (redox catalyst) of 5% was dripped constantly over 300 minutes. Thereafter, the mixture was aged for 1 hour, subjected to an oxidation-reduction reaction for 100 minutes, and then cooled to a pH of 7.

Mixing of tackifier and flame retardant (second step)

A mixture of antimony trioxide and antimony in a weight ratio of 1: 1 was blended in water at a weight ratio of 1: 1 and physically dispersed to prepare a flame retardant. Next, 60 parts by weight of the water-dispersible acrylic copolymer produced in the first step, 10 parts by weight of a rosin ester-based tackifier, and 30 parts by weight of the flame retardant were mixed. Then, 30 parts by weight of deionized water was mixed with 100 parts by weight of the mixture.

Mixing of hardener (third stage)

Before coating the mixture prepared in the second step with the adhesive sheet, 0.25 part by weight of a melamine curing agent was mixed and stirred to prepare an aqueous adhesive composition.

Example  2

7 parts by weight of methyl acrylate, 5 parts by weight of methyl acrylate, 1 part by weight of acrylic acid and 1 part by weight of maleic acid, and 0.01 parts by weight of trimethylolpropane triacrylate were dissolved in ethylene glycol dimethacrylate 0.1 part by weight, to prepare an aqueous pressure-sensitive adhesive composition.

Example  3

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that antimony trioxide and decabromodiphenyl ethanol were mixed and dispersed in water at a ratio of 1: 1 during the preparation of the flame retardant (second step).

Example  4

The aqueous adhesive composition was prepared in the same manner as in Example 1, except that 0.25 part by weight of the melamine curing agent was replaced with 0.15 part by weight of the melamine curing agent during the curing agent mixing (the third step).

Example  5

The aqueous adhesive composition was prepared in the same manner as in Example 1, except that 0.25 part by weight of the melamine curing agent was replaced with 0.5 part by weight of the melamine curing agent in the curing agent mixing (the third step).

Example  6

An aqueous adhesive composition was prepared in the same manner as in Example 1, except that 0.25 part by weight of melamine curing agent was replaced with 1.5 parts by weight of melamine curing agent in the curing agent mixing (the third step).

Example  7

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.25 part by weight of a melamine curing agent was used in place of the curing agent (third step) and 2.5 parts by weight of a melamine curing agent.

Example  8

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.25 part by weight of melamine curing agent was replaced with 0.25 part by weight of oxazoline curing agent at the time of mixing the curing agent (third step).

Example  9

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.25 parts by weight of a melamine curing agent was used in place of the curing agent (third step), and 0.5 parts by weight of an oxazoline curing agent.

Example  10

Except that 0.25 parts by weight of a melamine curing agent and 1.5 parts by weight of an oxazoline curing agent were used at the time of mixing the curing agent (the third step) to prepare a water-based pressure-sensitive adhesive composition.

Example  11

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.25 parts by weight of a melamine curing agent was used in place of the curing agent (third step), and 2.5 parts by weight of an oxazoline curing agent was used.

Comparative Example  One

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the melamine curing agent was not mixed.

Comparative Example  2

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that trimethylolpropane triacrylate was not used in the preparation of the water-dispersed acrylic copolymer (the first stage).

Comparative Example  3

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that trimethylolpropane triacrylate was not used in the preparation of the water-dispersed acrylic copolymer (the first stage) and no melamine curing agent was used.

Comparative Example  4

A pressure-sensitive adhesive composition having the same composition as that of a commercially available flame-retardant oil-based pressure-sensitive adhesive composition (Benif, LG Hausys) was prepared. Specifically, ethylhexyl acrylate, butyl acrylate, acrylic acid, and glycidyl methacrylate monomers were added to and mixed with an organic solvent to prepare an acrylic copolymer. Next, 30 parts by weight of antimony trioxide, 20 parts by weight of decabromodiphenylethane and 10 parts by weight of a rosin ester tackifier (softening point: 90 ° C) were mixed with 100 parts by weight of the acrylic copolymer to prepare an oil-based pressure-sensitive adhesive composition.

Comparative Example  5

Except that 0.2 part by weight of glycidyl methacrylate, which is an internal hardener for imparting flame retardancy, was added as a monomer of the water-dispersed acrylic copolymer in the preparation of the water-dispersed acrylic copolymer (first step) To prepare an aqueous pressure-sensitive adhesive composition.

Comparative Example  6

Except that 0.5 part by weight of glycidyl methacrylate as an internal hardener for imparting flame retardancy was added as a monomer of the water-dispersed acrylic copolymer in the preparation of the water-dispersed acrylic copolymer (the first step) To prepare an aqueous pressure-sensitive adhesive composition.

