KR20090079711A - Aqueous pressure-sensitive adhesive composition, process for preparing thereof and pressure-sensitive adhesive film comprising the same - Google Patents

Abstract

An aqueous adhesive composition, its preparation method, and an adhesive film containing the composition are provided to prevent the indoor environmental contamination by preventing the discharge of contaminant due to an organic solvent. An aqueous adhesive composition comprises a water dispersible acrylic copolymer which comprises a (meth)acrylate monomer, and a monomer containing flame retardant component capable of copolymerizing with the monomer. The content of the (meth)acrylate monomer is 30 ~ 50 parts by weight and the content of the monomer containing flame retardant is 0.01 ~ 10 parts by weight in the acrylic copolymer.

Description

Aqueous pressure-sensitive adhesive composition, process for preparing beautiful and pressure-sensitive adhesive film comprising the same

The present invention relates to an aqueous pressure-sensitive adhesive composition, a method for producing the same, and a pressure-sensitive adhesive film having the same properties as those of the existing pressure-sensitive adhesive composition and having excellent flame retardancy, flame retardancy, and environmental friendliness.

Up to now, oil-based adhesives have been generally used in various decorative materials such as interior / exterior materials for construction, flooring, advertising signs, and interior materials for vehicles or aircrafts. However, since the oil-based adhesive contains an organic solvent, there is a high possibility that the indoor environment is contaminated before and after work due to the undried residual organic solvent. Accordingly, the pressure-sensitive adhesive may have a very bad effect on the health of workers and consumers due to air pollution.

Due to such a problem, the demand for an aqueous pressure-sensitive adhesive (or water-dispersible pressure-sensitive adhesive) containing no organic solvent is increasing in recent years, and many researches and developments regarding such aqueous pressure-sensitive adhesives have been made at home and abroad.

Korean Patent Laid-Open Publication No. 1996-41303 discloses an aqueous pressure-sensitive adhesive composition prepared by adding a monomer or polymer of a polyhydric alcohol to an aqueous acrylic emulsion, and Korean Patent Laid-Open Publication No. 1997-42907 discloses a high molecular weight polyacrylic acid and the like. The aqueous adhesive composition which mix | blended etc. with specific weight ratio is disclosed. Japanese Unexamined Patent Publication No. 2005-146271 also 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 with the above; And an aqueous emulsion of a tackifying resin, wherein the aqueous emulsion-type pressure-sensitive adhesive having a limited viscosity, aggregate generation rate, and amount of nonvolatile components is disclosed.

By the way, the pressure-sensitive adhesive composition disclosed in the prior document has a similar adhesive properties to the conventional oil-based adhesive, but has a problem that the flame retardancy and flame retardant, etc. are greatly reduced. That is, in recent years, in order to prevent the combustion of products and the emission of toxic gases due to fire, the flame retardancy and flame retardancy requirements for the above-described building interior / exterior materials and floor materials have been strengthened. Accordingly, to date, mainly the flame retardant treatment is performed on the material itself, but in order to secure more perfect flame retardancy and flame retardancy, the adhesive used for the material requires a certain level of flame retardant treatment.

Accordingly, even in the case of the water-based pressure-sensitive adhesive it is necessary to be provided with flame retardancy of a certain level or more along with the basic pressure-sensitive adhesive properties, a method for adding a flame retardant inorganic particles to the composition can be considered. However, in the case of the above method, satisfactory flame retardancy cannot be secured by the low dispersibility of the inorganic particles, and there is a problem that the adhesive force is greatly reduced by the addition of the inorganic particles. In order to secure dispersibility of the inorganic particles, a method of using an organic solvent as a dispersion medium may be considered, but this may cause the same contamination problem as in the case of using an existing oil-based adhesive.

As such, while having an adhesive property equivalent to or higher than that of the existing oil-based adhesive, an environment-friendly aqueous adhesive having excellent flame retardancy and flame retardancy has not been developed until now.

The present invention has been made in consideration of the above-described prior art, and has an adhesive strength equal to or higher than that of an existing adhesive, and has an object of providing an aqueous adhesive composition having excellent flame retardancy, flame retardancy, and environmental friendliness, a method for preparing the same, and an adhesive film including the same. It is done.

The present invention as a means for solving the above problems, (meth) acrylic acid ester monomer; And it provides an aqueous pressure-sensitive adhesive composition comprising a water-dispersible acrylic copolymer containing a flame-retardant component-containing monomer copolymerizable with the monomer.

It is preferable that the acryl-type copolymer of the said invention further contains a hydrophilic functional group containing monomer.

In addition, the acrylic copolymer of the present invention may further include α, β-unsaturated carboxylic acid monomer.

The aqueous pressure-sensitive adhesive composition of the present invention preferably further comprises a flame-retardant tackifier, it is preferable to use that the flame-retardant tackifier is substituted or added to the tackifying resin.

