WO2019117539A1 - Aqueous acrylic pressure-sensitive adhesive for clothing, and preparation method therefor - Google Patents

Abstract

The present invention relates to an aqueous acrylic pressure-sensitive adhesive for clothing, and a preparation method therefor. Since a predetermined amount of a specific internal cross-linking agent is used during polymerization of an acrylic emulsion resin, glass transition temperature and degree of internal cross-linking are controlled while resin properties are maintained to be identical to those of a conventional adhesive, and thus the residual ratio of a pressure-sensitive adhesive can be greatly reduced when the pressure-sensitive adhesive is removed from a substrate such as fabric for clothing.

Description

 2019/117539 1 »(: 1 ^ {2018/015465

Title of the Invention

 Aqueous acrylic pressure-sensitive adhesive for clothes and a method for producing the same

 Mutual citation with related applications

 This application claims the benefit of priority based on Korean Patent Application No. 10-2017-01735 dated December 15, 2017, and Korean Patent Application No. 10-2018-0156144 dated December 6, 2018, The entire contents of which are incorporated herein by reference. The present invention relates to an aqueous acrylic pressure-sensitive adhesive for clothing, in which the residual property at the time of removing the pressure-sensitive adhesive in clothing fabrics and the like is greatly improved, and a method for producing the same.

BACKGROUND ART [0002]

Recently, the use of sticker-type surface finishing materials such as inner / outer materials, interior materials, and advertisement materials of the briquettes using pressure-sensitive adhesive (PSA) has been greatly increased. Conventional oil-based pressure-sensitive adhesives, as the pressure-sensitive adhesive, have a problem of causing headache, irritation of the eyes, cough, itching, dizziness, fatigue, loss of concentration, etc. due to the residual solvent being discharged into the air for a long time after the construction And exposure to prolonged exposure causes problems with Sick House Syndrome, which causes respiratory diseases, heart disease, and cancer. For this reason, water-based emulsion pressure sensitive adhesives that are environmentally friendly and do not emit harmful substances to the human body have been focused and replaced rapidly by using water as a dispersion medium. The aqueous emulsion pressure-sensitive adhesive can use a polymer having a higher molecular weight than the solvent-based polymer because the viscosity of the pressure-sensitive adhesive and the molecular weight of the dispersion polymer are independent of each other, and the concentration range of the solid content can be widely obtained and the aging resistance is low, It has good adhesiveness in a solid content region and has good compatibility with other polymers. 2019/117539 1 »(: 1 ^ {2018/015465

However, since water is used as a solvent, there is a problem that the drying speed is slow, the adhesiveness to the hydrophobic adhesive surface and the non-porous adhesive agent is low, the selection range of the curing agent is narrow and the initial adhesive force is low, And a dispersing agent, it has a problem that it can not reach the physical properties as the kerosene pressure-sensitive adhesive having a low water resistance. In addition, since many dusts adhere to the garment fabric itself, the water-based pressure-sensitive adhesive for clothing is difficult to exhibit the adhesive property, and after attaching, there are many cases where the garment is attached to the fabric more than the label. In particular, it is necessary to develop a pressure-sensitive adhesive which exhibits excellent adhesion to a cloth for clothing and simultaneously exhibits properties that are cleanly removed from a substrate. Both of these properties are opposite to each other, so that when one of them becomes higher, I have a problem that I am not satisfied with. DETAILED DESCRIPTION OF THE INVENTION

 [Technical Problem]

 The present invention relates to a water-based acrylic pressure-sensitive adhesive for clothing which is excellent in adhesive strength to a garment fabric itself and has a remarkably improved residue property to remain a pressure-sensitive adhesive on the fabric base material when the pressure- And a method for producing the same.

[Technical Solution]

 According to an embodiment of the present invention,

 (Meth) acrylic acid ester monomer together with a monomer mixture containing at least one comonomer containing a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group, and an aqueous acrylic emulsion Resin,

The internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide, allyl-methylcarbamate, 1,6-nucleic acid diol diacrylate, 2019/117539 1 »(: 1 ^ {2018/015465

Nucleic acid diol ethoxylate diacrylate, nucleic acid diol propoxylate diacrylate, pentaerythritol ethoxylate triacrylate,

Pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, and divinylbenzene,

 The internal crosslinking agent is added to 100 parts by weight of the acrylic emulsion resin,

0.02 to 0.25 parts by weight,

 An aqueous acrylic adhesive for clothing is provided. Further, according to another embodiment of the present invention,

 (Meth) acrylic acid ester monomer together with a monomer mixture containing at least one comonomer containing a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group, an internal cross- ≪ / RTI >

 And emulsion-polymerizing the pre-emulsion to prepare an acrylic emulsion resin,

 Wherein the internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide, allyl-methylcarbamate, 1,6-nucleic acid diol diacrylate, nucleic acid diol ethoxylate diacrylate, Diacrylate, pentaerythritol ethoxylate triacrylate,

Pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, and divinylbenzene,

 Wherein the internal cross-linking agent is mixed in an amount of 0.02 to 0.25 parts by weight based on 100 parts by weight of the monomer mixture,

There is provided a process for producing the aforementioned aqueous acrylic pressure-sensitive adhesive for clothing. Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or preliminary meaning and the inventor may define the concept of the term appropriately in order to describe his or her invention in the best way Based on principles 2019/117539 1 »(: 1 ^ {2018/015465

And should be construed in light of the meanings and concepts consistent with the technical idea of the invention. Also, " comprising " as used herein should be interpreted as specifying the presence of particular features, integers, steps, operations, elements and / or components, The present invention will now be described in more detail with reference to preferred embodiments of the aqueous acrylic pressure-sensitive adhesive for clothes of the present invention and a method for producing the same.