Test Example  1. Preparation of adhesive sheet and measurement of physical properties

A pressure-sensitive adhesive sheet was prepared using the pressure-sensitive adhesive composition thus prepared, and the properties of the pressure-sensitive adhesive composition were measured using the pressure-sensitive adhesive sheet. Specifically, the pressure-sensitive adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were coated on a release paper with a thickness of 50 탆 and dried at 90 캜 to 120 캜 using a PVC film as a substrate, and coated by a transfer method . Subsequently, aging was carried out at 40 ° C for 1 day, and the following adhesion, late adhesion, heat resistance, aging resistance, flame resistance and indoor air pollution were measured at 25 ° C and RH 55% under constant temperature and humidity conditions. However, PVC film was weak against heat when measuring heat resistance, so it was evaluated using PET film as a base material.

1. Initial Peel force  (Initial adhesion)

The pressure-sensitive adhesive sheet prepared using the pressure-sensitive adhesive compositions prepared in Examples and Comparative Examples was cut into a size of 25 mm x 20 cm (width x length) to prepare specimens. The specimens were subjected to three rounds of reciprocation with a 2 Kg roller in stainless steel (SUS 304) After 20 minutes had elapsed, the initial peeling force was measured using a tensile tester at a peeling speed of 300 mm / min and a peeling angle of 180 degrees.

2. Reviews Peel force  (Late adhesion)

After 1 day from the attachment to stainless steel (SUS 304), the late peeling force was measured in the same manner as the initial peeling force.

3. Aging

The same specimen as that used in the initial peel force measurement was stored at a temperature of 70 ° C for 5 days. Then, the peel force (P ₂ ) was measured in the same manner as the initial peel force, and the initial peel force (P ₁ ) The aging resistance was evaluated by substituting the general formula (1) to calculate the peeling force reduction ratio (? R).

[Formula 1]

? R = {(P ₁ - P ₂ ) / P ₁ } × 100

4. Flammability

The pressure-sensitive adhesive sheet prepared using the pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was cut into a size of 20 cm x 30 cm (width x length) to prepare specimens. The specimens were prepared according to KOFEIS 1001, The specimens were tilted at an angle of 45 degrees to evaluate flame retardancy. In this case, it is acceptable that the residue is turned off within 3 seconds, and that which can not be turned off within 3 seconds is rejected, and the flame retardancy is measured 20 times.

○: Pass 20 times / 20 times

?: Pass 15 to 19 times / 20 times

X: Pass 14 times or less / 20 times

5. Indoor air pollution

The amount of TVOC (Total Volatile Organic Compound) was evaluated according to ASTM 5116-90, and the amount of formaldehyde (HCHO) was evaluated according to EPA-11A.

The above physical property measurement results are summarized in the following Tables 1 and 2.

division Initial Adhesion (kgf / in) Late adhesion (kgf / in) Aging (%) Example 1 3100 4300 30 Example 2 3050 4250 30 Example 3 3090 4450 30 Example 4 3200 4500 15 Example 5 3000 4500 35 Example 6 2800 4450 37 Example 7 2600 4450 38 Example 8 3150 4500 33 Example 9 3000 4350 37 Example 10 2800 4450 41 Example 11 2700 4500 43 Comparative Example 1 3250 4500 30 Comparative Example 2 3300 4450 40 Comparative Example 3 3400 4450 45 Comparative Example 4 3100 4500 38 Comparative Example 5 3100 4450 65 Comparative Example 6 3100 4350 75

Flammability Indoor air pollution (mg / m ² h) Flame length: 4.5cm Flame length: 7cm TVOC HCHO Example 1 ○ X Less than 0.1 Less than 0.03 Example 2 ○ △ Less than 0.1 Less than 0.03 Example 3 ○ ○ Less than 0.1 Less than 0.03 Example 4 ○ ○ Less than 0.1 Less than 0.03 Example 5 ○ ○ Less than 0.1 Less than 0.03 Example 6 ○ ○ Less than 0.1 Less than 0.03 Example 7 ○ ○ Less than 0.1 Less than 0.03 Example 8 △ X Less than 0.1 Less than 0.03 Example 9 ○ △ Less than 0.1 Less than 0.03 Example 10 ○ ○ Less than 0.1 Less than 0.03 Example 11 ○ ○ Less than 0.1 Less than 0.03 Comparative Example 1 △ X Less than 0.1 Less than 0.03 Comparative Example 2 X X Less than 0.1 Less than 0.03 Comparative Example 3 X X Less than 0.1 Less than 0.03 Comparative Example 4 ○ ○ 0.2 to 0.4 0.05 to 0.12 Comparative Example 5 ○ △ Less than 0.1 Less than 0.03 Comparative Example 6 ○ ○ Less than 0.1 Less than 0.03

As can be seen from Tables 1 and 2, the aqueous pressure-sensitive adhesive composition prepared in Examples 1 to 11 of the present invention exhibited almost the same adhesive property as the oil-based pressure-sensitive adhesive composition of Comparative Example 4, It was found that the degree of emission of contaminants (TVOC and HCHO) was significantly reduced as compared with Comparative Example 4 corresponding to the conventional oil-based pressure-sensitive adhesive composition. In addition, in the case of Comparative Examples 1 to 3 which did not contain the curing agent and / or trimethylolpropane triacrylate of the present invention, the adhesive property was maintained, but the flame retardancy was remarkably decreased. In addition, in the case of Comparative Examples 5 and 6 in which glycidyl methacrylate was additionally contained in addition to the examples of the present invention, it was found that the degree of aging was remarkably improved as compared with the examples of the present invention.