In addition, the flame retardant component included in the flame retardant tackifier of the present invention may be at least one selected from the group consisting of phosphorus flame retardant, halogen flame retardant, organic flame retardant and inorganic flame retardant.

The aqueous pressure-sensitive adhesive composition of the present invention may further include a water dispersible flame retardant, wherein the water dispersible flame retardant is preferably at least one selected from the group consisting of a phosphorus flame retardant, a halogen flame retardant, an organic flame retardant, and an inorganic flame retardant.

The present invention also provides another means for solving the above problems,

(Meth) acrylic acid ester monomers through emulsion polymerization; And it provides a method of producing an aqueous pressure-sensitive adhesive composition comprising the step of preparing a water-dispersible acrylic copolymer by copolymerizing a flame-retardant component-containing monomer copolymerizable with the monomer.

The manufacturing method of the present invention may further include mixing at least one selected from the group consisting of a flame retardant tackifier and a water dispersible flame retardant to the prepared acrylic copolymer.

The present invention is another means for solving the above problems,

Base film; And a pressure-sensitive adhesive layer formed on the base film and containing the aqueous pressure-sensitive adhesive composition according to the present invention.

The aqueous pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer having flame retardancy and flame retardancy as a main component, and optionally contains a flame retardant tackifier and / or a water dispersible flame retardant. Accordingly, the composition of the present invention exhibits excellent flame retardancy and flame retardancy along with adhesive properties and anti-aging properties equivalent to those of existing adhesives, through synergistic effects of each of the components included or combinations thereof. In addition, the water-based pressure-sensitive adhesive of the present invention has no advantage of the release of contaminants due to the inclusion of the organic solvent, there is an advantage that can prevent indoor environmental pollution on the work site and after work.

The present invention, (meth) acrylic acid ester monomer; And a water-dispersible acrylic copolymer containing a flame retardant component-containing monomer copolymerizable with the monomer. The pressure-sensitive adhesive composition of the present invention is an aqueous type containing no organic solvent, and can secure adhesive properties equivalent to those of the oil-based pressure-sensitive adhesive without releasing contaminants harmful to the human body. In addition, the composition of the present invention has the advantage of having excellent flame retardancy and flame retardancy.

Hereinafter, the aqueous pressure-sensitive adhesive composition of the present invention will be described in more detail.

The aqueous pressure-sensitive adhesive composition of the present invention includes a water-dispersible acrylic copolymer having flame retardancy and flame retardancy. In the present invention, the acrylic copolymer maintains basic physical properties such as adhesion to the adherend. In addition, the copolymer serves to impart flame retardancy and flame retardancy by forming a film to prevent the transition of the flame by the curing system of the functional groups contained at the initial temperature of fire (about 300 ℃).

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%, there is a fear that the residual moisture content of the composition is excessively increased, if it exceeds 70%, the mechanical stability of the water-dispersible acrylic copolymer particles may be lowered. In addition, the acrylic copolymer preferably has a viscosity of 200 cps or less. When the said viscosity exceeds 200 cps, there exists a possibility that the processability of a composition may fall.

Preferably, the water-dispersible acrylic copolymer has a weight average molecular weight of 200,000 to 2 million. When the said molecular weight is less than 200,000, there exists a possibility that the durability of an adhesive may fall, and when it exceeds 2 million, there exists a possibility that adhesive physical property may fall. In addition, the water-dispersible acrylic copolymer preferably has a particle diameter of 100 to 500 nm. If the particle diameter is less than 100 nm, the particle stability may deteriorate. If the particle diameter exceeds 500 nm, the cohesion force of the particles after drying may decrease, and the adhesive physical property may be deteriorated.

The acrylic copolymer that can be used in the present invention is not particularly limited as long as it satisfies the above-described physical properties. For example, in the present invention, a copolymer including a (meth) acrylic acid ester monomer as a main component may be used, and the monomer serves to impart adhesive properties to the composition. Examples of such monomers include (meth) acrylic acid alkyl ester monomers containing an alkyl group having 1 to 13 carbon atoms, specifically 2-ethylhexyl (meth) acrylate, i-octyl (meth) acrylate, n -Octyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate and i-propyl And one or more selected from the group consisting of (meth) acrylates. At this time, when the carbon number of the alkyl contained in the (meth) acrylic acid ester monomer is in the form of a long chain of 10 or more, the initial adhesive force is good, but there is a fear that the cohesive force is lowered. Therefore, in the case of the above monomers, it is preferable to use it mixed with the (meth) acrylic-acid alkylester monomer which has a C2-C8 alkyl group. The (meth) acrylic acid ester monomer is preferably included in the acrylic copolymer of the present invention 30 to 50 parts by weight, more preferably 40 to 48 parts by weight. If the content is less than 30 parts by weight, there is a risk that the adhesive physical properties are lowered, if it exceeds 50 parts by weight, the heat resistance may be lowered.

