WO2020046060A1 - Adhesive composition and preparation method thereof - Google Patents

Abstract

The present invention can provide an adhesive composition, wherein the adhesive composition includes lysine, alpha-Ketoglutaric acid, and water, wherein the lysine and alpha-Ketoglutaric acid are in the form of an aqueous salt solution and do not form precipitates in the aqueous solution.

Description

Adhesive composition, and preparation method thereof

The present application relates to a novel adhesive composition, and a method for preparing the same.

Adhesives generally use petroleum-based monomers and oily solvents as raw materials. Monomers made from petroleum-derived raw materials and pressure-sensitive adhesives formed therefrom have problems of reduced production due to petroleum resource limitation, environmental hormones generated during manufacturing, and toxicity at disposal. In particular, organic solvents derived from petroleum are used in the manufacturing process in order to improve the adhesive strength in the conventional adhesive manufacturing, which impairs the health of workers and has environmental problems in terms of environmental protection. In addition, most adhesives are difficult to decompose naturally because the monomer units are made of covalent bonds, and environmental pollution problems are also raised by polymers that are not decomposed. For this reason, techniques of various water-separable pressure-sensitive adhesives for effectively removing the pressure-sensitive adhesive from the adherend have been developed. In the conventional water-separable pressure sensitive adhesive, high temperature and alkaline conditions are required to effectively remove the adhesive adhered to the adherend and the substrate and additional energy resource consumption is required. In addition, when the pressure-sensitive adhesive material molecules are discharged to the environment when the pressure-sensitive adhesive material adhered from the adherend or the substrate is separated by water, additional secondary environmental pollution may be caused.

An aspect of the present application is to provide an adhesive composition.

Another aspect of the present application is to provide a method for preparing the pressure-sensitive adhesive composition.

Hereinafter, an adhesive composition and a method of manufacturing the same according to one embodiment will be described in more detail.

Lysine, alpha ketoglutaric acid and water, wherein the lysine and alpha ketoglutaric acid are present in the form of a salt solution and do not form precipitates in the aqueous solution. A composition is provided.

As used herein, the term "adhesion" refers to a phenomenon in which two objects (but not gas) are in proximity and then require some force (or work) to pull them out. In some cases, some materials having adhesion may become solid after a certain time after the substrate is applied, and may be accompanied by irreversible physical breakdown if the adhesive is to be separated from the substrate. In addition, the "adhesion" may include "viscoelasticity", which requires some force for viscoelastic deformation when the adhesive material is separated from the substrate. The adhesive composition having a viscoelastic property is stored and distributed through a general processing form before being applied to a substrate, and its adhesion can be maintained even after a certain time. Examples of the adhesive article obtained by applying and drying such an adhesive composition on a substrate include a label and an oriented polypropylene (OPP) tape. By using the adhesive property, reversible adhesion and detachment are possible, and when the adhesive composition is applied and dried on the substrate, an adhesive layer containing a viscoelastic material is formed on the substrate.

Viscosity, on the other hand, originates from internal friction between molecules and refers to the nature of trying to hinder the flow of a substance. At this time, friction is a force to prevent a difference in the distribution of flow velocity. Adhesiveness and viscosity are separate properties, and even a composition having high viscosity may have little adhesiveness, and even a composition having low viscosity may have high adhesiveness.

Precipitates in the present application is that insoluble salt AB (s) is obtained by chemical changes of the aqueous solution of lysine A (aq) and alpha ketoglutaric acid solution B (aq), as shown in Scheme 1 below, Scheme 2 Lysine solid A (s) or alpha ketoglutaric acid solid B (s) is precipitated from lysine aqueous solution A (aq) or alpha ketoglutaric acid aqueous solution B (aq) as described above, or lysine solid A (s) or alpha keto Glutaric acid solid B (s) may include all cases that are not dissolved in the solvent and remain in an insoluble state.

Scheme 1

A (aq) + B (aq)-> AB (s)

Scheme 2

A (aq)-> A (s)

In addition, in the present application, “precipitation” may be precipitation generated before the substrate or the adhesive to be applied, during storage and distribution.

As used herein, the term “lysine” is one of basic α-amino acids, and the lysine may be biosynthesized from oxal acetic acid through a lysine biosynthetic pathway or chemically synthesized.

Lysine may comprise one lysine or a mixture of one or more lysines.

The lysine may be at least one selected from L-lysine represented by Formula 1, D-lysine represented by Formula 2, and salts thereof.

[Formula 1]

[Formula 2]

The lysine salts include, for example, lysine sulfate, lysine acetate, lysine monohydrochloride, lysine dihydrochloride, lysine monohydrate, lysine acetylsalicylate, lysine phosphate, lysine diphosphate, mixtures or combinations thereof. . Such lysine salts can be converted to lysine preforms.

In the present invention, the conversion of lysine salts to lysine preforms is known to those skilled in the art. It is also possible to use commercially available lysine raw materials. For example, the lysine may be D-lysine, L-lysine and / or DL-lysine, and since their physicochemical properties are the same or similar, the characteristics of the adhesive composition including them are also the same or similar, and thus, the present invention It can belong to the category of. In one embodiment, lysine may be obtained as a fermentation broth.

Alpha ketoglutaric acid is represented by the following general formula (3) as one of the organic acids.