 According to one embodiment of the present invention, there is provided a composition comprising (meth) acrylic acid ester monomer and at least one comonomer including a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a vinyl ester group, a cyano group, a styrene group and a carboxyl group And an aqueous acrylic emulsion resin obtained by emulsion-polymerizing a monomer mixture and an internal cross-linking agent, wherein the internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide, allyl-4-methylcarbamate, - nucleic acid diol diacrylate, nucleic acid diol ethoxylate diacrylate, nucleic acid diol propoxylate diacrylate, pentaerythritol ethoxylate triacrylate,

Pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, and divinylbenzene, and the internal crosslinking agent is used in an amount of 0.02 to 0.25 wt% based on 100 parts by weight of the acrylic emulsion resin A water-based acrylic pressure-sensitive adhesive for clothing. In the present specification, the aqueous acrylic pressure-sensitive adhesive is an acrylic emulsion pressure-sensitive adhesive using water as a dispersion medium, and includes an acrylic emulsion resin having water resistance and tackiness to a garment fabric. Also, as used herein, the term "monomer mixture ", as used herein, refers to a mixture of one or more monomers, 2019/117539 1 »(: 1 ^ {2018/015465

State, and the one or more monomers may be prepared by putting them together, or they may be sequentially added to one another, and the production method thereof is not limited. The monomer mixture is not particularly limited as long as the acrylic emulsion resin is polymerized, and one or more various monomers well known in the art can be used. The inventors of the present invention have conducted continuous experiments to solve the problem of residues in which the adhesive component remains much on the surface of the clothing when the conventional water-based adhesive for clothing is removed. According to the results of the experiment, when the kind and content of the specific internal cross- It is possible to maintain the physical properties equal to or greater than those of the prior art and to reduce the residual ratio when the aqueous adhesive is removed from the fabric for clothes. Preferably, the internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide and allyl-N-methylcarbamate, 1,6-nucleic acid diol diacrylate, nucleic acid diol ethoxylate diacrylate , Nucleic acid diol propoxylate diacrylate, pentaerythritol ethoxylate triacrylate,

Use pentaerythritol tall tree propoxy triacrylate, and vinyl trimethoxysilane, di least _one element selected from the group consisting of divinylbenzene. Particularly, the internal cross-linking agent has a high shear characteristic as a component to be added to reinforce the cohesive force at the most basic level in the reaction mixture. Thus, the cross-linking agent has an excellent effect of enhancing the net effect by connecting long polymer chains. The most important feature of the shear is the cohesive force between the polymers, which helps to firmly fix the dried latex without getting torn easily. In addition, it can also prevent the film produced in roll form from leaking sideways due to its weight. The internal crosslinking agents are characterized by having a double bond or an acrylate group reactive on both sides of the molecule. 2019/117539 1 »(: 1 ^ {2018/015465

The internal crosslinking agent may be used in an amount of about 0.02 part by weight to about 0.25 part by weight, or about 0.024 part by weight to about 0.15 part by weight, or about 0.029 part by weight to about 0.1 part by weight, If the amount of the internal cross-linking agent is less than about 0.02 parts by weight, there is a problem that the adhesive remains on the clothes, and when the amount of the cross-linking agent is more than about 0.25 parts by weight, . Although each of the other factors can occur, it has a feature that it sensitively affects the attachment of clothes even with a slight change in characteristics. Here, 100 parts by weight of the acrylic emulsion resin is a mixture of the content of the (meth) acrylic acid ester monomer and the content of a comonomer including a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group, Quot; refers to the sum of the content of the external crosslinking agent used in the process. For example, 100 parts by weight of the acrylic emulsion resin does not include the content of components added after the polymerization process as described later even if it is an external crosslinking agent. The present invention focuses on improving the residue characteristics of the adhesive remaining on the fabric for clothing while keeping the physical properties the same as before. In particular, when the method of the present invention is used in the course of polymerizing an aqueous adhesive for clothing, the physical properties can be maintained similar to the conventional ones while improving the residual properties. Thus, it is possible to overcome the problem of residues on the fabric for clothing while maintaining high physical properties, compared with the conventional method of lowering the adhesive force and eliminating the adhesive remaining on the substrate. As described above, the aqueous acrylic pressure sensitive adhesive of this embodiment may contain at least one comonomer containing a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrenic group and a carboxyl group together with a (meth) acrylic acid ester monomer The monomer mixture and the internal cross-linking agent are emulsion-polymerized 2019/117539 1 »(: 1 ^ {2018/015465

And an aqueous acrylic emulsion resin. The (meth) acrylic acid ester monomer is not limited as long as it is a (meth) acrylic acid ester monomer having an alkyl group of 0- (318), that is, an alkyl group having 1 to 18 carbon atoms. For example, the (meth) acrylic acid ester monomer may be selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate, _11-amyl (meth) acrylate, isoamyl (meth) acrylate, _11-haeksil (meth) acrylate, _11-heptyl (meth) acrylate, _11- octyl (meth) acrylate, octyl (meth) acrylate, _II gyetil haeksil (meth) acrylate, 2-ethyl haeksil (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, phenyl (Meta) acrylate, diallyl (meth) acrylate, dodecyl (meth) acrylate, and cyclohexyl (meth) acrylate, lauryl Acrylate, or a combination of two or more thereof. Specifically, one or two or more selected from among methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethyl nylon (meth) acrylate may preferably be used. The (meth) acrylic acid ester monomer may be present in an amount of about 30% by weight or greater, or about 30% by weight to about 99% by weight, or about 45% by weight, or about 55% Or from about 80% to about 98.5% by weight of the composition. When the content of the (meth) acrylic acid ester monomer is less than about 30% by weight, the initial adhesion can not be secured, and thus the problem may not be adhered to the clothes. However, when the monomer is constituted only by the (meth) acrylic acid ester monomer, 2019/117539 1 »(: 1 ^ {2018/015465

The transfer of the pressure-sensitive adhesive to the adherend occurs largely during the removal after use, and the detergency is deteriorated, which is not preferable. In a further preferred embodiment of the invention, the methyl (meth) acrylate in the (meth) acrylic acid ester monomer is present in an amount of from about 5% to about 25%, or from about 8% to about 20% , Or from about 10% to about 18% by weight, and the remaining (meth) acrylic acid ester monomers, such as butyl (meth) acrylate and 2-ethyl Or from about 25 wt% to about 94 wt%, alternatively from about 40 wt% to about 40 wt% to about 88 wt%, alternatively from about 50 wt% to about 50 wt% to about 85 wt% Or from about 55% to about 83% by weight of the composition. Particularly, in the case of only a monomer having a long-chain alkyl group such as butyl (meth) acrylate and 2-ethyl nylon (meth) acrylate, a polymer having a glass transition temperature of the resin (1 is extremely low and soft _0? ) Is formed , So that it is preferable that proper composition of the monomer and the comonomer is achieved since the residue is largely generated. In particular, the physical properties of the pressure-

, The content ratio of each of the monomer and the comonomer becomes important. It is desirable to adjust the proportion of the remaining monomers so as to obtain a suitable adhesive property. The monomer mixture may further comprise, in addition to the (meth) acrylate monomer, at least one comonomer including at least one selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group do. Among them, it is preferable to use a comonomer including a benzene group from the standpoint of stability. The comonomer may be present in an amount of up to about 10 parts by weight, or from about 0 to about 10 parts by weight, or up to about 6 parts by weight, or from about 1 to about 6 parts by weight, or up to about 4 parts by weight, based on 100 parts by weight of the (meth) acrylic acid ester monomer May be added in an amount of about 2 to 4 parts by weight. When the content of the comonomer is more than 10 parts by weight 2019/117539 1 »(: 1 ^ {2018/015465