The acrylic copolymer of the present invention is further characterized by comprising a flame retardant component-containing monomer copolymerizable with the (meth) acrylic acid ester monomer. At this time, the type of monomer that can be used is not particularly limited, but it is preferable that at least one flame retardant component selected from the group consisting of halogen-based flame retardants and organic flame retardants is a substituted or added vinyl-based or acrylic monomer. Examples of the halogen-based flame retardant include bromine-based flame retardants and chlorine-based flame retardants; Examples of the organic flame retardant include alkyl benzene substituted with an alkyl group having 1 to 5 carbon atoms. However, the types of flame retardants and monomers presented above are just one aspect of the present invention, and in addition to the above components, conventional flame retardants and monomers may be appropriately selected and used according to the use.

That is, the flame retardant component-containing monomer of the present invention is not particularly limited as long as it contains the above flame retardant component, and specific examples thereof include halogenated compounds such as monobromo styrene, dibromo styrene, tribromo styrene, and tetrabromo styrene. At least one selected from the group consisting of styrene and alkyl benzyl acrylic monomers substituted with alkyl groups is included. The flame retardant component-containing monomer as described above is preferably included in an amount of 0.01 to 10 parts by weight in the acrylic copolymer of the present invention. If the content is less than 0.01 parts by weight, the desired flame retardancy may not be obtained. If the content is more than 10 parts by weight, the adhesive force and the polymerization rate may be lowered, thereby deteriorating the physical properties of the pressure-sensitive adhesive.

The water dispersible acrylic copolymer of the present invention may further include 0.1 to 5 parts by weight of a hydrophilic functional group-containing monomer. The monomer contains at least one hydrophilic functional group, serves to increase the heat resistance of the pressure-sensitive adhesive and to provide a functional group for curing. At this time, the type of hydrophilic functional group is not particularly limited, and examples thereof include at least one selected from the group consisting of a hydroxy group, an amino group, an amide group, a methylol group, an epoxy group, a phosphoric acid group, a sulfonic acid group and an isocyanate group. Specific examples of the monomer containing such a hydrophilic functional group include 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ethylene glycol di ( Meth) acrylate, glycidyl (meth) acrylate, vinyl isocyanate, N-methylol (meth) acrylamide, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, vinyl pyrrolidone, sulfoxyl One or more selected from the group consisting of ethyl (meth) acrylic acid soda and acryloyl morpholine, but is not limited thereto. The monomer is preferably included in an amount of 0.1 to 5 parts by weight in the acrylic copolymer. If the content is less than 0.1 part by weight, the heat resistance and / or curing rate may be lowered. If the content is more than 5 parts by weight, the degree of crosslinking may be too high and the adhesive force may be lowered.

The water-dispersible acrylic copolymer of the present invention may further include 0.5 to 10 parts by weight of the α, β-unsaturated carboxylic acid monomer, and the component serves to increase the cohesion of the pressure-sensitive adhesive and provide a crosslinking point for curing. Specific examples of the monomer may include one or more selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic anhydride, and crotonic acid, but is not limited thereto. The component is preferably included in an amount of 0.5 to 10 parts by weight in the acrylic copolymer. If the content is less than 0.5 parts by weight, the adhesion, heat resistance and / or cohesion may be lowered, if it exceeds 10 parts by weight, the adhesion and / or water resistance is lowered, there is a fear that aging according to the temperature.

The acrylic copolymer comprising the above components is preferably included in an amount of 20 to 70 parts by weight in the composition of the present invention. If the content is less than 20 parts by weight, there is a fear that the adhesive physical properties are lowered, if it exceeds 70 parts by weight, economical efficiency is inferior.