 [Formula 3]

Lysine and alpha ketoglutaric acid in the adhesive composition may be present in the form of a salt solution. Specifically, even if lysine, alpha ketoglutaric acid and water are mixed, lysine and alpha ketoglutaric acid may be present in the form of an aqueous salt solution without forming covalent compounds or insoluble salts. In the adhesive composition of the present application, alphaketoglutaric acid is not present in the form of an insoluble substance which is not dissolved in water.

In the pressure-sensitive adhesive composition according to one embodiment, the content of lysine, alpha ketoglutaric acid and water may be controlled so that lysine and alpha ketoglutaric acid do not precipitate or form crystals. Thus, when the pressure-sensitive adhesive composition maintains a liquid state without forming crystals or precipitates, the pressure-sensitive adhesive is excellent in adhesion, and is easily applied to the substrate uniformly.

The mixed molar ratio of lysine and alpha ketoglutaric acid may be 1.7: 1 to 1: 3. For example, the mixed molar ratio of lysine and alpha ketoglutaric acid may be 1.6: 1 to 1: 2, 1.5: 1 to 1: 2, 1.4: 1 to 1: 2, 1.3: 1 to 1: 1.5, or 1.2: 1 to 1: 1.5. If the content of lysine to alpha ketoglutaric acid is more or less than the above-mentioned range, precipitation in the composition may be formed, leading to deterioration in adhesiveness or deterioration in storage stability or storage stability of the adhesive composition.

The content of solids in the adhesive composition may be 70 parts by weight or less, for example, 0.1 to 70 parts by weight, 1 to 70 parts by weight, and 10 to 70 parts by weight based on 100 parts by weight of the composition. When the content of the solid content is within the above range, it is easy to apply the pressure-sensitive adhesive on the substrate, and when the content of the solid content is more than 70 parts by weight, precipitation may be formed, which may be difficult to use as the adhesive composition. Even if the content of the solid content decreases, the precipitate does not form or lose the cohesion in the composition. Therefore, the content of the solid content may be adjusted to a level of 0.1 to 10 parts by weight depending on the field of application.

Alphaketoglutaric acid and lysine may be included as active ingredients in the adhesive composition. Specifically, the sum of the alpha ketoglutaric acid and the lysine content based on 100 parts by weight of the adhesive composition may be 60 to 100 parts by weight, 70 to 99 parts by weight, 80 to 98 parts by weight, or 85 to 97 parts by weight.

In addition to lysine and alpha ketoglutaric acid, the adhesive composition according to one embodiment may further include one organic acid selected from citric acid, itaconic acid, oxal acetic acid, and malic acid as a minor component. At this time, the content of the organic acid may be 0.1 to 10 parts by weight, for example 0.1 to 5 parts by weight, based on 100 parts by weight of alpha ketoglutaric acid. As such, when further comprising one organic acid selected from citric acid, itaconic acid, oxal acetic acid and malic acid, the adhesive force of the pressure-sensitive adhesive composition can be easily applied according to various applications.

In another embodiment, the alpha ketoglutaric acid and lysine of the present invention may be contained in the form of a condensate containing alpha ketoglutaric acid and lysine as a unit. For example, the condensate may be a dimer, trimer or oligomer, and the content of the condensate may be 20 parts by weight or less, 10 parts by weight or less, based on 100 parts by weight of the total content of lysine and alpha ketoglutaric acid, It may be 1 part by weight or less, and may include 0. When the condensate is included in the above range, the adhesive strength of the pressure-sensitive adhesive composition may be reduced or the liquid state may not be maintained.

Referring to the effect of the adhesive composition according to one embodiment showing the adhesiveness as described above are as follows. This effect does not mean that it is limited to the matters to be described later, but may be described by other effect within the scope without scientific contradiction.

Lysine has two amino groups and alpha ketoglutaric acid has two carbonyl groups. The non-covalent electron pair of oxygen of the carbonyl group of alpha ketoglutaric acid and the hydrogen of the amino group of lysine can interact through an ionic hydrogen bond.

Therefore, when components of the pressure-sensitive adhesive composition of the present invention are analyzed by liquid chromatography, lysine and alpha ketoglutaric acid can be identified as raw materials. From this, it can be seen that lysine and alpha ketoglutaric acid in the adhesive composition are bonded through an ionic hydrogen bond, and they exist in the form of a salt solution. In the pressure-sensitive adhesive composition of the present invention, lysine and alpha ketoglutaric acid may exhibit excellent adhesion characteristics while maintaining a liquid state without precipitation in a crystalline form (solid state) or a precipitate form at room temperature (25 ° C.).

The adhesive composition of the present invention has water separation property. Therefore, when the pressure-sensitive adhesive composition of the present invention is used as the pressure-sensitive adhesive, it is easily removed because it is dissociated by water during separation and removal from the substrate or the adhesive to which the pressure-sensitive adhesive is applied. Specifically, the pressure-sensitive adhesive applied to the substrate or the adherend may be dissociated within 12 hours, specifically within 6 hours, and more specifically within 2 hours through stirring or washing with water at room temperature (25 ° C.). . The adhesive composition of the present invention is easily dissociated with water, and the dissociated components are also environmentally friendly because they are harmless to life and the environment.

