KR20210150874A - Acrylic emulsion adhesive composition and adhesive comprising the same - Google Patents

Abstract

The present invention relates to an acrylic emulsion adhesive composition that exhibits excellent adhesion, does not leave a residue on an adhered material upon removal of an adhesive after long-term storage, and is easily re-peelable. The present invention is the acrylic emulsion adhesive composition comprising: (A) latex particles comprising, a1) a first repeating unit derived from an alkyl (meth)acrylate monomer, a2) a second repeating unit derived from an unsaturated carboxylic acid monomer, and a3) a third repeating unit derived from a vinyl monomer; and (B) quaternary ammonium hydroxide.

Description

Acrylic emulsion adhesive composition and adhesive member {ACRYLIC EMULSION ADHESIVE COMPOSITION AND ADHESIVE COMPRISING THE SAME}

The present invention relates to an acrylic emulsion pressure-sensitive adhesive composition and an adhesive member.

Recently, the use of sticker-type surface finishing materials such as interior/exterior materials, interior materials, and advertisement materials for buildings to which pressure-sensitive adhesive (PSA) is applied is increasing significantly. As the adhesive, the conventional oil-based adhesive causes symptoms such as headache, irritation of the eyes and nose, cough, itching, dizziness, fatigue, and decreased concentration to people living inside the building because the residual solvent is discharged into the air for a long time after construction. When exposed for a long period of time, it causes the problem of sick house syndrome, which causes respiratory diseases, heart disease, and cancer.

For this reason, interest in water-based emulsion pressure-sensitive adhesives that are environmentally friendly and do not emit substances harmful to the human body by using water as a dispersion medium are concentrated and rapidly replaced. Aqueous emulsion pressure-sensitive adhesives are independent of the viscosity of the pressure-sensitive adhesive and the molecular weight of the dispersion polymer, so a polymer having a higher molecular weight than solvent-based polymers can be used, and a wide range of solids concentration can be obtained, aging resistance is small, low viscosity, low It has good adhesion in the solid content region and good compatibility with other polymers.

However, since water is used as a solvent, the drying speed is slow, the hydrophobic adhesive surface, the adhesiveness to the non-porous adherend is low, the selection range of the curing agent is narrow, and the initial adhesive strength is poor, as well as the emulsification. And since it contains a dispersing agent, it has problems such as not reaching the same physical properties as oil-based adhesives such as low water resistance. In particular, the water-based adhesive for clothes has a lot of dust attached to the fabric itself, so it is difficult to show adhesive properties, and after attachment, it is more often attached to the fabric than to the label. In particular, it is necessary to develop an adhesive that has excellent adhesion to the fabric for clothing and simultaneously expresses the property of being cleanly removed from the substrate. I have a problem that I am not satisfied with.

In addition, there is a problem in that the adhesive is easily exposed to a high temperature and high humidity environment in the process of being packaged and shipped to an export container after being attached to the clothing substrate, and in this process, the adhesive is strongly adhered to the clothing. In the case of the known water-based pressure-sensitive adhesive for clothes, the aging peel strength is rapidly increased to about 3 to 5 times the initial peel strength, and there is a problem in that the clothes are damaged.

An object of the present specification is to provide an acrylic emulsion pressure-sensitive adhesive composition that exhibits excellent adhesion, does not leave a residue on an adherend when the pressure-sensitive adhesive is removed after long-term storage, and is easily re-peelable.

The present specification is, a1) an alkyl (meth) acrylate-based monomer-derived first repeating unit, a2) an unsaturated carboxylic acid-based monomer-derived second repeating unit, and a3) a third repeating unit derived from a vinyl-based monomer, Latex comprising It provides an acrylic emulsion pressure-sensitive adhesive composition comprising particles (A) and quaternary ammonium hydroxide (B).

The acrylic emulsion pressure-sensitive adhesive composition has a pH of about 7 or more, specifically, about 7 to about 10, or about 8 to about 9, and may have weak basicity.

According to an embodiment of the invention, the alkyl (meth) acrylate-based monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and It may include at least one selected from the group consisting of lauryl (meth)acrylate.

In addition, the unsaturated carboxylic acid-based monomer is acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid (citraconic acid), mesaconic acid (mesaconic acid), glutaconic acid (glutaconic acid), and may include at least one selected from the group consisting of allylmalonic acid (allylmalonic acid).

In addition, the vinyl-based monomer may include alkenyl (meth)acrylate having 3 to 5 carbon atoms. Specifically, the vinyl-based monomer may include, for example, allyl (meth)acrylate, butenyl (meth)acrylate, and pentenyl (meth)acrylate.

According to another embodiment of the invention, the latex particles, with respect to 100 parts by weight of the first repeating unit, about 0.1 to about 10 parts by weight of the second repeating unit, preferably, about 0.1 to about 5 parts by weight, Or about 0.5 to about 3 parts by weight may be included.