The water-based pressure-sensitive adhesive composition of the present invention may further include 3 to 30 parts by weight of a tackifier together with the above-described acrylic copolymer, wherein the component is a tackifier in which a flame retardant component is substituted or added (hereinafter referred to as “flame retardant adhesive”. Imparting agent "). The tackifier of the component supplements the adhesive properties of the acrylic copolymer, and the flame retardant component may serve to further improve the flame retardancy and flame retardancy of the composition. In particular, when the water-dispersible flame retardant described later in the composition of the present invention, the flame-retardant tackifier may play a role of extinguishing the flame through the flame retardant mechanism with the water-dispersible flame retardant. Examples of the tackifiers include rosin resins, male rosin resins, terpene resins, styrene-added terpene resins, terpene phenol resins, phenol resins and petroleum resins, but are not limited thereto. . The term "petroleum resin" as used above is a general term referring to a hydrocarbon resin having 5 to 9 carbon atoms, and the resin includes aliphatic (C ₅ ), aromatic (C ₉ ), aliphatic and aromatic petroleum. there may be mentioned a copolymer-based and (hydrogenated) C ₉ petroleum resins such as a resin. In addition, examples of the flame retardant component that may be substituted or added to the tackifying resin include conventional phosphorus flame retardants, halogen flame retardants, organic flame retardants and inorganic flame retardants. Phosphorus-Nitrogen intumescent FR (Reogard ^® 1000, Great Lakes), triaryl phosphates isopropylated, cresyl diphenyl phosphate (Phosphorus-Nitrogen intumescent FR) cresyl diphenyl phosphate, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, butylated triaryl phosphates butylated, resorcinol bis (diphenyl phosphate) phosphate)), bisphenol A bis (diphenyl phosphate), ammonium polyphosphate and phosphorus polyol; Examples of halogen flame retardants include poly (dibromostyrene), dibromostyrene copolymer, brominated polystyrene, tetrabromophthalate ester composition, tetrabromophthalic anhydride (tetrabromophthalic anhydride), tetrabromophthalate diol, tetrabromophthalate ester, tetrabromobenzoate ester, hexabromocyclododecane, tetrabromobisphenol A, tetrabromobisphenol A bis (2,3-dibro Mopropyl ester), tetrabromobisphenol A bis (allyl ester), phenoxy-terminated carbonate oligomer of tetrabromobisphenol A, decabromodiphenylethane, decabromodiphenyl jade Seed, 2,4,6-tribromophenol allyl ester, tribromophenyl allyl s Le, bis (tribromo phenoxy) ethane, a chlorinated paraffin (chlorinated paraffin) and is incorporated with a halogen compound or a resin such as a chlorinated polyolefin; Examples of the organic flame retardant include an alkylbenzyl acrylic monomer substituted with an alkyl group having 1 to 5 carbon atoms; Examples of inorganic flame retardants include, but are not limited to, aluminum hydroxide, magnesium hydroxide, antimony trioxide, antimony pentoxide, calcium carbonate and zinc borate. It is preferable that such a tackifier is included in the amount of 3 to 30 parts by weight in the composition. If the content is less than 3 parts by weight, the adhesive force and the flame retardant effect may be lowered. If the content is more than 30 parts by weight, the durability of the pressure-sensitive adhesive may be lowered.

The aqueous pressure-sensitive adhesive composition of the present invention may also contain 10 to 50 parts by weight of water-dispersible flame retardant, which exhibits synergistic (synergistic effect) with the acrylic copolymer and / or flame-retardant tackifier to further improve the flame retardancy of the pressure-sensitive adhesive. Can be. Examples of such water-dispersible flame retardants include phosphorus flame retardants, halogen flame retardants, organic flame retardants, and / or inorganic flame retardants, and specific examples thereof are as illustrated in the flame retardant tackifiers. Among the flame retardants of the present invention, in particular, the phosphorus-based flame retardant is converted to polyphosphoric acid by heating during combustion. The polyphosphate film thus formed acts as a protective film, and the carbon film formed by dehydration acts as oxygen. Blocking results in a flame retardant effect. In addition, the halogen-based flame retardant exhibits a flame retardant effect by stabilizing radical reaction during combustion reaction and blocking oxygen by halogenated combustion gas. The flame retardants listed above are mostly in powder form, and in the present invention, it is preferable to use flame retardants having a particle diameter of 500 nm to 1 μm. If the particle diameter is less than 500 nm, the flame retardant may aggregate in the medium. If the particle size exceeds 1 μm, the adhesive physical property of the pressure-sensitive adhesive may be lowered. If the content of such a water-dispersible flame retardant is less than 10 parts by weight, the desired flame retardancy may not be secured. If it exceeds 50 parts by weight, the adhesiveness of the composition may be lowered.

The present invention also provides a method for preparing an aqueous pressure-sensitive adhesive composition comprising the step of preparing a water dispersible acrylic copolymer by copolymerizing a (meth) acrylic acid ester monomer and a flame retardant-containing monomer copolymerizable with the monomer through emulsion polymerization. .

In the production method of the present invention, following the above steps,

Mixing at least one selected from the group consisting of a flame retardant tackifier and a water-dispersible flame retardant to the prepared acrylic copolymer may be further performed.

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

In the production method of the present invention, using an emulsion polymerization method, a step of preparing a water-dispersible acrylic copolymer contained in the pressure-sensitive adhesive composition. Emulsion polymerization is a kind of radical polymerization, a method of performing polymerization in an emulsion composed of water, monomers, surfactants and the like. In the present invention, in applying the emulsion polymerization as described above, a (meth) acrylic acid ester monomer and a flame retardant component-containing monomer are used as the monomer to be polymerized. At this time, of course, the above-mentioned hydrophilic functional group containing monomer and / or the (alpha), (beta)-unsaturated carboxylic acid monomer can further copolymerize. Such emulsion polymerization is usually carried out in the presence of a pH buffer, an initiator, a redox catalyst, a molecular weight regulator, an emulsifier and / or ionized water, and the like will be described in detail with respect to the components.