The adhesive composition of the present invention may further include one or more alcohol solvents selected from the group consisting of primary alcohols, polyhydric alcohols, diols and triols. Adding a solvent to the pressure-sensitive adhesive composition can increase the drying speed of the pressure-sensitive adhesive composition and increase the processability.

According to one embodiment, the mixed weight ratio of the deionized water and the alcohol in the pressure-sensitive adhesive composition may be 1: 1 to 10: 0. More specifically, the mixed weight ratio of deionized water and alcohol in the adhesive composition may be 1: 1 to 10: 1, 1: 1 to 5: 1, or 1: 1 to 3: 2. As the content of alcohol in the pressure-sensitive adhesive composition increases, the drying is better, the coating property is improved, the peel strength may increase. However, when the content of the alcohol in the adhesive composition is 1.5 times or more than the deionized water, phase separation may occur in the adhesive composition.

The alcohol solvent may be monohydric alcohol, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, or mixtures thereof. The monohydric alcohol may be at least one selected from methanol, ethanol, propan-2-ol, butan-1-ol, pentan-1-ol and hexadecane-1-ol. The polyhydric alcohols include ethane-1,2-diol, propane-1,2-diol, propane-1,2,3-triol ( propane-1,2,3-triol, butane-1,3-diol, butane-1,2,3,4-tetraol butane-1,2,3,4 -tetraol), pentane-1,2,3,4,5-pentol (pentane-1,2,3,4,5-pentol), hexane-1,2,3,4,5,6-hexole (hexane -1,2,3,4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptol (heptane-1,2,3,4,5,6,7- heptol).

Unsaturated aliphatic alcohols include, for example, Pro-2-ene-1-ol, 3,7-dimethylocta-2,6-diene-1-ol (3,7-Dimethylocta -2,6-dien-1-ol), pro-2-yn-1-ol (Prop-2-yn-1-ol) may be one or more selected.

The alicyclic alcohol is, for example, cyclohexane-1,2,3,4,5,6-hexol (cyclohexane-1,2,3,4,5,6-hexol), 2- (2-propyl)- 5-methylcyclohexane-1-ol (2- (2-propyl) -5-methyl-cyclohexane-1-ol) may be one or more selected from.

The pH of the pressure-sensitive adhesive composition is 2 to 11, specifically 2 to 9.5, more specifically 2 to 8.5. The pressure-sensitive adhesive composition having a pH range is excellent in storage stability and storage stability, and even if stored for a long time, there may be no change in formulation or quality. The pressure-sensitive adhesive composition is excellent in tackiness and does not form a precipitate even when used after being stored for a long time, as well as when used immediately.

When the lysine, alpha keto glutaric acid and water are mixed, alpha ketoglutaric acid may be added to the aqueous solution of lysine, or lysine, alpha ketoglutaric acid, and water may be mixed at the same time.

Specifically, the adhesive composition may be one in which no precipitation is formed after storage or distribution for 14 days or more. For example, 14 days or more, for example, 12 months or more, even if stored, the composition is stable and the physical properties can be maintained as it is. In addition, the temperature of the environment in which the adhesive composition is stored may be -18 ℃ to less than 40 ℃, specifically -18 ℃ to 35 ℃, 0 ℃ to 60 ℃, or 20 ℃ to 35 ℃. Even if stored in a low temperature or high temperature environment, if the temperature of the environment in which the pressure-sensitive adhesive composition is used at room temperature may have no effect on the formulation and quality. For example, when stored at low temperature, it can be used after leaving it to room temperature for a predetermined time before use.

According to another aspect of the present invention there is provided a method for preparing the above-mentioned pressure-sensitive adhesive composition comprising mixing lysine, alpha ketoglutaric acid and water and stirring it below 40 ° C.

When the step of mixing the lysine, alpha ketoglutaric acid and water and stirring it at less than 40 ℃ is carried out outside the temperature range, side reaction substances, impurities, etc. may be formed, in some cases, the adhesive composition having the desired adhesiveness Can be difficult to obtain.

Stirring at less than 40 ℃ may be performed at less than 40 ℃ 0 for example. More specifically, the step may be carried out at 0 ° C or more and less than 40 ° C, 0 ° C to 30 ° C, or 0 ° C to 25 ° C.

The step of stirring below 40 ° C is i) the first step of mixing and stirring at 0 ° C or above 40 ° C, 0 ° C to 30 ° C, or 0 ° C to 25 ° C and ii) room temperature (20 to 30 ° C) It may include a second step of cooling to).

When the lysine, alpha keto glutaric acid and water are mixed, alpha ketoglutaric acid may be added to the aqueous solution of lysine, or lysine, alpha ketoglutaric acid, and water may be mixed at the same time.

The pressure-sensitive adhesive composition may further include the step of removing the water and the solvent by concentration under reduced pressure to control the solid content in a predetermined range.

According to another aspect of the present invention there is provided an adhesive product comprising the above-mentioned adhesive composition on the substrate. The adhesive product is a substrate; And a pressure-sensitive adhesive layer obtained by applying and drying the pressure-sensitive adhesive composition described above on the substrate. Through the drying, the solvent in the composition can be removed. Drying can be performed at 25-45 degreeC.