If it is contained, it is undesirable because it becomes excessively firm and a decrease in adhesion may occur. However, since the pressure-sensitive adhesive becomes too soft to exhibit excessive adhesive property and transfer may occur, it is preferable to include a comonomer in a minimum amount or more. As one example of the comonomer, the monomer containing a hydroxy group is at least one monomer selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypoly (meth) acrylate,

Hydroxypropyl (meth) acrylate, and hydroxypropyl (meth) acrylate. The monomer containing the hydroxy group may be added in an amount of about 10 parts by weight or about 0 to 10 parts by weight, about 5 parts by weight or about 1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer , Preferably about 1 to 3 parts by weight, per 100 parts by weight of the reaction mixture. The monomer containing an epoxy group includes, but is not limited to, glycidyl methacrylate and allyl glycidyl ether. Here, the monomer containing the epoxy group may be added in an amount of about 10 parts by weight or about 0 to 10 parts by weight, or about 5 parts by weight or about 1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer , Preferably about 1 to 3 parts by weight, per 100 parts by weight of the reaction mixture. The monomer containing the cyano group includes, but is not limited to, acrylonitrile and methacrylonitrile. Here, the monomer containing the cyano group may be added in an amount of about 10 parts by weight or less, about 0 to 10 parts by weight, about 5 parts by weight or about 1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer And preferably about 1 to 3 parts by weight. 2019/117539 1 »(: 1 ^ {2018/015465

The styrenic monomers containing styrenic groups include, but are not limited to, styrene and (X-methyl styrenes). The styrenic monomer may be added in an amount of about 10 parts by weight or less, or about 0 to 10 parts by weight, or about 6 parts by weight or about 1 to 6 parts by weight, based on 100 parts by weight of the (meth) acrylic acid ester monomer May be mixed in about 1 to 4 parts by weight. In addition, the monomer containing a carboxyl group includes, but is not limited to, acrylic acid, itaconic acid, maleic anhydride, fumaric acid, crotonic acid methacrylic acid, and ethylmethacrylic acid. In particular, by using the monomer containing a carboxyl group, the storage stability of the latex can be improved. Herein, the monomer containing a carboxyl group may be added in an amount of about 10 parts by weight or less, or about 0 to 10 parts by weight, about 5 parts by weight or about 1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer , Preferably about 1 to 3 parts by weight, per 100 parts by weight of the reaction mixture. According to a preferred embodiment of the present invention, the monomer mixture contains about 55% by weight to about 99% by weight or about 80% by weight of the (meth) acrylic acid ester monomer under the condition that the total weight of the whole mixture is 100% To 98.5% by weight, and may include about 0.5% by weight to about 10% by weight, or about 1% by weight to about 5% by weight, of the comonomer containing the styrene group, and the comonomer To about 10% by weight, or from about 0.5% to about 3% by weight, based on the total weight of the composition. Specifically, the monomer mixture may include, for example, 2-ethylnucyl acrylate From about 30 wt% to about 60 wt%, or from about 45 wt% to about 55 wt%, of styrene 1) from about 0.5 wt% to about 10 wt%, or from about 1 wt% to about 5 wt% , And methyl methacrylate (MMA , From about 5 wt% to about 25 wt%, or from about 10 wt% to about 20 wt%, of butyl acrylate, from about 20 wt% to about 40 wt%, or from about 25 wt% 2019/117539 1 »(: 1 ^ {2018/015465

To about 35% by weight, and may include acrylic acid (about 0.5% to about 10% by weight, or about 0.5% to about 3% by weight, based on the weight of the acrylic acid). According to one embodiment of the present invention, The acrylic emulsion resin may contain other additives in addition to the above-mentioned components, without any particular limitation, so long as it does not deteriorate the object of the invention. For example, the additive may include a surfactant, a buffer, an external crosslinking agent, And may further include one or two or more of them. Specifically, the polymerization reaction may further include a surfactant used for initial particle generation, size control of the generated particles, stability of particles, and the like Such a surfactant is composed of a hydrophilic group and a lipophilic group, and is divided into an anion, a cation and a nonionic surfactant, and mainly contains an anion and a nonionic surfactant The surfactant may be, for example, sodium polyoxyethylene alkyl ether sulfate (various kinds depending on the EO group), di But are not limited to, diphenyl oxide disulfonate, sodium lauryl sulfate, sodium alkyldiphenyl oxide disulfonate, or sodium methyl allyl sulfonate. For example, a surfactant having a phenyl group can attract non-polar monomers, and a surfactant having a methyl ally group can accept a large number of monomers because the molecule is not so large in _particular, each of the surfactant composition is adjusted to be able to slightly About 1 part by weight or about 0.3 part by weight to about 1 part by weight, or about 0.8 part by weight based on 100 parts by weight of the above acrylic emulsion resin is about 1.3 parts by weight or about 0 part by weight to about 1.3 parts by weight, Or from about 0.5 part by weight to about 0.8 2019/117539 1 »(: 1 ^ {2018/015465

If the amount of the surfactant is more than 1.3 parts by weight, the adhesive property may be changed, which is not preferable. In one embodiment, the composition of the surfactant is about 0.2 parts by weight to about 0.8 parts by weight or about 0.3 parts by weight to about 0.7 parts by weight of sodum polyethylene alkyl ether sulfate, and diphenyl oxide disulfonate and sodium lauryl sulfate 0.1 part by weight to about 0.5 part by weight or about 0.2 part by weight to 0.4 part by weight. In addition, it may further include an electrolyte or a buffer to adjust the pH in the polymerization reaction and to impart polymerization stability. For example, sodium bicarbonate, sodum carbonate, sodium phosphate, soymium sulfate, But is not limited thereto. These may be used alone or in combination of two or more. The buffer may be included in an amount of about 0.5 part by weight or about 0 to about 0.5 part by weight, about 0.3 part by weight or about 0 to about 0.3 part by weight based on 100 parts by weight of the acrylic emulsion resin. Further, it may further include an external crosslinking agent serving as an intercross linker, which is added to the acrylic emulsion resin at the end portion of the polymerization process to link the polymer and the polymer. Specifically, the external crosslinking agent is designed so that a crosslinking reaction takes place mainly on the outside using diacetone acrylamide (DAAM) and adipic acid dihydride (ADH) as an external crosslinking agent. About 0.5 parts by weight or less, or about 0.5 parts by weight to about 1.2 parts by weight, or about 0.9 parts by weight or less, or about 0.6 parts by weight or less, based on 100 parts by weight of the acrylic emulsion resin 0.9 part by weight. In addition, it may further include a wetting agent which acts as an emulsifier for lowering the surface tension for the purpose of coating, and the content thereof may be used within a range well known in the art. For example, the wetting agent may include dioctyl sodium sulfosuccinate-based compounds, 2019/117539 1 »(: 1 ^ {2018/015465