The kind of pH buffer material used at the time of emulsion polymerization of the manufacturing method of this invention is not specifically limited, For example, one or more selected from the group which consists of sodium bicarbonate, sodium acetate, and potassium bicarbonate is mentioned. The pH buffer material is preferably used in an amount of 0.01 to 1 parts by weight in the present invention. When the amount of use is less than 0.01 part by weight, it is difficult to control the molecular weight, and when it exceeds 1 part by weight, problems such as deterioration of polymerization degree and / or formation of aggregated particles may occur.

The kind of initiator used in the manufacturing method of this invention is not specifically limited, For example, one or more selected from the group which consists of potassium persulfate, sodium persulfate, and ammonium persulfate is mentioned. In the present invention, it is preferable to use the initiator in an amount of 0.05 to 5 parts by weight. If the amount of use is less than 0.05 part by weight, the degree of polymerization may be lowered. If it is more than 5 parts by weight, the molecular weight may be lowered.

In the preparation method of the present invention, a redox catalyst may be used, and specific examples thereof include t-butylhydroperoxide, benzoyl peroxide, cumene hydroperoxide, longalite (sodium formaldehyde sulfoxylate dehydrate), sodium metabisulfite, One or more selected from the group consisting of sodium persulfate, ammonium persulfate, sodium thiosulfate, hydrogen peroxide and L-ascorbic acid. In the present invention, one or more catalysts of the catalysts may be used, and preferably, two or more catalysts of the catalysts are selected and used to form a redox combination. It is preferable that the usage-amount of the said catalyst is also 0.01-1 weight part. If the amount is less than 0.01 part by weight, it may be difficult to control the reaction time and remove the unreacted substance. If the amount is more than 1 part by weight, there may be a problem of contamination of the polymer.

Examples of molecular weight modifiers that can be used in the present invention include one or more selected from the group consisting of thioglycolic acid ester compounds, n-dodecylmercaptan and lower alcohols (ex. Methanol, ethanol and butanol). In this case, it is preferable that the usage-amount is 0.005-1 weight part. If the amount of use is less than 0.005 parts by weight, it is difficult to control the molecular weight, and if it exceeds 1 part by weight, heat resistance may deteriorate.

In the present invention, an emulsifier may also be used, and at this time, it is preferable to use two or more selected from the group consisting of polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, carboxylate and sulfonate. In addition, the emulsifier is preferably used in an amount of 1 to 5 parts by weight in 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 be lowered.

In the present invention, deionized water may also be added, in which the amount is preferably 30 to 50 parts by weight. If the amount is less than 30 parts by weight, there is a problem of deterioration of the reaction process due to viscosity and the formation of precipitates. If the amount is more than 50 parts by weight, it may be difficult to dry after processing.

Each component described above is just one example that can be used in the emulsion polymerization of the present invention, in the present invention can be used without limitation additives used in normal emulsion polymerization according to the desired copolymer.

In this invention, a polymerization reaction is advanced using the mixture which suitably selected and mixed each above-mentioned component, and the conditions at this time are not specifically limited. One aspect of such emulsion polymerization conditions is as follows. First, deionized water and pH buffer material are placed in a reactor, heated to about 65-75 ° C., and held for 20-30 minutes. Subsequently, an initiator and an emulsifier aqueous solution are added to the reactor and heated to about 75 to 85 ° C., and then a portion of the mixture in which the monomer to be polymerized and deionized water is pre-emulsified with an aqueous emulsifier solution is added to form a seed. Thereafter, at about 5 to 30 minutes, the remaining preemulsion mixture and the aqueous initiator solution are slowly added dropwise for about 20 to 300 minutes. Thereafter, after the mixture is aged for about 1 hour, the temperature is lowered to about 50 to 60 ° C. and redoxed for about 30 to 200 minutes, followed by cooling, to prepare the water-dispersible acrylic copolymer of the present invention. have. 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. When content of the said residual monomer is 300 ppm or more, there exists a possibility that the adhesiveness of the whole composition may fall.

In the production method of the present invention, after the emulsion polymerization step, a step of adding a water-retardant tackifier and a water-dispersible flame retardant to the water-dispersible acrylic copolymer, and mixing, and further water dispersion. At this time, the mixing of the components is preferably carried out through a physical dispersion method using a conventional mixing means such as homo mixer, homo disper, planetary mixer, high speed mixer, dynomill, sambon roll mill or sand mill. In the present invention, an emulsifier and / or dispersant may also be added in an amount of about 0.01 to 5 parts by weight in order to improve dispersibility of the tackifier and / or flame retardant and maintain the dispersed state. Examples of the emulsifier that can be used at this time include one or more selected from the group consisting of polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, carboxylate and sulfonate, and examples of the dispersant include fatty amine acetate (fatty amine acetate), acetylenic glycol compounds, acetylenic diol compounds, fatty acid alcohol esters, metal soaps, polar acidic esters of long chain alcohols (polar acidic esters) And polyether modified polysiloxane (polyether modified polysiloxane) may be one or more selected from the group consisting of, but is not limited thereto.