And, the latex particles, based on 100 parts by weight of the first repeating unit, about 0.01 to about 0.5 parts by weight of the third repeating unit, preferably about 0.01 to about 0.1 parts by weight, or about 0.01 to about 0.05 parts by weight may include

In addition, the latex particles may further include a fourth repeating unit derived from diacetone acrylamide.

In this case, the fourth repeating unit derived from diacetone acrylamide is used in an amount of 0.1 to 5 parts by weight, preferably about 0.1 to about 1 part by weight, or about 0.5 to 5 parts by weight based on 100 parts by weight of the first to third repeating units. It may be included in about 1 part by weight.

According to one embodiment of the invention, the latex particles may further include adipic acid dihydrazide.

According to another embodiment of the present invention, the quaternary ammonium hydroxide may be a compound represented by the following formula (1).

[Formula 1]

(N(R1)(R2)(R3)(R4)) ⁺ (OH) ^-

In Formula 1,

R1 to R4 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 10 carbon atoms, or phenylalkyl having 7 to 10 carbon atoms.

And, the quaternary ammonium hydroxide may be included in an amount of about 0.1 to about 5 parts by weight, preferably about 0.1 to about 1 part by weight, or about 0.1 to about 0.5 parts by weight, based on 100 parts by weight of the latex particles. .

In addition, the present specification, a1) an alkyl (meth) acrylate-based monomer, a2) an unsaturated carboxylic acid-based monomer, a3) a vinyl-based monomer, and a4) a hydroxyalkyl (meth) acrylate-based monomer, including a monomer emulsion polymerization of the mixture in the presence of an emulsifier to obtain latex particles (A), a polymerization step; and adding a quaternary ammonium hydroxide (B) to the latex particles (A), comprising a neutralization step, a method for producing an acrylic emulsion pressure-sensitive adhesive composition is provided.

In addition, the present specification provides a pressure-sensitive adhesive member comprising a substrate and an adhesive layer formed on the substrate, wherein the adhesive layer includes the acrylic emulsion adhesive composition according to claim 1 .

In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

In addition, the terminology used herein is used only to describe exemplary embodiments, and is not intended to limit the present invention.

The singular expression includes the plural expression unless the context clearly dictates otherwise.

In this specification, terms such as "comprises", "comprises" or "have" are used to describe embodied features, numbers, steps, components, or combinations thereof, and include one or more other features, numbers, or steps. , components, combinations or additions thereof are not excluded.

Also in this specification, when it is said that each layer or element is formed "on" or "over" each layer or element, it means that each layer or element is formed directly on each layer or element, or other It means that a layer or element may additionally be formed between each layer, on the object, on the substrate.

Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, and should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, a1) a first repeating unit derived from an alkyl (meth)acrylate-based monomer, a2) a second repeating unit derived from an unsaturated carboxylic acid-based monomer, and a3) a third repeating unit derived from a vinyl-based monomer Including, including latex particles (A) and quaternary ammonium hydroxide (B), an acrylic emulsion pressure-sensitive adhesive composition is provided.

The inventors of the present invention, in an acrylic emulsion pressure-sensitive adhesive composition, including an emulsion of latex particles prepared by emulsion polymerization of acrylate-based monomers, etc., in addition to latex particles prepared by combining specific monomers, quaternary ammonium hydroxyl In the case of using the side, it was found that, while having excellent adhesion, it is possible to effectively prevent the occurrence of residues during peeling, and thus the present invention has been completed.

First, the acrylic emulsion pressure-sensitive adhesive composition according to an embodiment of the present invention includes an emulsion polymer of a specific monomer, that is, latex particles, and each monomer is present in the latex particle in the form of a repeating unit derived from the monomer. can

monomer

First, in the emulsion polymerization for producing the latex particles, an alkyl (meth) acrylate-based monomer may be used, which may be referred to as a first monomer. Accordingly, the latex particles may include a repeating unit derived from an alkyl (meth)acrylate-based monomer, which may be referred to as a first repeating unit.

The alkyl (meth) acrylate-based monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and lauryl (meth)acrylate It may be one or more selected from the group consisting of, and these may be used alone or in a mixture of two or more.

And, in the emulsion polymerization for producing the latex particles, an unsaturated carboxylic acid-based monomer may be used, which may be referred to as a second monomer. Accordingly, the latex particles may include a repeating unit derived from an unsaturated carboxylic acid-based monomer, which may be referred to as a second repeating unit.

In addition, the unsaturated carboxylic acid-based monomer is acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid (citraconic acid), mesaconic acid (mesaconic acid), glutaconic acid (glutaconic acid), and may include at least one selected from the group consisting of allylmalonic acid (allylmalonic acid).

The latex particles include, based on 100 parts by weight of the first repeating unit, about 0.1 to about 10 parts by weight of the second repeating unit, preferably, about 0.1 to about 5 parts by weight, or about 0.5 to about 3 parts by weight. can do.