An acrylic emulsion resin can be included as about 1.5 parts by weight or less based on 100 parts by weight or about 0.5 parts by weight to about _L5 parts by weight, or about _1.2 parts by weight or less, or about 0.8 parts to about 1.2 parts by weight. On the other hand, the resin may serve as a chain transfer agent (CTA) during the polymerization reaction of the resin, and may further include a molecular weight controlling agent which is attached to the end of the molecule to transfer the radical to another site and to perform a termination reaction. , It can play a role in improving the initial adhesive strength by reducing the molecular weight by using a little amount or using a small amount because residue may be generated when using as a pressure sensitive adhesive for clothes. For example, a very small amount of 3-Mercaptopropionic acid or the like which can be adjusted only by a small amount in a shorter length than a well-known n-DDM (1-dodecanethiol) can be used in a very small amount. Since there is a high possibility that a wig may be produced, it is preferable not to use it in a pressure sensitive adhesive for clothes. The acrylic emulsion resin may have a glass transition temperature (Tg) of about -60 ^° C to -20 ^° C, or about -50 ^° C to -30 ^° C, or about -45 ^° C to -40 ^° C. The glass transition temperature (Tg) of the acrylic emulsion resin can be measured using a differential scanning calorimeter (DSC, DSC 2920, manufacturer: TA instrument). Specifically, the acrylic emulsion resin was heated up to 80 ^° C, maintained at that temperature for 5 minutes, cooled again to -50 ^° C, and then increased in temperature. 5 ^° C / min. In the 2nd cycle, acrylic emulsion resin can measure glass transition temperature (Tg). Process for producing aqueous acrylic pressure-sensitive adhesive for clothing

According to another embodiment of the present invention, there is provided a method for producing an aqueous acrylic pressure-sensitive adhesive for clothing as described above _. The method for producing an aqueous acrylic pressure-sensitive adhesive for clothing according to the present invention comprises: \ ¥ 0 2019/117539 1 »(: 1 '/ ¾32018 / 154641

(Meth) acrylic acid ester monomer together with a monomer mixture containing at least one comonomer containing a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group, an internal cross- ≪ / RTI >

 Emulsion polymerization of the pre-emulsion to prepare an acrylic emulsion resin;

 Lt; / RTI >

 Wherein the internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide and allyl-methylcarbamate, 1,6-nucleic acid diol diacrylate, nucleic acid diol ethoxylate diacrylate, Diacrylate, pentaerythritol ethoxylate triacrylate,

Pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyl trimethoxy silane, and divinyl benzene,

 The internal cross-linking agent is used in an amount of 0.02 to 100 parts by weight,

0.25 parts by weight. In particular, the internal cross-linking agent may be present in an amount of from about 0.02 parts by weight to about 0.25 parts by weight, or from about 0.024 parts by weight to about 0.15 parts by weight, or from about 0.029 parts by weight to about 0.1 parts by weight, If the amount of the internal cross-linking agent used is less than about 0.02 part by weight, there is a problem that the final produced pressure-sensitive adhesive remains on the clothes, and when the amount of the internal cross-linking agent is more than about 0.25 parts by weight, There is a problem in not sticking to the surface. Although each of the other factors can occur, it has a feature that it sensitively affects the attachment of clothes even with a slight change in characteristics. The method according to one embodiment of the present invention includes preparing a pre-emulsion by using a specific internal cross-linking agent in an optimal range, adding a surfactant, an initiator, etc. to the acrylic- And a step of producing an acrylic pressure-sensitive adhesive using a car exterior crosslinking agent. 2019/117539 1 »(: 1 ^ {2018/015465

Specifically, the method of the present invention will be described step by step. Wherein the step of preparing the pre-distemper dog comprises the step of preparing a monomer mixture comprising at least one comonomer including a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrenic group and a carboxyl group together with a (meth) acrylic acid ester monomer, And the cross-linking agent may be respectively taken in the content ranges as described above, mixed with water and stirred for a predetermined time. The comonomer containing the functional group selected from the group consisting of the (meth) acrylic acid ester monomer and the hydroxyl group, the epoxy group, the cyano group, the styrene group and the carboxyl group, the components, the composition and the content of the internal crosslinking agent are as described above. The pre-emulsion may contain, in addition to the (meth) acrylic acid ester monomer, the comonomer, and the internal cross-linking agent, other additives without particular limitation within a range not to deteriorate the desired effect of the invention. For example, the additive may include a surfactant, a buffer, an external crosslinking agent, a wetting agent, and the like, and one or more of the additives may be further included. The composition, content, etc. of the surfactant, buffer, external crosslinking agent, wetting agent, and other additives are as described above. In order for the preparation of the pre-emulsion to be smooth, the order in which the awakening ingredients are injected is important. At the beginning of the polymerization process, additives such as a surfactant and a buffering agent are first dissolved in water and dissolved. Thereafter, a monomer mixture such as a (meth) acrylic acid ester monomer and a comonomer, an internal cross-linking agent, . On the other hand, the step of producing the acrylic emulsion resin comprises: 2019/117539 1 »(: 1 ^ {2018/015465

The pre-emulsion can be added in proportion to the polymerization initiator. In order to manifest the characteristics of the external crosslinking agent, a cross-linking point must exist outside the polymer. Therefore, the external crosslinking agent may be added to the polymerization end to carry out the reaction. And emulsion polymerization in the presence of an external crosslinking agent at the end of the polymerization. Particularly, the polymerization initiator may be a water-soluble polymerization initiator such as persulfate of ammonium or alkali metal, hydrogen peroxide, peroxide, hydroperoxide and the like, and may be used together with one or more reducing agents to perform emulsion polymerization reaction at low temperatures, But is not limited thereto. At this time, the content of the polymerization initiator may be about 0.1 part by weight to about 1.5 parts by weight based on 100 parts by weight of the acrylic emulsion resin. Further, the polymerization initiator may be appropriately divided in the above-mentioned range after being divided at least one time in the polymerization step of the acrylic emulsion resin described later. In addition, an external crosslinking agent serving as an intercross linker, which is added to the acrylic emulsion resin at the end portion of the polymerization process to link the polymer and the polymer, can be further used. The emulsion polymerization may be carried out at a temperature of from about 70 [deg.] C to about 90 for about 3 hours to about 8 hours. In consideration of the physical properties of the pressure-sensitive adhesive, the polymerization temperature may be about 75 ° C to about 85 ^° C. The polymerization initiator may be used alone or in combination with one or more of a polymerization initiator and a reducing agent . The components such as the polymerization initiator and the reducing agent used in the polymerization reaction can be applied to the above-described components and contents of the acrylic emulsion resin of the present invention without any particular limitation. In the present invention, in order to reduce the residual monomer, a stripping process is applied and a vacuum is used together with water to remove residual monomer. However, in recent years, the addition time of the polymerization initiator is increased, The time was extended to allow additional reaction. If the reaction is continued at a high temperature, the change over time is greatly reduced and a more stable product can be supplied. 2019/117539 1 »(: 1 ^ {2018/015465