The present invention also provides a base film; And

It is related with the adhesive film formed on the said base film, and containing the adhesive layer containing the aqueous adhesive composition which concerns on this invention.

With reference to the accompanying Figure 1 will be described in detail the adhesive film of the present invention.

As the base film 10 of the pressure-sensitive adhesive film of the present invention, a general film in this field can be used without limitation, and examples thereof include a polyethylene film, a polypropylene film, and an EVA film. ), PVC film (polyvinylchloride film), PVDC film (polyvinyliolene chloride film), PS film (polystyrene film), PC film (polycarbonate film), PA film (polyamide film), PET film (poly (ethylene terephthalate) film), PVAC A film (polyvinylalcohol film), a PU film (polyurethane film), a PTFE film (polytetrafluoroethylene film), an acrylic resin film, etc. are mentioned. The film may also have a release treatment on its surface. Examples of the releasing agent used in the releasing treatment may include alkyd, silicone, fluorine, unsaturated ester, polyolefin or wax, and among them, it is preferable to use alkyd, silicone or fluorine-based releasing agent. .

In the pressure-sensitive adhesive film of the present invention as described above, the thickness of the base film 10 and the pressure-sensitive adhesive layer 20 is not particularly limited, and may be appropriately selected according to the use to which the pressure-sensitive adhesive film is applied. In addition, the method of manufacturing such an adhesive film is not specifically limited, either, For example, the aqueous adhesive composition of this invention can be apply | coated to a base film with a predetermined thickness, and can be manufactured through a post process, such as drying.

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

Example  One

Preparation of Water Dispersible Acrylic Copolymer (Step 1)

15 parts by weight of deionized water and 0.1 parts by weight of sodium bicarbonate were placed in a reactor equipped with a stirrer, a reflux condenser, a dropping machine and a thermometer, purged with nitrogen gas, and then heated to 70 ° C and maintained for 30 minutes. Subsequently, 0.05 weight part of 5% aqueous potassium persulfate aqueous solution and 0.03 weight part of an emulsifier (SE-10N, Adecaria sorbate company make; Sodium Erythorbate) aqueous solution were added as an initiator, and it heated up at 80 degreeC. 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, 0.2 part by weight of glycidyl acrylate, 0.01 part by weight of trimethylolpropane triacrylate, and 0.5 weight part of dibromo styrene was added, and 0.01 weight part of thioglycolic acid ester compounds were added as a molecular weight regulator. After that, 40 parts by weight of deionized water and 0.5 parts by weight of anionic emulsifier (SE-10N, made by Adeka Riaso Co., Ltd.), and 0.3 parts by weight of non-ionic emulsifier (Aqualon RN-50, Daiichi Kogyo Seiyaku (made)) A portion (1.25% by weight) of the added preemulsion liquid was added dropwise to the reactor. It was aged for about 10 minutes in that state, and the remaining preemulsion liquid and 5% of ammonium persulfate aqueous solution were dripped uniformly over 300 minutes. Thereafter, the mixture was aged for 1 hour, the redox reaction was performed for 100 minutes, and then cooled to calibrate to pH 7.

Mixing flame retardant tackifier and water dispersible flame retardant (second step)

Antimony trioxide and decabromodiphenyl oxide were combined with water 1: 1 and physically dispersed to prepare a water dispersible flame retardant. Subsequently, 60 parts by weight of the water-dispersible acrylic copolymer prepared above, 10 parts by weight of a flame retardant tackifier (a mixture of rosin ester and triphenyl phosphate) and 30 parts by weight of the prepared water dispersible flame retardant were mixed. Subsequently, 30 parts by weight of deionized water was mixed with respect to 100 parts by weight of the prepared mixture to obtain an aqueous pressure-sensitive adhesive composition.

Example  2

In preparing the water-dispersible acrylic copolymer, 7 parts by weight of methyl acrylate is added 5 parts by weight of methyl methacrylate, 1 part by weight of acrylic acid is 1 part by weight of maleic acid, and 0.01 part by weight of trimethylolpropane triacrylate is 2-hydroxypropyl methacrylate. An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.1 parts by weight was used.

Example  3

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that antimony trioxide and decabromo diphenyl ethane were mixed with water 1: 1 to prepare a water-dispersible flame retardant.

Comparative example  One

An aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that dibromo styrene was not added in preparing the water-dispersible acrylic copolymer, and rosin ester containing no triphenyl phosphate was used as a tackifier.