The acrylic emulsion pressure-sensitive adhesive composition according to an embodiment of the present invention has an advantage in that, due to the content range as described above, it is possible to exhibit excellent adhesion and prevent residue generation during peeling.

And, in the emulsion polymerization for producing the latex particles, a vinyl-based monomer may be used, which may be referred to as a third monomer. Accordingly, the latex particles may include a repeating unit derived from a vinyl-based monomer, which may be referred to as a third repeating unit.

In addition, the vinyl-based monomer may include alkenyl (meth)acrylate having 3 to 5 carbon atoms. Specifically, the vinyl-based monomer may include, for example, allyl (meth)acrylate, butenyl (meth)acrylate, and pentenyl (meth)acrylate.

The latex particles may include, with respect to 100 parts by weight of the first repeating unit, about 0.01 to about 0.5 parts by weight, preferably about 0.01 to about 0.1 parts by weight, or about 0.01 to about 0.05 parts by weight of the third repeating unit. can

The acrylic emulsion pressure-sensitive adhesive composition according to an embodiment of the present invention has an advantage in that, due to the content range as described above, it is possible to exhibit excellent adhesion and prevent residue generation during peeling.

And, in the emulsion polymerization for producing the latex particles, diacetone acrylamide may be further used, which may be referred to as a fourth monomer. Accordingly, the latex particles may include a repeating unit derived from such a monomer, which may be referred to as a fourth repeating unit.

When diacetone acrylamide is used together with adipic acid dihydrazide to be described later, it is possible to increase cohesive force, aging cohesive force and water resistance without deterioration of adhesive properties.

In this aspect, the latex particles, based on a total of 100 parts by weight of the first to third repeating units, from about 0.1 to about 5 parts by weight of the fourth repeating unit, preferably from about 0.1 to about 1 part by weight, or about 0.5 to about 1 part by weight.

If the content of diacetone acrylamide is too small, the above-described effects may not be sufficiently exhibited, and there may be problems in that cohesive force, aging cohesive force and water-resistant adhesive force are lowered. If the content of diacetone acrylamide is too large, aggregates during polymerization Occurs a lot, and the initial adhesive force and peeling force may be lowered.

emulsion polymerization

The emulsion polymer included in the composition according to an embodiment of the present invention, that is, latex particles, comprises the step of emulsion polymerization of a polymerization composition comprising a monomer mixture comprising the above-described monomer component, a polymerization initiator, and an emulsifier, It can be prepared by emulsion polymerization.

In this case, the polymerization temperature and polymerization time may be appropriately determined depending on the case. For example, the polymerization temperature may be from about 50 °C to about 200 °C, and the polymerization time may be from about 0.5 hours to about 20 hours.

As the polymerization initiator usable during the emulsion polymerization, an inorganic or organic peroxide may be used, for example, a water-soluble polymerization initiator containing potassium persulfate, sodium persulfate, ammonium persulfate, and the like, cumene hydroperoxide, Oil-soluble polymerization initiators including benzoyl peroxide and the like can be used.

In addition, an activator may be further included to promote the initiation of the reaction of the peroxide together with the polymerization initiator, and such activators include sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, ferrous sulfate, and dextrose. At least one selected from the group consisting of may be used.

The polymerization initiator may be included in an amount of about 0.1 to about 10 parts by weight, preferably about 0.1 to about 5 parts by weight, based on 100 parts by weight of the monomer mixture on a dry weight basis.

According to an embodiment of the present invention, the acrylic emulsion pressure-sensitive adhesive composition may include, in addition to the above-described components, other additives within a range that does not reduce the desired effect of the invention without any particular limitation.

Specifically, it may further include an electrolyte to adjust the pH in the polymerization reaction and impart polymerization stability, for example, sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate, sodium chloride, etc. may be mentioned, but is not limited thereto. In addition, these may be used alone or in combination of two or more.

Emulsion polymerization may be specifically carried out through the following steps.

Dispersing the emulsifier in a solvent to prepare an emulsion, a first step;

A second step of preparing a pre-emulsion by mixing a monomer mixture including each monomer component and an emulsifier, etc.;

A third step of mixing the emulsion of the first step and the pre-emulsion of the second step in the presence of a polymerization initiator, and proceeding with emulsion polymerization.

In a specific embodiment of the present invention, the above-described acrylic emulsion pressure-sensitive adhesive composition, specifically, may be prepared by the following method, but is not necessarily limited thereto.

First, as a first step, an emulsion containing an emulsifier is prepared. This is separate from the following pre-emulsion preparation process.

The emulsifier may be an anionic emulsifier alone, or an anionic emulsifier, a cationic emulsifier and a nonionic emulsifier may be used together, and the emulsifier component and a solvent such as water may be mixed to prepare an emulsion.