Further, in order to facilitate the stability of the reaction and the pH control, an electrolyte or a buffer component may be further added in the polymerization step. Specific components may be added to the acrylic emulsion resin of the present invention, . ≪ / RTI > A wetting agent serving as an emulsifier for lowering the surface tension for coating can be used as a main ingredient. The specific components of the wetting agent can be applied to the acrylic emulsion resin of the present invention, However, instead of applying the electrolyte, buffer, wetting agent, and other additives at a room temperature, they are added at a high temperature, which is in a state of being aged after the polymerization is completed, to obtain a stable product having a good viscosity and pH It is possible. The aqueous acrylic pressure-sensitive adhesive provided according to this method can be specifically applied as a pressure-sensitive adhesive sheet for clothes. Therefore, the aqueous acrylic pressure-sensitive adhesive can be effectively applied to the fabric base material for clothing, and when the pressure-sensitive adhesive is removed, the residual rate of the pressure-sensitive adhesive can be reduced while meeting the same or better physical properties. For example, the acrylic pressure sensitive adhesive according to the present invention can reduce the residual rate of the garment fabric to at least about 8% or from about 0 to about 8%, more preferably the residual rate of the acrylic pressure sensitive adhesive is less than about 6% Or about 6%, or about 5% or less, or about 0 to about 5%, or about 4.5% or about 0 to about 4.5%. The retention rate can be applied to the KOTITI garment testing laboratory in the same manner as the analysis method. After the label sample is pressed on the selected clothing fabric 5 times with a roller of about 5 kg load, the glass sample is sandwiched between glass 4 or 5 sample stacks), the samples attached at a load of about 5 kg in a thermostat at a temperature of about 60 ° C and a relative humidity of 95% are pressed and aged for 3 days (5 kg Weight). Here, 100% polyester fabric or 100% cotton fabric or 52% polyester fabric and 48% cotton fabric are used for the garment fabric. The sample aged for 3 days was taken out and applied with a load of about 5 kg. The sample was allowed to stand in a constant temperature and humidity chamber (about 24 ° C, about 60%) for about 24 hours and taken out. TA (Texture Analyzers) 180 degree peel By removing the label fountains by regular method, 2019/117539 1 »(: 1 ^ {2018/015465

It can be measured by applying the residual rate to the amount of adhesive remaining on the substrate. Further, according to the present invention, in addition to the improvement of the residual ratio, the peeling force, the initial tack, and the shear value of the acrylic pressure-sensitive adhesive can all show excellent results. For example, the aqueous acrylic pressure sensitive adhesive may also have a peel force of about 2.4 N / inch or greater, or about 2.4 N / inch to about 12 N / inch, or about 3.0 N / inch or about 3.0 N / inch To about 12 N / inch, or about 4.0 N / inch or about 4.0 N / inch to about 12 N / inch. Here, the peel force is measured by the test method FINAT TEST

METHOD NO. 2 can be measured. For example, a label specimen for an acrylic emulsion pressure sensitive adhesive garment may be reciprocated one or more times at a speed of about 300 mm / min with a roller of about 2 kg to adhere it onto a glass or HDPE, stainless steel plate (bright steel steel plate) After aging at room temperature for 20 minutes, measure with a TA Texture Analyzer at a rate of about 300 mm / min and peel at 90 degrees. The target value may be about 2.4 N / inch or more, preferably about 3.0 N / inch or more, on a stainless steel plate. The aqueous acrylic pressure sensitive adhesive may also have an initial tack of at least about 6.0 N / inch or about 6.0 N / inch to about 24 N / inch, or about 9.0 N / inch or about 9.0 N / inch, About 2.5 N / inch or about 2.5 N / inch to about 12 N / inch, or about 3.0 N / inch or about 3.0 N / inch to about 12 N / inch for HDPE film . Here, the initial tack can be measured using glass or HDPE as the adherend, and the temperature is about 22 ± 2 ^° C and the relative humidity is about

5 < RTI ID = 0.0 > 5% RH. ≪ / RTI > For example, the specimen is made into a loop shape and fixed to the clamp, and the specimen is attached to glass or high density polyethylene (HDPE) film at a constant speed. After about 5 seconds, measure the force corresponding to the peak value at the measurement speed of about 300 mm / min when separating in the opposite direction by the loop tack peel force. The target value is about 2019/117539 1 »(: 1 ^ {2018/015465

More than about 6.0 N / inch, preferably about 9.0 N / inch or more, and about 2.5 N / inch or more, and preferably about 3.0 N / inch or more, for HDPE film. The aqueous acrylic pressure sensitive adhesive may also have a shear of at least about 3600 minutes, or at least about 4500 minutes, or at least about 4800 minutes. Here, the holding force may be determined by a holding power test (shear test) method, and may be a value measured under a condition of a temperature of about 22 ± 2 ^° C and a relative humidity of about 5 ± 5% RH. For example, a bright stainless steel plate (Bright SUS: shiny and slippery) was prepared, and the pressure-sensitive adhesive specimen was reciprocated once with a roller of about 2 kg and attached to the adherend surface, Retention force is measured without dwell time. After applying a fixed load of about 1 kg to the bottom of the sample, measure the time when the adhesive sample has fallen. The target value can be set to about 3600 minutes or more.

【Effects of the Invention】

 In the present invention, the internal crosslinking agent such as allyl methacrylate is optimally used in the process of polymerizing the water-based pressure-sensitive adhesive for clothing to maintain the physical properties equal to or more than that of the prior art, and the pressure- Thereby realizing stable residue characteristics.