The substrate can be used as long as the adherend to which the adhesive composition can be applied in the art. The substrate may be, for example, glass, stainless steel (SUS), a polymer film, or the like. The polymer film is mainly a polyolefin film such as a mixture of polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, ethylene / vinyl acetate copolymer, polyethylene / styrene butadiene rubber, or polyvinyl chloride film. Can be used. In addition, plastics such as polyethylene terephthalate, polycarbonate, poly (methyl methacrylate), thermoplastic elastomers such as polyurethane, polyamide-polyol copolymer, and mixtures thereof can be used.

Unevenness may be formed on the surface of the substrate to increase adhesion between the substrate and the adhesive composition. According to another embodiment, the surface of the substrate may be hydrophilic. r By using a hydrophilic substrate as described above, the coating composition of the pressure-sensitive adhesive composition can be more uniformly carried out on the substrate having hydrophilicity, so that the film forming property is excellent.

When using glass as a base material, application | coating of the adhesive composition on glass which has hydrophilicity can be performed more uniformly, and film forming property is excellent. When SUS is used as the substrate, the alpha ketoglutaric acid in the adhesive composition causes interaction with the SUS, so that the adhesion of the adhesive layer formed from the substrate and the adhesive composition is excellent.

Bonding the adhesive composition to the first substrate by applying the adhesive composition to the first substrate according to another aspect of the present invention; And attaching the first substrate and the second substrate to each other by contacting the first substrate, to which the composition is bonded, with the second substrate, to provide a method for attaching the first substrate and the second substrate.

The first substrate and the second substrate may be independently selected from one or more selected from glass, stainless steel, polymer film, metal, plastic, paper, fiber, and soil, but is not limited thereto. . The first substrate and the second substrate may be the same material, for example.

The adhesive composition or adhesive product according to one embodiment may be used as an adhesive tape, a label sheet, a spray adhesive, a dust remover, etc. as a water-separable adhesive, and may be easily removed without damaging the adherend by using water. Packaging materials can be easily recycled. And when the composition is applied to the pesticides and seeds field, it can be easily removed with water after using the pressure-sensitive adhesive-containing composition can be used in a wider range of applications. In addition, the water-separable pressure-sensitive adhesive of the present specification, as compared to the conventional organic solvent-type pressure-sensitive adhesives, as well as cost reduction and easy handling, workability is improved and the working environment can be cleaned.

The adhesive composition according to the present application may select a bio-derived monomer as a starting material to be used in the manufacture, and may be a monomer that can be utilized in vivo. Environmental pollution by an oligomer can be prevented beforehand. Structures such as an adhesive tape, a sheet for labels, and the like, wherein the composition of the present application is formed using a water-separable pressure-sensitive adhesive, have improved mechanical strength such as tensile shear strength and peel force.

According to another embodiment, the pressure-sensitive adhesive composition or adhesive material of the present application, if necessary, reactive diluents, emulsifiers, tackifiers, plasticizers, fillers, antioxidants, curing accelerators, flame retardants, flocculants, surfactants, thickeners, Sunscreens, elastomers, pigments, dyes, fragrances, antistatic agents, antiblocking agents, slip agents, inorganic fillers, kneading agents, stabilizers, modifying resins, coupling agents, leveling agents, fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet rays It may comprise one or more additives selected from the group consisting of absorbents, waxes, wetting agents, antioxidants, preservatives and lubricants. The total content of such additives is not particularly limited and may include various additives in various weight ranges depending on the intended use. The content of each of the additives listed above may be used at levels conventionally used in the art.

The reactive diluent is a diluent which helps each component of the composition to be evenly applied to the object to which the composition is applied. For example, n-butylglycidyl ether, aliphatic glycidyl ether, 2-ethylhexyl glycidyl Ether, phenylglycidyl ether, o-cresylglycidyl ether, nonylphenylglycidyl ether, p-tertbutylphenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, neopentylglycidyl ether, 1,4-cyclohexanedimethylol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl Ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, hydrogenate bisphenol eglycidyl ether, trimethylolpropenetriglycidyl ether, glycerol polyglycidyl ether, diglyl Cerrol polyglycidyl ether, penterrititol polyglycidyl ether, castor oil glycidyl ether, sorbitol polyglycidyl ether, neodecanoic acid glycidyl ether, diglycidyl-1.2-cyclohexane Dicarboxylate, diglycidyl-o-phthalate, N, N-diglycidylamine, N, N-diglycidyl-o-toluidine, triglycidyl-p-aminophenol, tetraglycidyl- Diaminodiphenylmethane, triglycidyl-isocyanate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropyleneglycidyl diglycidyl ether and triethylolpropene It may be at least one selected from the group consisting of triglycidyl ether.

The emulsifying agent may be, for example, at least one selected from the group consisting of copolymers of polyoxyethylene and polyoxypropylene, copolymers of polyoxyethylene and polyoctylphenyl ether, and sodium dodecylbenzene sulfide.