During the emulsion preparation process, micelles having a size of several nanometers may be stably formed.

And, as a second step, in the process of preparing a pre-emulsion, including the above-mentioned monomer mixture, each of the above-mentioned monomers, emulsifiers, etc. are mixed with water to prepare a pre-emulsion. Each of the monomers may be added to the polymerization in a state of being mixed in the pre-emulsion from the beginning, and in some cases, to vary the composition according to each part of the latex particles, they may be added at different times. For example, in the case of a monomer that is added to polymerization in a mixed state from the beginning, it is uniformly distributed in the central and outer portions of the latex particles, but in the case of monomers added later at different times, it is mainly distributed in the outer portion of the latex particles. This will affect the surface properties of the latex particles.

In particular, according to an embodiment of the present invention, the first to fourth monomers are mixed with the pre-emulsion from the beginning and subjected to polymerization, and the repeating units derived therefrom are uniformly distributed in the central and outer parts of the latex particles. Preferably, the fifth monomer is added later at a different time from the first to fourth monomers, and the repeating units derived therefrom are mainly distributed in the outer shell of the latex particles, adipic acid dihydra, which will be described later. This may be desirable in terms of interaction with Zaid.

At this time, too, as the emulsifier, an anionic emulsifier may be used alone, or an anionic emulsifier and a nonionic emulsifier may be used together. In this process, in the pre-emulsion, nano-sized latex particles may be formed.

That is, the above-mentioned emulsifier may be used in any one or more of the emulsion preparation step, and the pre-emulsion preparation step.

And, as a third step, after the polymerization initiator is added to the emulsion prepared above, the pre-emulsion and the polymerization initiator are continuously added at an equal ratio for a predetermined time.

In a non-limiting embodiment of the present invention, the content of the polymerization initiator added to the emulsion may be about 0 to about 1 part by weight based on 100 parts by weight of the monomer mixture, and the content of the polymerization initiator added together with the pre-emulsion is, It may be about 0.1 to about 2 parts by weight based on 100 parts by weight of the monomer mixture, and the continuous input time may be about 3 hours to about 7 hours.

Through this process, suspended monomers or polymers in the pre-emulsion can be introduced into the initial particles produced in the emulsion.

The results of this reaction may then be subjected to a process of warming polymerization in the presence of an additional polymerization initiator, through which polymerization of the remaining monomers takes place.

In this case, the polymerization initiator may be added in an amount of about 0.1 to about 10 parts by weight based on 100 parts by weight of the monomer mixture, and the warming polymerization may proceed for about 40 minutes to about 80 minutes at a temperature of about 75 to about 85 ° C. .

The production method of such an acrylic emulsion pressure-sensitive adhesive composition is divided into an emulsion production process and a pre-emulsion production process, and thereafter, it can be carried out by a simple method of mixing the pre-emulsion with the emulsion. Process stability and productivity can be improved compared to methods for preparing an emulsion pressure-sensitive adhesive composition.

emulsifier

And, the emulsifier used in the emulsion polymerization may include at least one selected from the group consisting of anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers.

Such an emulsifier is a material having a hydrophilic group and a hydrophobic group at the same time, and during the emulsion polymerization process, a micelle structure is formed, and polymerization of each monomer can occur inside the micellar structure.

Emulsifiers generally used in emulsion polymerization may be divided into anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers, and two or more types may be mixed and used in terms of polymerization stability in emulsion polymerization.

Specifically, the nonionic emulsifier may include at least one selected from the group consisting of polyethylene oxide alkyl aryl ethers, polyethylene oxide alkyl amines, and polyethylene oxide alkyl esters.

And, the anionic emulsifier is sodium alkyl diphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene aryl ether sulfate, sodium alkyl sulfate, sodium alkyl benzene sulfonate, and dialkyl sodium sulfosuccinate It may include one or more selected from the group consisting of nates.

These may be used alone or in mixture of two or more, and may be more effective when an anionic emulsifier and a nonionic emulsifier are mixed and used, but the present invention is not necessarily limited to the type of these emulsifiers.

And, the emulsifier, for example, based on 100 parts by weight of the total monomer component used in the preparation of the latex particles, about 0.1 to about 10 parts by weight, or, about 1 to about 5 parts by weight may be used.

When the amount of the emulsifier used is too large, the particle diameter of the latex particles becomes small, and there may be problems that points and adhesion are lowered. The stability of the generated latex particles may also be deteriorated.

menstruum

According to an embodiment of the present invention, the polymerization composition may further include an aqueous solvent such as water in addition to the above-described emulsifier or monomer component.

At this time, the aqueous solvent, in terms of stability and viscosity control of the latex particles, based on 100 parts by weight of the latex particles, may be used in about 10 to about 1,000 parts by weight, for example, based on the total amount of the composition, the total It can be used so that the total solid content (TSC) is adjusted to about 10 to about 60% by weight.