DETAILED DESCRIPTION OF THE INVENTION

 BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

<Examples>

 Example 1

The preemulsion was prepared by mixing the monomer mixture, the internal crosslinking agent and water as follows, and then the preemulsion was subjected to emulsion polymerization to prepare an acrylic emulsion resin. 2019/117539 1 »(: 1 ^ {2018/015465

First, 290.2 g of a potion and 290.2 g of a 26% by weight sodium polyoxyethylene lauryl ether sulfate as a surfactant were added to a 2 L glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser ) Was added, and the inside of the reactor was replaced with nitrogen while stirring. Then, the temperature was raised to about 80 ° C under a nitrogen atmosphere, and the temperature was maintained for about 60 minutes. _. Separately, about 314.9 g of butyl acrylate (BA), about 503.0 g of 2-ethylhexyl acrylate (2-EHA) and about 1 M of methyl methacrylate (MMA) in a beaker. ³ g, the styrene (SM) was prepared from about 20.3 g, acrylic acid (AA) monomer mixture 1000.0 g mixed for huyak In 30 minutes about 10.5 g. Then, about 0.3 g of allyl methacrylate (AMA) as an internal cross-linking agent, about 25 g of sodium polyoxyethylene lauryl ether sulfate (about 26% by weight) as a first surfactant, about 25 g of sodium polyoxyethylene lauryl ether sulfate 2 surfactant consisting of about 30% by weight of sodium lauryl sulfate, about 10 g of sodium lauryl sulfate, about 2 g of sodium carbonate as a wetting agent, about 2 g of sodium methylallylsulfonate as a third surfactant, and about 220 g of water And the mixture was mixed with a stirrer to prepare a white emulsion pre-emulsion. To the 2 L glass reactor containing the surfactant, about 5% by weight of ammonium persulfate and about 10 g of ammonium sulfate were added and dissolved by stirring for about 10 minutes. The pre-emulsion prepared above and about 150 g of about 5% by weight aqueous ammonium sulfate solution were continuously added to the glass reactor continuously for about 4 hours. After about 3 hours from the start of the polymerization, (DAAM) as a primary external crosslinking agent in an amount of about 50% aqueous solution and about 14 g of DAAM (about 7 g of DAAM), which is about 0.7 part by weight based on 100 parts by weight of the acrylic emulsion resin, Respectively. Thereafter, about 5 g of an aqueous solution of ammonium persulfate of about 5 wt% was further added to the reactor in which the polymerization proceeded, the temperature was maintained ^at about 80 ^° C for about 1 hour, Acrylic emulsion resin was prepared. 2019/117539 1 »(: 1 ^ {2018/015465

Then, about 10 wt% aqueous ammonia solution was added to the acrylic emulsion resin to adjust the pH to about 7 to about 8.5. Thereafter, adipic acid dihydride (ADH) was prepared as an about 10% aqueous solution as a secondary external crosslinking agent to be injected in the subsequent step, and about 0.35 parts by weight of an about 0.35 part by weight based on 100 parts by weight of the acrylic emulsion resin Was added to the reaction mixture in which the pH was adjusted to a content of 35 g (about 3.5 g of ADH in an actual weight), and further added with a wetting agent serving as an emulsifier for lowering the surface tension for coating, About 1 part by weight of Dioctyl sodium sulfosuccinate was added to 100 parts by weight of the acrylic emulsion resin and the mixture was stirred at a temperature of about 25 ^° C for about 60 minutes to prepare an acryl based pressure sensitive adhesive composition. Example 2

As it is shown in the following Table 1, butyl acrylate and 2-ethyl _§ 500.0田reagent haeksil acrylic ray

To about 312.0 _& internal cross-linking agent is allyl acrylate standing meta except for using in an amount of about 1 _§, in Example 1, the acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner. Example 3

As shown in following Table 1, butyl acrylate and 2-ethyl yeosi 312.0 is haeksil acrylate (2-班1 shows) to about 500.0 _and about an internal cross-linking agent allyl methacrylate (used in an amount of about _£ 0.07 when show 1 , An acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 1. Comparative Example 1

To a 2 L glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, about 290.2 g of water and 26 wt% sodium polyoxyethylene lauryl ether sulfate as a first surfactant ) Was added, and the inside of the reactor was replaced with nitrogen while stirring, and then a nitrogen atmosphere 2019/117539 1 »(: 1 ^ {2018/015465

RTI ID = 0.0 &gt; 80 C &lt; / RTI &gt; and maintained for about 60 minutes. Separately, about 314.4 g of butyl acrylate, about 401.8 g of 2-ethylhexyl acrylate, about 50.4 g of methyl methacrylate, about 202.6 g of vinyl acetate, about 20.3 g of styrene (SM) and 10.5 g of acrylic acid were added to the beaker, 1000.0 g of a monomer mixture mixed for 30 minutes was prepared. Then, about 1.5 g of polyethylene glycol 400 diacrylate (M280) as internal crosslinking agent, about 25 g of sodium polyoxyethylene lauryl ether sulfate (about 26% by weight as a first surfactant), about 25 g of sodium polyoxyethylene lauryl ether sulfate About 10 g of sodium lauryl sulfate, about 2 g of sodium carbonate as a buffer, about 2 g of sodum methyl allylsulfonate as a third surfactant, and about 230 g of water as a second surfactant Methacrylamidoethyl ethylene urea (WAM) was prepared in an about 50% aqueous solution, added in an amount of about 2 silver, and mixed with a stirrer to prepare a white emulsion pre-emulsion. To the 2 L glass reactor containing the surfactant, about 5% by weight of ammonium persulfate and about 10 g of ammonium sulfate were added and dissolved by stirring for about 10 minutes. Then, about 150 g of the pre-emulsion prepared as described above and about 5% by weight aqueous ammonium sulfate solution were continuously and continuously injected into the glass reactor for about 4 hours. After about 3 hours from the initiation of the polymerization, diacetone acrylamide (DAAM) was prepared as a primary external crosslinking agent to be added to the polymerization process in an about 50% aqueous solution, and about 0.7 part by weight per 100 parts by weight of the acrylic emulsion resin About 14 g (about 7 g of DAAM in an actual weight) was added while stirring. Thereafter, about 5% by weight of an aqueous solution of ammonium sulfate and about 5 g of an aqueous solution of ammonium sulfate were added to the reactor in which the polymerization proceeded, the temperature was maintained at about 80 ° C for about 1 hour, To prepare an emulsion resin. Then, about 10 wt% aqueous ammonia solution was added to the acrylic emulsion resin to adjust the pH to about 7 to about 8.5. 2019/117539 1 »(: 1 ^ {2018/015465