The tackifiers are for example rosin and its modified products (eg rosin, hydrogenated rosin, polymerized rosin, maleated rosin, rosin glycerin, rosin modified phenolic resin, etc.), terpene-based resins ( Terpene-based resins (e.g. terpene resin, terpene-phenol resin, terpene-styrene resin, terpene-phenolic resin), Petroleum resin (e.g. C5 petroleum resin, C9 resin, bicyclic nonadiene petroleum resin, hydrogenated petroleum resin, styrene-terpene resin, phenolic resin, polymethylstyrene resin, ketonealdehyde resin, xylene formaldehyde resin, cashew oil modified phenolic resin, tall oil modified phenolic resin (Tall) oil modified phenolic resins, rubbers, resin emulsions (e.g. rosin emulsions, TPR water based resins, 2402 resin emulsions, petroleum resin emulsions), coumaroneindene resins.

The plasticizer may be contained in the composition to serve to improve processing flow or drawing. And the plasticizer can improve the functions of the electrical insulation, adhesion, cold resistance, light resistance, oil resistance, non-leak resistance, flame retardant flame resistance, thermal stability, biprocessing (molecular activity), activity (intermolecular activity), nontoxicity of the composition.

Plasticizers for improving functions such as cold resistance may be dioctyl adipate (DOA), dioctyl azelate (DOZ), dioctyl sebacate (DOS), Flexol TOF (UCC), polyethylene glycol esters, and the like. The plasticizer for improving the heat resistance (non-volatile) and non-performance can be a polymer blend such as polyester, NBR (nitrile butadiene rubber), trimellitic acid ester, pentaerythritol ester and the like. Plasticizers for improving light resistance properties may be DOP, DOA, DOS, polyester, epoxidized soybean oil (ESBO) and the like.

The plasticizer for oil resistance improvement may be phosphplex aromatic phosphate ester (trade name: TPP, TCP, 112 (CDP), 179A (TXP)), polyester-based, NBR, etc., and plasticizers for soap resistance are TCP, ESBO. , Polyester-based, and the like.

The plasticizer for flame retardant flame retardant may be phosphate such as TCP, TXP, paraffin chloride, alkyl stearate, NBR, or the like, and the plasticizer for thermal stability may be ESBO, DOZ, DOS, DOP, polyethylene glycol ester, or the like.

Plasticizers for processability include DOA. BBP, TOF, TCP, octyldiphenyl phosphate and the like, the plasticizer for the activity may be DOZ, DOS, dibasic lead phosphate (DLP), ESBO, polyethylene glycol ester and the like.

Plasticizers for non-toxicity may be BPBG, octyldiphenylphosphate, ESBO, citric acid esters, NBR and the like.

The plasticizer is specifically dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (DnOP), diisooctyl phthalate (DIOP), didecyl Phthalates (DDP), Diisodecylphthalate (DIDP), C8 ~ C10 mixed higher alcohol phthalates, Butylbenzylphthalate (BBP), Dioctyl adipate (DOA), Dioctyl azelate (DOZ), Dioctyl sebacate (DOS ), Tricresyl phosphate (TCP), trikisilenyl phosphate (TXP), monooctyl diphenyl phosphate (Santicizer 141), monobutyl- dikisylenyl phosphate, trioctyl phosphate (TOF), aromatic oils, polybrodenes, Paraffin and the like can be used.

Thickeners herein include, for example, alginine, alginic acid, sodium alginate, guar gum, xanthan gum, collagen, alginate ), Gelatin, furcellaran, agar, carrageenan, casein, locust bean gum, pectin, polyethylene oxide, polyethylene glycol, poly Vinyl alcohol, polyvinylpyrrolidone and the like can be used.

The surfactant may be used as long as it is commonly used in the art. For example C8 to C18 alkyl sulfates, up to 40 ethylene oxide or propylene oxide units and C8 to C18 alkyl ether sulfates having hydrophobic groups or C8 to C18 alkyl arylether sulfates, C8 to C18 alkyl sulfates Esters and semiesters of sulfosuccinic acids with alkylates, alkylaryl sulfonates, monohydric alcohols or alkylphenols, C8 to C40 alkyl polyglycol ethers having ethylene oxide units or C8 to 40 alkyl aryl polyglycol ethers. . Alkyl sulfates having a chain length of C8 to C18, alkyl ether sulfates or alkyl arylether sulfates having a hydrophobic group and having ethylene oxide or propylene oxide units of C8 to C18, alkyl sulfonates of C8 to C18, alkylaryl Esters and semiesters of sulfosuccinic acids with sulfonates, monohydric alcohols or alkylphenols, alkyl polyglycol ethers or alkyl aryl polyglycol ethers having ethylene oxide units of C8 to 40. For example, sodium dodecyl sulfate (SDS), sodium silicate (Na-silicate) and the like can be used.

The filler is added to improve the strength, durability, and workability of the composition, for example calcium carbonate, talc, ceramic, silica, dolomite, cray, titanium bag, zincation, carbon (anti-shrink, anti-blocking), potassium carbonate, Titanium oxide, liquid polysulfide polymer, volatile diluents, magnesium oxide, processing oil, and the like.

Examples of the curing accelerators include dibutyltin dilaurate, JCS-50 (manufactured by Johoku Chemical Co., Ltd.), formate TK-1 (manufactured by Mitsui Chemical Co., Ltd.), and the like. And antioxidants are, for example, dibutylhydroxytoluene (BHT), Irganox (registered trademark) 1010, Irganox (registered trademark) 1035FF, Irganox (registered trademark) 565 (all, Chiba specialty chemicals) Product of the company.