When the solvent is used too little, the viscosity increases in the acrylic emulsion pressure-sensitive adhesive composition, and during emulsion polymerization, there may be problems that the stability of the latex particles is lowered. There may be problems with performance degradation.

Acrylic emulsion adhesive composition

The acrylic emulsion pressure-sensitive adhesive composition used for the pressure-sensitive adhesive member according to an aspect of the present invention includes latex particles prepared by emulsion polymerization and quaternary ammonium hydroxide as described above.

Since quaternary ammonium hydroxide contains aliphatic residues, unlike other general bases such as sodium hydroxide or aqueous ammonia, it has relatively high hydrophobicity. When applied to latex particles prepared by emulsion polymerization using such quaternary ammonium hydroxide, an ionic bond is formed with the acid group of the latex particles. The speed becomes slow and the coating property is excellent, so that a film-type adhesive surface can be formed on the coated surface. The adhesive surface in the form of a film has excellent water resistance, and it is possible to realize the advantage of reducing the build-up phenomenon of the adhesive surface.

Specifically, the quaternary ammonium hydroxide may cause the acid-base neutralization reaction with the latex particles described above. Therefore, the acrylic emulsion pressure-sensitive adhesive composition according to an aspect of the present invention includes the latex particles (A) and the quaternary ammonium hydroxide. At least a portion of the hydroxide (B) may be included in the form of a salt of latex particles (A) and quaternary ammonium hydroxide (B).

According to another embodiment of the present invention, the quaternary ammonium hydroxide may be a compound represented by the following formula (1).

[Formula 1]

(N(R1)(R2)(R3)(R4)) ⁺ (OH) ^-

In Formula 1,

R1 to R4 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 10 carbon atoms, or phenylalkyl having 7 to 10 carbon atoms.

And, the quaternary ammonium hydroxide may be included in an amount of about 0.1 to about 5 parts by weight, preferably about 0.1 to about 1 part by weight, or about 0.1 to about 0.5 parts by weight, based on 100 parts by weight of the latex particles. .

When the content of quaternary ammonium hydroxide is too small or too large, aggregation of latex particles occurs, making it difficult to implement the above-mentioned advantageous effect of forming a film-type adhesive surface on the surface to which the adhesive is applied. can

According to one embodiment of the invention, the latex particles may further include adipic acid dihydrazide.

The above-described fourth monomer, that is, diacetone acrylamide, can rapidly polymerize with various types of comonomers to form a copolymer, especially at room temperature, because it can react with the ketone group of adipic acid dihydrazide. , Adipic acid dihydrazide may be added to the acrylic emulsion pressure-sensitive adhesive composition produced by the emulsion polymerization reaction to induce a reaction between diacetone acrylamide and adipic acid dihydrazide.

When used together with diacetone acrylamide and adipic acid dihydrazide, cohesive force, aging cohesive force and water resistance can be improved without deterioration of adhesive properties.

The adipic acid dihydrazide may be included in a weight ratio of about 0.2 to about 1.0 compared to diacetone acrylamide.

If the content of adipic acid dihydrazide is too small, the interaction with diacetone acrylamide is not sufficient, so the cohesive force of the pressure-sensitive adhesive is lowered, the adhesion properties may be lowered, and residues may be generated on the adherend during peeling. can When the content of adipic acid dihydrazide is too large, the initial adhesive strength and peeling strength may be reduced, and the coating property may be deteriorated.

And, the acrylic emulsion pressure-sensitive adhesive composition has a pH of about 7 or more, specifically, about 7 to about 10, or about 8 to about 9, and may have weak basicity.

In addition, the present specification, a1) an alkyl (meth) acrylate-based monomer, a2) an unsaturated carboxylic acid-based monomer, a3) a vinyl-based monomer, and a4) a hydroxyalkyl (meth) acrylate-based monomer, including a monomer emulsion polymerization of the mixture in the presence of an emulsifier to obtain latex particles (A), a polymerization step; and adding a quaternary ammonium hydroxide (B) to the latex particles (A), comprising a neutralization step, a method for producing an acrylic emulsion pressure-sensitive adhesive composition is provided.

The polymerization step is replaced with the description of the emulsion polymerization described above.

In the neutralization step, the above-mentioned quaternary ammonium hydroxide is added to the latex particles prepared by emulsion polymerization or the acrylic emulsion and neutralized while mixing, and other neutralization reaction conditions are not particularly limited. .

adhesive member

The acrylic emulsion pressure-sensitive adhesive composition of the present invention prepared according to the above-described method may be applied to an adhesive member such as an adhesive sheet, and may be an interior material, an advertisement film, or an adhesive film or sheet of a label for clothing, but the present invention It is not necessarily limited only to these.

However, considering that the acrylic pressure-sensitive adhesive composition according to an embodiment of the present invention has a large effect of improving the residue during peeling, it may be most preferable to apply it to a label for clothing.