Thereafter, adipic acid dihydride (ADH) was prepared as an about 10% aqueous solution as a secondary external crosslinking agent to be injected in the subsequent step, and about 0.35 parts by weight of an about 0.35 part by weight based on 100 parts by weight of the acrylic emulsion resin 35 g (added to the pH-adjusted reaction mixture at an ADH net weight of about 3.5, and further added with a wetting agent serving as an emulsifier to lower the surface tension for coating properties, such as dioctylsodium sulfosuccinate About 1 part by weight of Dioctyl sodium sulfosuccinate was added to 100 parts by weight of the acrylic emulsion resin and the mixture was stirred at a temperature of about 25 ^° C for about 60 minutes to prepare an acrylic emulsion pressure-

As shown in following Table 1 and those conducted in the same manner as the acrylic emulsion pressure-sensitive adhesive composition as in Example 2, except in place of allyl methacrylate (AMA) as an internal crosslinking agent was used to form about 0.1 _§ polyethylene glycol 400 diacrylate (M280) . Comparative Example 3

 As shown in the following Table 1, an acrylic emulsion pressure-sensitive adhesive composition was prepared by the same method as in Comparative Example 2, except that no intragastric was used. Comparative Example 4

 As shown in the following Table 1, an acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that: an allyl methacrylate (AMA) as an internal crosslinking agent was used in an amount of about 0.1 silver. Comparative Example 5

As shown in Table 1 below, allyl methacrylate

An acrylic emulsion pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition was used in an amount of about 3.0 _§ . 2019/117539 1 »(: 1 ^ {2018/015465

Comparative Example 6

 Except that about 0.03 g of diallyl maleate (DAM) was used instead of allyl methacrylate (AMA) as an internal cross-linking agent, as shown in the following Table 1, to obtain an acrylic emulsion pressure- A composition was prepared. Comparative Example 7

 As shown in the following Table 1, except that 0.03 g of tripropylene glycol diacrylate (TPGDA) was used instead of allyl methacrylate (AMA) as an internal crosslinking agent, To prepare an acrylic emulsion pressure-sensitive adhesive composition. Comparative Example 8

 Except that 0.03 g of ethylene glycol dimethacrylate (EGDMA) was used instead of allyl methacrylate (AMA) as an internal crosslinking agent as shown in the following Table 1 To prepare an acrylic emulsion pressure-sensitive adhesive composition. The specific components and contents used to prepare the acrylic emulsion resin in the acrylic emulsion pressure-sensitive adhesive composition according to the examples and the comparative examples are as shown in Table 1 below.

[Table 1]

2019/117539 1 »(: 1 ^ {2018/015465

2019/117539 1 »(: 1 ^ {2018/015465

(% By weight) of the (meth) acrylic acid ester monomer which is the main component of the acrylic emulsion resin in the composition of Table 1 and the content (weight%) of the comonomer including a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group %) Was added so as to be 100% by weight, and the amount of the remaining components was indicated by the ratio (parts by weight) to the total amount of the monomer mixture of 100 parts by weight.

<Experimental Example>

 Manufacture of Adhesive Coated Adhesive Specimen

The acrylic emulsion pressure sensitive adhesive prepared in the above Examples and Comparative Examples was coated on a release paper coated with silicone and dried in an oven at about 120 ^° C for about 1 minute to make the pressure sensitive adhesive layer about 20 _ thick. This was laminated with a polyethylene terephthalate film to produce a label for clothing, and cut to a size of 1 inch x 150 mm to prepare a label sample for clothing. The adhesion properties of the acrylic emulsion-type adhesives prepared in Examples and Comparative Examples were tested by the following methods. The results are shown in Table 2 below. Peel test (N / inch)

Test method FINAT TEST METHOD NO. 2, the acrylic-based emulsion pressure-sensitive adhesive paper label specimen was reciprocated twice at a speed of about 300 mm / min with a roller of about 2 kg, adhered on HDPE (high density polyethylene) film, aged at room temperature for about 20 minutes, (90 ° C) at a speed of about 300 mm / min using a Texture Analyzer. The target value is about 2.4 N / inch or more, preferably about 3.0 N / inch or more.

1x) ₀₁ ) Specimen Preparation 2019/117539 1 »(: 1 ^ {2018/015465

- Sample size: 25mm X 150mm

 - Adhesive: G1 laser or HDPE

- Measurement conditions: 22 ± 2 ^° C, 5 ± 5% RH

- Measuring method: The specimen was made into a loop shape and fixed to the clamp, and the specimen was attached to glass or high density polyethylene (HDPE) film at a constant speed. After about 5 seconds, the peak force was measured by the loop tack peeling force when the measurement speed was about 300 mm / min. The target value is about 6.0 N / inch or more, preferably about 9.0 N / inch or more for the glass plate, and about 2.5 N / inch or more, and preferably about 3.0 N / inch or more for the HDPE film. Holding power _(shear)

 Holding power test (Shear test) was performed by the following method. - Sample size: 25 mm X 25 mm

 - Adhesive: A bright stainless steel plate was prepared (Bright SUS: glossy and slippery)

- Measurement conditions: 22 ± 2 ^° C, 5 ± 5% RH

 - Measurement method: The sample was reciprocated once with a roller of about 2 kg and attached to the adhered surface, and then the holding force was measured (dwell time: 300 mm / min) without dwell time. After a load of about 1 kg was applied to the bottom of the specimen, the time when the specimen detached was measured. The target value should be at least 4500 minutes. Residual rate

 - Sample size: 25mm X I 50mm

 - Adhesive: Cloth fabric

- Measurement conditions: 22 ± 2 ^° C, 60 ± 5% RH

- Measuring method: The label sample was pressed on the selected clothing fabric 5 times with a roller of about 5 kg under load, and then subjected to a load of about 3.5 kg in a thermo-hygrostat with a temperature of about 60 ^° C and a humidity of 95% 2019/117539 1 »(: 1 ^ {2018/015465

The attached sample was pressed and aged for 7 days. Here, 100% polyester fabric or 100% cotton fabric or 52% polyester fabric and 48% cotton fabric were used as the fabric for clothing. The aged sample was taken out for 7 days and applied with a load of about 3.5 kg. The sample was then left in a constant temperature and humidity chamber (about 24 ° C, about 60%) for about 24 hours and taken out to remove the label sample by hand. The apparel size sticker test was applied to the KOTITI garment testing laboratory in the same manner as the analysis method.) In the apparel testing institute, the residual rate was measured by visually looking adhesive or by hand When we touched, we observed the presence of adhesion, the damage of clothing, and the color change of clothing.