The antistatic agent is not particularly limited, and specifically 1-hexyl-4-methylpyridinium hexafluorophosphate, dodecylpyridinium hexafluorophosphate, fluorinated organometallic compound (eg, 3M's HQ-115), alkali metal salt (Eg, NaPF ₆ , NaSbF ₆ , KPF ₆ , KSbF _6, etc.), conductive polymers (eg, polythiophene (PEDOT from Bayer), polyaniline, polypyrrole, etc.), metal oxides (eg, indium doped tin oxide (ITO), Antimony-doped tin oxide (ATO), tin oxide, zinc oxide, antimony oxide, indium oxide, etc.), quaternary ammonium salts (e.g. poly (acrylamide-co-diallyldimethylammonium chloride) solution from Sigma-Aldrich), 1- Butyl-3-methylimidazolium hexafluorophosphate [BMIM] [PF ₆ ], 1-butyl-3- (2-hydroxyethyl) imidazolium bis (trifluoromethanesulfonyl) imide [BHEIM] [NTf ₂ ], tetrabutylmethylammonium bis (trifluoromethanesulfonyl) De [TBMA] [NTf ₂ ] and the like, these may be used alone or in combination of two or more.

The elastomer refers to a polymer having rubber or elastomeric properties, for example, ethylene-vinyl acetate copolymer, acrylic rubber, natural rubber, isoprene rubber, styrenebutadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, styrene-ethylene -Butylene-styrene copolymer, acrylonitrile-butadiene copolymer and the like can be used.

The stabilizer serves to stabilize the adhesive strength of the composition, and examples thereof include polyhydric alcohol, polyvalent amine, and the like. For example, alkylene glycol, dialkylene glycol, benzenediol, benzenetriol, dialcoalamine, trialcoholamine, arabitol, mannitol, isomalt, glycerol, xylitol, sorbitol, maltitol, erythritol, ribitol, It may be at least one selected from the group consisting of dulsitol, lactitol, tracer, iditol, polyglycitol, alkylenediamine, alkenylenediamine, phenylenediamine and n-aminoalkyl alkanediamine.

The fluorescent brightener may be a benzooxazole compound, a benzothiazole compound, or a benzoimidazole compound.

The pigments may be natural or synthetic pigments, and these may be inorganic or organic pigments as another class. ,

The fragrance may be, for example, but not limited to, peppermint oil, spearmint oil, carbon or menthol, or the like.

The flame retardant may be melamine cyanurate, magnesium hydroxide, leadstone, zeolite, sodium silicate, aluminum hydroxide, antimony-based (antimony trioxide), or the like. And the water resistance improving additive may be glyoxal (glyoxal).

Examples of the modified resins include polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, epoxy resins, epoxidized polybutadiene resins, and the like.

The coupling agent may improve adhesion and adhesion reliability between the adhesive composition and the packaging material. The addition of such a coupling agent can improve adhesion reliability when the composition is left for a long time under high temperature and / or high humidity conditions. Examples of the coupling agent include γ-glycidoxypropyl triethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl methyldiethoxy silane, γ-glycidoxy propyl triethoxy silane , 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy propyl triethoxy silane, γ-aminopropyl tri Methoxy silane, γ-aminopropyl triethoxy silane, 3-isocyanato propyl triethoxy silane, γ-acetoacetate propyl trimethoxysilane, γ-acetoacetate propyl triethoxy silane, β-cyanoacetyl Silane compounds such as trimethoxy silane, β-cyanoacetyl triethoxy silane, acetoxyaceto trimethoxy silane and the like can be used.

The kneading agent may be an aromatic hydrocarbon resin.

* The anti-aging agent may be N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.

The humectant may be, for example, a mixture of saccharides, glycerin, sorbitol aqueous solution or amorphous sorbitol aqueous solution alone or mixed.

The ultraviolet absorber is ethylhexyl methoxycinnamate (eg 2-Ethylhexyl 4-methoxycinnamate), ethylhexyl salicylate, 4-methylbenzylidene camphor, isoamyl p-methoxycinnamate, octocrylene, phenyl Benzimidazolesulphonic acid, homosalate, synoxate, ethylhexyltrizone, polysilicone-15, tie-salicylate, popba (PABA), ethylhexyldimethylpava, glycerylpava and the like. These may be used alone or in combination of two or more.

The pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is, in addition to the above-mentioned additives, US Pat. The additives disclosed in Japanese Patent Laid-Open No. 5959867 and Korean Patent No. 989942 are incorporated by reference in their entirety.

The adhesive composition or adhesive product according to one embodiment may be used to attach a label or the like to various packaging materials including metal, glass and plastic. The packaging materials may for example be containers for food, drinks or household goods and these containers may be made of glass, metal or plastic.

The adhesive composition or adhesive product may be used for an adhesive, a coating agent, a carrier, a food additive, and the like according to its composition and properties.

When the adhesive composition or adhesive product of the present application is used as an adhesive, for labeling, sealing, papering, cigarette paper, adhesive block toys, sand sculpture, food, bathroom / kitchen cleaner, animal ointment spray , Exfoliation, hair fixation, hair gel. It can be applied to soil stabilizers, water pools and intensifiers, corrugated cardboard, and zone adhesives. Soil stabilizer is used to remove fine dust such as yellow sand or dust generated in plant.