The adhesive member includes a substrate and an adhesive layer formed on the substrate, and the adhesive layer may include the acrylic emulsion adhesive composition according to claim 1 .

The substrate may be paper such as art paper, imitation paper, mirage paper, gold and silver paper, thermal paper, kraft paper, fluorescent paper, sterile paper, photo paper, or polymer films such as PET, PVC, PE, PP, PS, PI. have.

As described above, the acrylic emulsion pressure-sensitive adhesive composition according to an embodiment of the present invention has the advantage that it is possible to implement excellent adhesion and almost no residue is generated during peeling, and even after peeling, the surface of the adhesive target is damaged or Since it leaves almost no residue on the surface to which it was adhered, it can be preferably used as a label for clothes, etc. in particular.

Hereinafter, through specific examples of the invention, the operation and effect of the invention will be described in more detail. However, these embodiments are merely presented as an example of the invention, and the scope of the invention is not defined thereby.

<Example>

emulsion polymerization

Example 1

200 g of water and 1.5 g of emulsifier Disponil FES-77 (BASF) were placed in a 3 L glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen gas inlet tube and reflux condenser, and the inside of the reactor was substituted with nitrogen while stirring. Then, the temperature was raised to 80° C. under a nitrogen atmosphere and maintained for 60 minutes.

Separately, in a 2 L beaker, 300 g of 2-ethylhexyl acrylate (first monomer), 195 g of butyl acrylate (first monomer), 96 g of methyl methacrylate (first monomer), 6 g of acrylic acid (second monomer) Monomer), 0.2 g of allyl methacrylate (third monomer) was added and stirred for 30 minutes to prepare a monomer mixture.

Here, a solution consisting of 23 g of an emulsifier Disponil FES-77 (BASF), 2 g of sodium carbonate, and 185 g of water was added and stirred to prepare a cloudy free emulsion.

In a glass reactor containing the emulsion, 6 g of ammonium persulfate having a concentration of 5% by weight was added and dissolved by stirring for 10 minutes.

The pre-emulsion and 36 g of ammonium persulfate having a concentration of 5% by weight were evenly and continuously added to the glass reactor for 6 hours, and polymerization was carried out at 80° C., and after about 4 hours from the start of the introduction, 35% by weight of di 12 g of acetone acrylamide (fourth monomer) was added.

After the input was completed, the emulsion polymerization reaction proceeded while maintaining it at 80° C. for about 1 hour, and then it was cooled to room temperature. Here, 42 g of adipic acid dihydrazide having a concentration of 10% by weight was added and mixed for 2 hours to prepare an acrylic emulsion containing latex particles.

The acrylic emulsion was neutralized by adding 3.5 g of benzyltrimethylammonium hydroxide at a concentration of 40% by weight to obtain an acrylic emulsion pressure-sensitive adhesive composition.

Example 2

200 g of water and 1.5 g of emulsifier Disponil FES-77 (BASF) were placed in a 3 L glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen gas inlet tube and reflux condenser, and the inside of the reactor was substituted with nitrogen while stirring. Then, the temperature was raised to 80° C. under a nitrogen atmosphere and maintained for 60 minutes.

Separately, in a 2 L beaker, 300 g of 2-ethylhexyl acrylate (first monomer), 195 g of butyl acrylate (first monomer), 96 g of methyl methacrylate (first monomer), 6 g of acrylic acid (second monomer) Monomer), 0.2 g of allyl methacrylate (third monomer) was added and stirred for 30 minutes to prepare a monomer mixture.

Here, a solution consisting of 23 g of an emulsifier Disponil FES-77 (BASF), 2 g of sodium carbonate, and 185 g of water was added and stirred to prepare a cloudy free emulsion.

In a glass reactor containing the emulsion, 6 g of ammonium persulfate having a concentration of 5% by weight was added and dissolved by stirring for 10 minutes.

The pre-emulsion and 60 g of ammonium persulfate having a concentration of 5% by weight were evenly and continuously added to the glass reactor for 6 hours, polymerization was carried out at 80° C., and after about 4 hours from the start of the introduction, di 8.5 g of acetone acrylamide (fourth monomer) was added.

After the input was completed, the emulsion polymerization reaction proceeded while maintaining it at 80° C. for about 1 hour, and then it was cooled to room temperature. Here, 30 g of adipic acid dihydrazide having a concentration of 10 wt% was added and mixed for 2 hours to prepare an acrylic emulsion containing latex particles.

The acrylic emulsion was neutralized by adding 5.25 g of benzyltrimethylammonium hydroxide at a concentration of 40% by weight to obtain an acrylic emulsion pressure-sensitive adhesive composition.

Example 3

200 g of water and 1.5 g of emulsifier Disponil FES-77 (BASF) were placed in a 3 L glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen gas inlet tube and reflux condenser, and the inside of the reactor was substituted with nitrogen while stirring. Then, the temperature was raised to 80° C. under a nitrogen atmosphere and maintained for 60 minutes.