10, 20: adhesive sheet 11: pressure-sensitive adhesive layer
21: release film 30,40,50: wallpaper
31: Base material 32: Printed layer
41: Primer layer

Claims (27)

(Meth) acrylic acid ester monomers; a,? -unsaturated carboxylic acid containing monomers; And a polymer of a monomer mixture comprising at least one flame retardant-containing monomer selected from the group consisting of monobromostyrene, dibromostyrene, tribromostyrene and tetrabromostyrene;
At least one curing agent selected from the group consisting of melamine and oxazoline; And
Wherein the flame retardant comprises at least two flame retardants selected from the group consisting of phosphorus flame retardants, halogen flame retardants, organic flame retardants and inorganic flame retardants. delete The method according to claim 1,
(Meth) acrylic acid ester monomer is at least one selected from the group consisting of 2-ethylhexyl (meth) acrylate, i-octyl (meth) acrylate, n-octyl (Meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate and i-propyl (meth) acrylate. The method according to claim 1,
Wherein the (meth) acrylic acid ester monomer is contained in an amount of 30 to 50 parts by weight in the water-dispersible acrylic copolymer. The method according to claim 1,
wherein the a,? -unsaturated carboxylic acid-containing monomer is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride and crotonic acid. The method according to claim 1,
wherein the?,? - unsaturated carboxylic acid-containing monomer is contained in the water-dispersible acrylic copolymer in an amount of 0.5 to 10 parts by weight. delete The method according to claim 1,
Wherein the flame retardant component-containing monomer is contained in an amount of 0.01 to 10 parts by weight in the water-dispersible acrylic copolymer. The method according to claim 1,
Wherein the water-dispersed acrylic copolymer further comprises trimethylolpropane triacrylate comonomer. 10. The method of claim 9,
Wherein the trimethylolpropane triacrylate comonomer is contained in the water-dispersible acrylic copolymer in an amount of 0.01 part by weight to 1 part by weight. The method according to claim 1,
Wherein the water-dispersible acrylic copolymer is contained in an amount of 20 to 70 parts by weight in the aqueous pressure-sensitive adhesive composition. The method according to claim 1,
Wherein the pressure-sensitive adhesive composition further comprises a tackifier. 13. The method of claim 12,
Wherein the tackifier is one wherein the tackifier resin selected from the group consisting of rosin resin, hydrogenated rosin resin, terpene resin, styrene-added terpene resin, terpene phenol resin, phenolic resin and hydrocarbon resin is substituted with a flame- Composition. 13. The method of claim 12,
Wherein the tackifier is contained in an amount of 3 to 30 parts by weight in the aqueous adhesive composition. delete The method according to claim 1,
Wherein the flame retardant is contained in an amount of 10 to 50 parts by weight in the aqueous pressure-sensitive adhesive composition. The method according to claim 1,
Wherein the flame retardant has a particle diameter of 500 nm to 1 占 퐉. The method according to claim 1,
Wherein the curing agent is contained in an amount of 0.01 to 5 parts by weight in the aqueous pressure-sensitive adhesive composition. (Meth) acrylic acid ester monomers through emulsion polymerization; a,? -unsaturated carboxylic acid containing monomers; Containing acrylic copolymer according to any one of claims 1 to 14, and 16 to 18, wherein the acrylic pressure-sensitive adhesive composition and the flame-retardant component-containing monomer are copolymerized to prepare a water- Gt; 20. The method of claim 19,
A method for producing an aqueous pressure-sensitive adhesive composition, which further comprises mixing a viscosity-imparting agent and a flame-retardant agent with the prepared water-dispersed acrylic copolymer. 21. The method of claim 20,
And mixing the prepared mixture with a curing agent. 20. The method of claim 19,
Wherein the emulsion polymerization is carried out using at least one selected from the group consisting of a pH buffer substance, an initiator, an oxidizing source catalyst, a molecular weight regulator, an emulsifier and ionized water. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing a cured product of the aqueous pressure-sensitive adhesive composition according to any one of claims 1 to 14, and 16 to 18. 18. A wallpaper comprising a pressure-sensitive adhesive layer containing a cured product of the aqueous pressure-sensitive adhesive composition according to any one of claims 1, 3 to 14 and 16 to 18. 25. The method of claim 24,
materials;
A printing layer formed on the substrate; And
And a pressure-sensitive adhesive layer formed on the printing layer. 26. The method of claim 25,
A wallpaper further comprising a primer layer formed between the substrate and the print layer. 26. The method of claim 25,
And a release film formed on the pressure-sensitive adhesive layer.

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