When the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is used as a coating agent, it may be used for forest fire control, fruit vegetables, cut flower stem cut surfaces, and the like, and may be used for dyes, antifouling pretreatment coating agents and the like. The antifouling pretreatment coating agent may be used in the process of coating the composition on a medium contaminated easily, and then simply washing with water when the composition is contaminated.

When the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is used as a carrier, it is applicable to forest protection, forest fire control, toilet fragrance, disinfectant, agricultural materials, household goods, toys and the like. Forest protection may include, for example, forest protection such as pine tree nematodes, and disinfectants may include, for example, bird flu disinfectants and foot and mouth disease disinfectants. And agricultural materials include fertilizers, taping, seed coating and the like.

When the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is applied to agricultural materials, it may be used for seed coating agents, plant taping agents, insecticide additives, fertilizer excipients, natural insecticides and the like. And when the composition of the present application is applied to household goods, it is added to the paint does not flow down to stick to paper or food coloring can be used in the manufacture of edible paints used by infants. As another example that the composition of the present application is applied to household goods, it may be used as a decontamination pretreatment agent, which will be described in more detail when the composition of the present application is sprayed on contaminated media such as insect screens, window frames, automobiles, etc. Decontamination can be quickly removed.

When the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application performs a carrier function, it is possible to implement oxygen barrier properties, water barrier properties, oil resistance, and heat sealing functions, and when used in an eco-friendly food packaging coating layer, it prevents moisture from penetrating the outside. It has the effect of preventing and delaying food rot and oxidation. In addition, when the adhesive composition or the adhesive product of the present application is used as a food additive, it refers to a case where it is used for flour gluten substitute material, jelly, starch syrup, medicine, pigment, ice cream, anti-icing agent and the like.

The adhesive composition according to one embodiment has water-separable adhesion, coating and carrier functions. When the pressure-sensitive adhesive composition is used as a water-separable pressure-sensitive adhesive can be dissociated by water from the adherend or the substrate according to one embodiment can be easily removed from the adherend or the substrate. Therefore, such a pressure-sensitive adhesive is environmentally friendly as a water separation material.

Hereinafter, the following examples will be described in more detail, but it is not meant to be limited only to the following examples.

Example 1 Evaluation of Stability of Compositions Containing Lysine and Various Organic Acids

When the compositions were prepared by mixing lysine, which is a basic amino acid, with various organic acids, the stability (precipitation formation) of each composition was evaluated.

Method for preparing an adhesive composition comprising lysine and alpha ketoglutaric acid:

84.5 g of DIW (distilled water) was added to 100 g of an aqueous 61.5 wt% L-Lysine free form solution, and the mixture was diluted with stirring at room temperature (25 ° C.) for 30 minutes. 61.47 g of alpha ketoglutaric acid (aKG) was added to the diluted lysine at room temperature (25 ° C.) slowly and stirred for 1 hour, followed by stirring for 1 hour at RT (Room Temp.). Subsequently, after the reaction mixture reached room temperature (25 ° C.), the reaction was terminated to obtain 245.97 g of an adhesive composition. The content of solids in this composition is about 50 parts by weight based on 100 parts by weight of the composition, the mixing molar ratio of lysine and alpha ketoglutaric acid is 1: 1 and the solvent is deionized water.

In the same manner as the above method, the composition was prepared by varying only the type of organic acid. Except that each of the organic acids shown in Table 1 was used, the composition was prepared in the same manner as in Example 1.

In the same manner as the above method, the composition was prepared by varying only the type of organic acid. Except that each of the organic acids shown in Table 1 was used, the composition was prepared in the same manner as in Example 1.

No.	mountain	Lysic acid: mol ratio	menstruum	Solid content (parts by weight)
1-1	Alpha keto glutaric acid	1: 1	DIW	50
1-2	Acetic acid	1: 1
1-3	Glutamic acid	1: 1
1-4	Glutaric acid	1: 1
1-5	Tartaric acid	1: 1
1-6	Aspartic acid	1: 1
1-7	Fumaric acid	1: 1
1-8	Glyoxylic acid	1: 1
1-9	4-ketopimelic acid	1: 1
1-10	Pyruvic acid	1: 1
1 -11	1,3-acetonedicarboxylic acid	1: 1

The precipitation of the composition prepared according to Table 1 was evaluated. Specifically, each composition was applied to a thickness of about 50 μm using a bar coater on a 50 μm thick OPP film (Samyoung Chemical). After the film to which the composition was applied was left for 14 days at room temperature (25 ° C., 60 ± 10% relative humidity), the surface change of the pressure-sensitive adhesive composition present on the OPP film was confirmed to evaluate the shape change. 2 is shown.

No.	mountain	Lysic acid: mol ratio	menstruum	Solid content (parts by weight)	Check shape
1-1	Alpha keto glutaric acid	1: 1	DIW	50	Liquid maintenance
1-2	Acetic acid	1: 1			Sedimentation
1-3	Glutamic acid	1: 1			Sedimentation
1-4	Glutaric acid	1: 1			Sedimentation
1-5	Tartaric acid	1: 1			Sedimentation
1-6	Aspartic acid	1: 1			Sedimentation
1-7	Fumaric acid	1: 1			Sedimentation
1-8	Glyoxylic acid	1: 1			Sedimentation
1-9	4-ketopimelic acid	1: 1			Sedimentation
1-10	Pyruvic acid	1: 1			Sedimentation
1 -11	1,3-acetonedicarboxylic acid	1: 1			Sedimentation

Referring to the results of Table 2, the composition containing lysine and alpha ketoglutaric acid did not form a precipitate, while the composition containing other organic acids and lysine could form a precipitate to evaluate the adhesiveness. That is, when the composition is prepared by mixing lysine and various organic acids, it was confirmed that not all compositions exhibit stickiness without forming a precipitate.