Separately, in a 2 L beaker, 300 g of 2-ethylhexyl acrylate (first monomer), 195 g of butyl acrylate (first monomer), 96 g of methyl methacrylate (first monomer), 6 g of acrylic acid (second monomer) Monomer), 0.2 g of allyl methacrylate (third monomer) was added and stirred for 30 minutes to prepare a monomer mixture.

Here, a solution consisting of 23 g of an emulsifier Disponil FES-77 (BASF), 2 g of sodium carbonate, and 185 g of water was added and stirred to prepare a cloudy free emulsion.

In a glass reactor containing the emulsion, 6 g of ammonium persulfate having a concentration of 5% by weight was added and dissolved by stirring for 10 minutes.

The pre-emulsion and 90 g of ammonium persulfate having a concentration of 5% by weight were evenly continuously added to the glass reactor for 6 hours, polymerization was carried out at 80° C., and after about 4 hours from the start of the introduction, di 12 g of acetone acrylamide (fourth monomer) was added.

After the input was completed, the emulsion polymerization reaction proceeded while maintaining it at 80° C. for about 1 hour, and then it was cooled to room temperature. Here, 21 g of adipic acid dihydrazide having a concentration of 10% by weight was added and mixed for 2 hours to prepare an acrylic emulsion containing latex particles.

The acrylic emulsion was neutralized by adding 5.25 g of benzyltrimethylammonium hydroxide at a concentration of 40% by weight to obtain an acrylic emulsion pressure-sensitive adhesive composition.

Comparative Example 1

In Example 1, in the same manner as in Example 1, except that, instead of using benzyltrimethylammonium hydroxide in the last step, 24 g of an aqueous solution of sodium hydroxide having a concentration of 10% by weight was used, the acrylic emulsion adhesive A composition was obtained.

Comparative Example 2

In Example 2, in the same manner as in Example 2, an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 2, except that, instead of using benzyltrimethylammonium hydroxide in the last step, 4.5 g of ammonia water having a concentration of 28 wt% was used. got it

Comparative Example 3

In Example 3, in the same manner as in Example 3, except that, instead of using benzyltrimethylammonium hydroxide in the last step, 32 g of an aqueous solution of sodium hydroxide having a concentration of 10% by weight was used, the acrylic emulsion adhesive A composition was obtained.

Adhesive property evaluation

The acrylic emulsion pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was applied on silicone-coated release paper, respectively, and dried in an oven at about 120° C. for about 1 minute so that the dry thickness of the pressure-sensitive adhesive layer was about 16 μm.

This was laminated with a BOPP film (Bi-Axially Oriented PP Film) to make a label for clothing, and cut to a size of 1 inch x 150 mm to prepare a label specimen for clothing.

The adhesive properties of the label specimens for clothing using the acrylic emulsion pressure-sensitive adhesive composition prepared in Examples and Comparative Examples were tested as follows. The results are shown in the table below.

Initial peel force test (90degree peel, N/inch)

Test method FINAT TEST METHOD NO. According to 2, the acrylic emulsion adhesive clothing label specimen is reciprocated once with an approximately 2 kg roller at a speed of approximately 300 mm/min, attached to a stainless steel plate, aged at room temperature for approximately 20 minutes, and then aged at room temperature for TA Texture The initial peel force (A) was measured while peeling at 90 degrees (90 degrees) at a speed of about 300 mm/min using an Analyzer device.

Aging peel force test (90degree peel, N/inch)

After attaching the label specimen to a bright stainless steel plate (SUS) substrate, press the attached sample under a load condition of about 5 kg in a thermo-hygrostat at a temperature of 25 ° C. and a relative humidity of 50%, and leave it for 4 days. The aging peel force (B) was measured in the same manner.

Build-up evaluation

With respect to the initial peel force (A) measured in 2-1, the ratio ((B-A)/A*100, %) of the aging peel force (B) measured in 2-2 was measured.

The degree of build-up of the pressure-sensitive adhesive can be measured through the change rate, and when it exceeds 70%, it can be confirmed that the build-up is not suitable as a pressure-sensitive adhesive for clothes.

Peel force (180 degree peel, N/inch) and residual rate (%) test for clothing fabric

- Sample size 1inch X 150mm

- Substrate: 100% cotton fabric or 100% polyester fabric

- Measurement conditions: 25±2℃, 50±5%RH

-Measuring method: After pressing the label sample on the selected adherend with a roller with a load of about 5 kg 5 times, inserting a glass specimen between the glasses (stacking 4 to 5 samples), temperature about 60 ℃, relative humidity After pressing the attached sample under a load of about 10 kg in a 95% thermo-hygrostat, it was aged for 2 days. After taking out the sample aged for 2 days, applying a load of about 5 kg, leaving it for about 24 hours in a constant temperature and humidity room (25±2℃, 50±5%RH) Peel force (N/inch) was measured while peeling 180 degrees (180 degrees) at a rate of /min.