[Table 2]

From the results shown in the above Table 2, it was confirmed that Examples 1 to 3 had an excellent adhesive strength while maintaining an extremely low residual rate of about 1% to 3% by controlling the internal crosslinking degree. Particularly, Example 1 exhibited excellent initial adhesion while significantly reducing internal crosslinking. In Examples 2 and 3, the internal crosslinking degree was increased, but the retention of the adhesive agent on the clothing fabric was about 6000 minutes or more You can see that it is excellent. 2019/117539 1 »(: 1 ^ {2018/015465

On the other hand, Comparative Examples 1 to 8 using an internal crosslinking agent in a conventional manner produced excessive residues or deteriorated adhesiveness and were not able to adhere to clothes. First, in Comparative Examples 1 to 3, the use of polyethylene glycol 400 diacrylate instead of allyl methacrylate as an internal crosslinking agent increased the initial cohesion and increased the residual ratio. Particularly, in Comparative Example 1, about 80% of the residue remained largely due to too high initial adhesive force when polyethylene glycol 400 diacrylate was used at about 1.5, and the retention of the adhesive agent on the clothing fabric was about 360 minutes, In Comparative Examples 2 and 3, the use of polyethylene glycol 400 diacrylate instead of allyl methacrylate in Example 2 lowered the crosslinking efficiency, so that the initial adhesive strength was good, but the peel strength &amp; ₆ ^ 10% to 20% of residues were generated, resulting in unstable overall properties, which resulted in lower reliability of various adhesive forces depending on the type of fabric. Furthermore, in the case of Comparative Example 3, while the surfactant is sodium lauryl except this sulfate _{(30 \ 1111 13} ^ ₁ ^ to reduce the latex foam, impaired, the pressure-sensitive adhesive attached to the garment fabric, the holding force in the garment fabric of about 10% On the other hand, in Comparative Example 4, when the content of allylmethacrylate as an internal cross-linking agent was reduced to about 0.10 _너무 , initial adhesion was increased, but about 90% excess residue remained . On the contrary, in the case of Comparative Example 5, the content of allyl methacrylate as an internal cross-linking agent was applied to an excess amount of about 3 _하여 so that the initial adhesion was about 3.8 phantoms and about 1.4

And the problem of not being adhered to clothes appeared. Further, in the case of Comparative Examples 6 to 8, by using diarylmalate, tripropylene glycol diacrylate and ethylene glycol dimethacrylate instead of the internal crosslinking agent allyl methacrylate in the composition of Example 1, about 20% To about 30%, which is a problem that can not be used for clothes. 2019/117539 1 »(: 1 ^ {2018/015465

In particular, in the case of diaryl malate in Comparative Example 6, the length of the cross-linking agent was long and the problem of adhesion was remarkably lowered by the limited reaction point as compared with Example 1. Further _, in the case of tripropylene glycol diacrylate in Comparative Example ₇ , the chain length was long, so that when the amount of allyl methacrylate was the same as that of allyl methacrylate, the crosslinking was less and the desired adhesion was not obtained. Finally, in the case of Comparative Example 8 using ethylene glycol dimethacrylate, the crosslinking length was similar but the reactivity was different. Thus, about 20% of residue was generated. If a residue of about 20% or more is generated, the adhesive sample is adhered to the fabric more than the label when removing the label sample after the label sample is attached to the fabric, so that the mark remains clearly and easily visible to the naked eye.

Claims

2019/117539 1 »(: 1 ^ {2018/015465

Claims:

 Claim 11

 (Meth) acrylic acid ester monomer together with a monomer mixture containing at least one comonomer containing a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group, and an aqueous acrylic emulsion Resin,

 Wherein the internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide, allyl-methylcarbamate, 1,6-nucleic acid diol diacrylate, nucleic acid diol ethoxylate diacrylate, Pentaerythritol ethoxylate triacrylate, pentaerythritol triacrylate,

Pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, and divinylbenzene,

 Wherein the internal crosslinking agent is contained in an amount of 0.02 to 0.25 parts by weight based on 100 parts by weight of the acrylic emulsion resin.

 Aqueous acrylic adhesive for clothing.

[Claim 2]

 The method according to claim 1,

 Wherein the comonomer is contained in an amount of 10 parts by weight or less based on 100 parts by weight of the (meth) acrylic acid ester monomer.

 Aqueous acrylic adhesive for clothing.

[Claim 3]

 The method according to claim 1,

 Wherein the monomer mixture comprises 5 to 25% by weight of methyl methacrylate, 30 to 60% by weight of 2-ethylhexyl acrylate, 0.5 to 10% by weight of styrene, 20 to 40% by weight of butyl acrylate, , And from 0.5% to 10% by weight of acrylic acid.

Aqueous acrylic adhesive for clothing. 2019/117539 1 »(: 1 ^ {2018/015465

Claim 4

 The method according to claim 1,

 And a residual ratio on the clothing fabric is 8% or less.

 Aqueous acrylic adhesive for clothing.

[Claim 5]

 (Meth) acrylic acid ester monomer together with a monomer mixture containing at least one comonomer containing a functional group selected from the group consisting of a hydroxyl group, an epoxy group, a cyano group, a styrene group and a carboxyl group, an internal cross- &Lt; / RTI &gt;

 And emulsion-polymerizing the pre-emulsion to prepare an acrylic emulsion resin,

 The internal cross-linking agent is selected from the group consisting of allyl methacrylate, polyethylene glycol diacrylate, polycarbodiimide, allyl-methylcarbamate,

6-nucleic acid diol diacrylate, nucleic acid diol ethoxylate diacrylate, nucleic acid diol propoxylate diacrylate, pentaerythritol ethoxylate triacrylate,

Pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, and divinylbenzene,

 Wherein the 4-part additive is mixed with 0.02 part by weight to 0.25 part by weight with respect to 100 parts by weight of the monomer mixture,

 A method for producing an aqueous acrylic pressure-sensitive adhesive for clothing according to claim 1. [Claim 6]

 6. The method of claim 5,

Wherein the pre-emulsion further comprises at least one member selected from the group consisting of a surfactant, a buffer, an external crosslinking agent, and a wetting agent. 2019/117539 1 »(: 1 ^ {2018/015465

7.

 6. The method of claim 5,

 Characterized in that the emulsion polymerization is carried out in the presence of a polymerization initiator and an external crosslinking agent.

 (Method for producing aqueous acrylic pressure sensitive adhesive for clothing).

[8]

 6. The method of claim 5,

Lt; RTI ID = _0.0 &gt; 1, &lt; / RTI &gt;

 A method for producing an aqueous acrylic pressure sensitive adhesive for clothing.