Comparative example  2

In the preparation of the water-dispersible acrylic copolymer, without adding dibromo styrene and using a rosin ester without triphenyl phosphate as a tackifier, the content of the water-dispersible flame retardant was increased from 30 parts by weight to 45 parts by weight. And an aqueous pressure-sensitive adhesive composition was prepared in the same manner as in Example 1.

Comparative example  3

The pressure-sensitive adhesive of the same composition as the flame-retardant oil-based pressure-sensitive adhesive composition used in the prior art was prepared. Specifically, ethylhexyl acrylate, butyl acrylate, acrylic acid and glycidyl methacrylate monomer were added to the organic solvent and mixed to prepare an adhesive resin. Subsequently, 30 parts by weight of antimony trioxide, 20 parts by weight of decabromodiphenylethane, and a rosin ester tackifier (softening point: 90 ° C.) were mixed with respect to 100 parts by weight of the prepared adhesive resin to prepare an adhesive composition.

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

After the pressure-sensitive adhesive film was prepared using the prepared pressure-sensitive adhesive composition, the physical properties of the pressure-sensitive adhesive composition were measured using the pressure-sensitive adhesive composition. Specifically, based on the PVC film, the pressure-sensitive adhesive compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were applied to a release paper at a thickness of 50 μm, dried at 90 to 120 ° C., and coated by transfer. Thereafter, the mixture was aged at 40 ° C. for 1 day, and the adhesion, late adhesion, heat resistance, aging resistance, flame resistance, and indoor air pollution were measured under constant temperature and humidity conditions of 25 ° C./55 RH%. However, when measuring the heat resistance was evaluated using a PET film instead of a PVC film that is weak to heat.

1. Initial Peel force  (Initial Adhesion)

The prepared pressure-sensitive adhesive film was cut into 25 mm × 20 cm (width × length) to prepare a test piece, which was attached to stainless steel (SUS 304) by reciprocating three times with a roller of 2 kg and 300 mm / min after 20 minutes. The peel force was measured at the peel rate.

2. Reviews Peel force  (Late adhesion)

The measurement was performed in the same manner as in the initial peel force measurement described above, except that the peel force was measured one day after the attachment.

3. Anti-aging

The same test piece as used for peeling force evaluation was stored at 70 degreeC for 5 days. This was attached to stainless steel (SUS 304), and after 20 minutes, the peeling force was measured in the same manner as the initial peeling force measurement, and the falling ratio with respect to the initial peeling force was calculated.

4. Flameproof

Flame retardant performance was evaluated by tilting the test specimen at a 45 degree angle in accordance with the KOFEIS 1001 standard. At this time, it is a pass that an image is extinguished within 3 seconds, and it is a rejection that is not extinguished within 3 seconds, and it was repeated 20 times and flameproofness was measured.

○: 20 passes / 20 trials

△: 15 to 19 times pass / 20 times

Ｘ: 14 or less pass / 20 pass

5. Indoor Air Pollution Degree

The amount of TVOC (total volatile organic compound) was evaluated by ASTM 5116-90 method, and the amount of formaldehyde (HCHO) was evaluated by EPA-11A method.

Physical properties measured as described above are summarized in Tables 1 and 2 below.

TABLE 1

Initial adhesion (( kgf ) / in ) Late stage adhesion (( kgf ) / in ) Aging (%) Example  One 3050 4400 61 Example  2 3050 4350 55 Example  3 3100 4450 63 Comparative example  One 3350 4600 62 Comparative example  2 2750 3650 59 Comparative example  4 3100 4450 40

TABLE 2

Flameproof Indoor air pollution degree ( mg / m ² h) Fireworks (4.5 cm ) Fireworks (7 cm ) TVOC HCHO Example  One ○ ○ 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 Comparative example  One X X Less than 0.1 Less than 0.03 Comparative example  2 ○ ○ Less than 0.1 Less than 0.03 Comparative example  3 - - 0.2 to 0.4 0.05 to 0.12

As can be seen from Tables 1 and 2, the water-based pressure-sensitive adhesive composition prepared in Examples 1 to 3 of the present invention has excellent anti-flame properties while showing nearly the same adhesive properties as those of Comparative Examples 1 and 3, In particular, it was found that the degree of release of contaminants was significantly reduced compared to Comparative Example 3 corresponding to the existing oil-based pressure-sensitive adhesive composition. In addition, in Comparative Example 2, which does not include the flame retardant component-containing monomer according to the present invention, but includes a large amount of water-dispersible flame retardant, the flame retardant and contaminant release characteristics were relatively excellent, but it was found that the adhesive properties were remarkably inferior.

1 is a cross-sectional view of an adhesive film according to one embodiment of the present invention.