In addition, after peeling, the residual ratio was applied to the amount of adhesive remaining on the fabric base material (clothing size sticker test was applied in the same manner as in the analysis method at the KOTITI clothing testing institute). The clothing testing institute observed the visible aspect of the adhesive, the presence or absence of adhesiveness when touched with the naked eye, whether the clothing was damaged, and the change in the color of the clothing to determine the residual rate.

division 90° peel
(N/inch, SUS) 180° peel
(N/inch, clothing fabric) initial peel force
(A) aging peel strength
(B) rate of change (%) peel force
(100% cotton) peel force
(100% polyester) residual rate
(100% cotton) residual rate
(100% polyester) Example 1 4.5 4.6 2 0.8 1.3 0 0 Example 2 5.5 6.2 13 1.0 1.8 0 0 Example 3 6.4 7.6 19 1.3 1.7 0 0 Comparative Example 1 3.8 5.5 45 0.6 1.4 0 0 Comparative Example 2 4.5 8.3 84 1.2 2.1 0 30 Comparative Example 3 5.6 15.0 168 1.4 2.0 20 70

As can be seen in Table 1, the Examples of the present invention can realize excellent adhesion, and it can be confirmed that the adhesion build-up phenomenon is significantly reduced after long-time storage, and that almost no residue occurs during peeling could check

In contrast, in the case of the comparative example, when compared to the example, the peel strength after aging was significantly increased, and residues were generated on the adhesive surface after peeling, and it was confirmed that problems such as poor appearance occurred when the adhesive was removed.

Claims (14)

Latex particles (A) comprising a1) a first repeating unit derived from an alkyl (meth)acrylate-based monomer, a2) a second repeating unit derived from an unsaturated carboxylic acid-based monomer, and a3) a third repeating unit derived from a vinyl-based monomer and quaternary ammonium hydroxide (B);
Acrylic emulsion adhesive composition.
According to claim 1,
A pH of 7 or more, an acrylic emulsion pressure-sensitive adhesive composition.
According to claim 1,
The alkyl (meth) acrylate-based monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and lauryl (meth)acrylate An acrylic emulsion pressure-sensitive adhesive composition comprising at least one selected from the group consisting of.
The method of claim 1,
The unsaturated carboxylic acid-based monomer is acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid acid), mesaconic acid, glutaconic acid, and allylmalonic acid comprising at least one selected from the group consisting of, acrylic emulsion pressure-sensitive adhesive composition.
The method of claim 1,
The vinyl-based monomer, an acrylic emulsion pressure-sensitive adhesive composition comprising an alkenyl (meth)acrylate having 3 to 5 carbon atoms.
The method of claim 1,
Based on 100 parts by weight of the first repeating unit, 0.1 to 10 parts by weight of the second repeating unit is included,
Acrylic emulsion adhesive composition.
According to claim 1,
Based on 100 parts by weight of the first repeating unit, containing 0.01 to 0.5 parts by weight of the third repeating unit,
Acrylic emulsion adhesive composition.
The method of claim 1,
The latex particles, further comprising a fourth repeating unit derived from diacetone acrylamide, acrylic emulsion pressure-sensitive adhesive composition.
9. The method of claim 8,
The diacetone acrylamide-derived fourth repeating unit is included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of a total of the first to third repeating units, the acrylic emulsion pressure-sensitive adhesive composition.
The method of claim 1,
Further comprising adipic acid dihydrazide, acrylic emulsion pressure-sensitive adhesive composition.
The method of claim 1,
The quaternary ammonium hydroxide is represented by the following formula (1), an acrylic emulsion pressure-sensitive adhesive composition:
[Formula 1]
(N(R1)(R2)(R3)(R4)) ⁺ (OH) ^-
In Formula 1,
R1 to R4 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 10 carbon atoms, or phenylalkyl having 7 to 10 carbon atoms.
The method of claim 1,
The quaternary ammonium hydroxide is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the latex particles, the acrylic emulsion pressure-sensitive adhesive composition.
A monomer mixture comprising a1) an alkyl (meth)acrylate-based monomer, a2) an unsaturated carboxylic acid-based monomer, a3) a vinyl-based monomer, and a4) a hydroxyalkyl (meth)acrylate-based monomer in the presence of an emulsifier By emulsion polymerization to obtain latex particles (A), polymerization step; and
A method for producing an acrylic emulsion pressure-sensitive adhesive composition comprising a neutralization step of adding a quaternary ammonium hydroxide (B) to the latex particles (A).
A substrate, and an adhesive layer formed on the substrate,
The pressure-sensitive adhesive layer comprising the acrylic emulsion pressure-sensitive adhesive composition according to claim 1, the pressure-sensitive adhesive member.