<Description of Drawing>

10: base film

20: adhesive layer

Claims (21)

(Meth) acrylic acid ester monomers; And a water-dispersible acrylic copolymer containing a flame retardant component-containing monomer copolymerizable with the monomer. The method of claim 1, (Meth) acrylic acid ester monomer is 2-ethylhexyl (meth) acrylate, i-octyl (meth) acrylate, n-octyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acryl Aqueous, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate and i-propyl (meth) acrylate is an aqueous adhesive composition, characterized in that at least one selected from the group consisting of. The method of claim 1, (Meth) acrylic acid ester monomer is an aqueous adhesive composition, characterized in that contained in the acrylic copolymer in an amount of 30 to 50 parts by weight. The method of claim 1, The flame-retardant component-containing monomer is an aqueous pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of halogen-based flame retardant and organic flame retardant is a substituted or added vinyl or acrylic monomer. The method of claim 1, The flame-retardant component-containing monomer is an aqueous pressure-sensitive adhesive composition, characterized in that contained in the acrylic copolymer in an amount of 0.01 to 10 parts by weight. The method of claim 1, An aqueous adhesive composition, wherein the acrylic copolymer further comprises 0.1 to 5 parts by weight of a hydrophilic functional group-containing monomer. The method of claim 6, Hydrophilic functional group-containing monomers include 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, glycidyl ( Meta) acrylate, vinyl isocyanate, N-methylol (meth) acrylamide, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, vinyl pyrrolidone, sulfoxyl (meth) acrylic acid soda and acryloyl Aqueous pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of morpholine. The method of claim 1, The acrylic copolymer further comprises 0.5 to 10 parts by weight of an α, β-unsaturated carboxylic acid monomer. The method of claim 8, The aqueous adhesive composition, wherein the α, β-unsaturated carboxylic acid monomer is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid and crotonic acid. The method of claim 1, An aqueous adhesive composition, wherein the acrylic copolymer is included in the composition in an amount of 20 to 70 parts by weight. The method of claim 1, An aqueous pressure-sensitive adhesive composition, characterized by further comprising a flame-retardant tackifier in which the flame-retardant component is substituted or added to the tackifying resin in an amount of 3 to 30 parts by weight. The method of claim 11, The tackifying resin is at least one selected from the group consisting of a rosin resin, a water addition rosin resin, a terpene resin, a styrene-added terpene resin, a terpene phenol resin, a phenol resin and a petroleum resin. The method of claim 11, The flame retardant component is an aqueous pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of a phosphorus flame retardant, halogen flame retardant, organic flame retardant and inorganic flame retardant. The method of claim 13, Phosphorus-based flame retardants include phosphorus-nitrogen intumescent FR, isopropylated triaryl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, butylated triaryl phosphate, resorcinol bis (di Phenyl phosphate), bisphenol A bis (diphenyl phosphate), ammonium polyphosphate and phosphorus polyols, Halogen-based flame retardants include poly (dibromostyrene), dibromostyrene copolymer, brominated polystyrene, tetrabromophthalate ester composition, tetrabromophthalic anhydride, tetrabromophthalate diol, tetrabromophthalate ester, tetrabromo Benzoate ester, hexabromocyclododecane, tetrabromobisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ester), tetrabromobisphenol A bis (allyl ester), tetrabromobisphenol Phenoxy-terminal carbonate oligomer of A, decabromodiphenylethane, decabromodiphenyl oxide, 2,4,6-tribromophenol allyl ester, tribromophenyl allyl ester, bis (tribromophenoxy) At least one selected from the group consisting of ethane, chlorinated paraffin, and chlorinated polyolefin, The organic flame retardant is an alkylbenzyl acrylic monomer substituted with an alkyl group having 1 to 5 carbon atoms, The inorganic flame retardant is an aqueous pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, antimony trioxide, antimony pentoxide, calcium carbonate and zinc borate. The method of claim 1, An aqueous pressure-sensitive adhesive composition, characterized in that it further comprises in an amount of 10 to 50 parts by weight of the water-dispersible flame retardant. The method of claim 15, The water-dispersible flame retardant is an aqueous pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of a phosphorus flame retardant, halogen flame retardant, organic flame retardant and inorganic flame retardant. The method of claim 15, The water-dispersible flame retardant is an aqueous pressure-sensitive adhesive composition, characterized in that the particle size is 500 nm to 1 ㎛. A method for producing an aqueous pressure-sensitive adhesive composition comprising the step of preparing a water-dispersible acrylic copolymer by copolymerizing a (meth) acrylic acid ester monomer and a flame retardant-containing monomer copolymerizable with the monomer through emulsion polymerization. The method of claim 18, And a step of mixing at least one selected from the group consisting of a flame retardant tackifier and a water dispersible flame retardant to the prepared water dispersible acrylic copolymer. The method of claim 18, Emulsion polymerization is carried out using at least one selected from the group consisting of pH buffers, initiators, redox catalysts, molecular weight regulators, emulsifiers and ionized water. Base film; And The adhesive film formed on the said base film, and containing the adhesive layer containing the adhesive composition of any one of Claims 1-17.

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