Example 2 Evaluation of Solubility According to the Solvent of the Composition

According to the preparation method described in Example 1, an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared. (Molar ratio of lysine and alpha ketoglutaric acid = 1: 1, 50 parts by weight of solids content) To the prepared 50 g of the pressure-sensitive adhesive composition, 25 g of the additional solvent of Table 3 were added and stirred for 1 hour. After stirring, the solubility in each solvent of the pressure-sensitive adhesive composition was confirmed. The solubility evaluation results of the pressure-sensitive adhesive composition according to the type of solvent and each solvent added are shown in Table 3 below.

No.	Additional solvent	Dissolution result
2-1	Methanol	Dissolved
2-2	toluene	Insoluble
2-3	benzene	Insoluble
2-4	chloroform	Insoluble
2-5	Methylene chloride	Insoluble
2-6	Dichloromethane	Insoluble
2-7	Tetrahydrofuran (THF)	Insoluble
2-8	Ethyl acetate	Insoluble
2-9	Dimethylformamide (DMF)	Insoluble
2-10	Dimethyl Sulfoxide (DMSO)	Insoluble
2 -11	n-hexane	Insoluble

Referring to Table 3, the pressure-sensitive adhesive composition of the present application was dissolved when an alcohol such as methanol was used as a solvent, but was not dissolved in other organic solvents.

[ Example  3] With lysine Alphaketoglutaric acid In mixed molar ratio  Shape, viscosity and Initial adhesion  analysis

The stability, viscosity and initial adhesion of the composition according to the molar ratio of lysine and alpha ketoglutaric acid in the adhesive composition of the present application were analyzed.

According to the preparation method described in Example 1, an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared. However, the molar ratio of lysine and alpha ketoglutaric acid was 3: 1. An adhesive composition was prepared at 2.5: 1, 2: 1, 1.5: 1, 1: 1, 1: 1.5, 1: 2, 1: 2.5 and 1: 3. (50 parts by weight of solid content)

(1) stability evaluation

Specific methods for evaluating the stability of each pressure-sensitive adhesive composition having a variety of molar ratios are as follows. Each adhesive composition was weighed about 1 g in an aluminum dish with a diameter of 5 cm. Thereafter, it was confirmed whether or not crystallization of the adhesive composition was carried out under the following drying conditions.

i) Drying condition 1

For 14 days at room temperature (25 ℃), 60 ± 10% relative humidity conditions were confirmed the formation of precipitates and surface changes in the adhesive composition.

ii) Drying condition 2

For 48hr in the oven controlled at 40 ℃ was confirmed whether the precipitate formed in the adhesive composition and the surface change.

(2) viscosity evaluation

Viscosity was measured using a rotary viscometer (manufacturer: LAMYRHEOLOGY) under conditions of 25 rpm, 1 ° C LV-1 spindle, 60 rpm.

(3) initial tack

Initial adhesion was evaluated for the composition in which no precipitation was formed in the stability evaluation. Initial adhesive force was used by Anton Paar's Rheometer measuring equipment, through which the initial adhesive strength of the adhesive composition was compared. A probe made of SUS material having a diameter of 25 mm was contacted with the adhesive composition for 1 minute to maintain a 0.01 mm gap, and then the force generated by peeling the probe at the same speed was measured. Quantitative evaluation was performed.

The evaluation results are shown in Table 4 below.

No.	Lysine: aKG (mol ratio)	Solid content (parts by weight)	Viscosity (mPa.s)	Initial Adhesion (mJ)	shape
3-1	3: 1	50	45.57	-	Sedimentation
3-2	2.5: 1		42.00	-	Sedimentation
3-3	2: 1		39.36	-	Sedimentation
3-4	1.5: 1		34.13	0.30	Liquid maintenance
3-5	1: 1		31.80	0.31	Liquid maintenance
3-6	1: 1.5		29.98	0.30	Liquid maintenance
3-7	1: 2		29.79	0.31	Liquid maintenance
3-8	1: 2.5		28.89	0.34	Liquid maintenance
3-9	1: 3		29.20	0.31	Liquid maintenance

* In Table 4, room temperature indicates drying condition 1 and oven indicates drying condition 2.

Referring to Table 4, precipitation was formed in the case of the 3: 1 to 2: 1 adhesive composition with a molar ratio of lysine and alpha ketoglutaric acid.

Precipitation was formed when the molar ratio of lysine and alpha ketoglutaric acid was 2: 1, whereas no precipitation was formed when the molar ratio of lysine and alpha ketoglutaric acid was 1.5: 1. In order to identify a more specific critical point, the adhesive composition was prepared by subdividing the molar ratio of lysine and alpha ketoglutaric acid into 2.0: 1, 1.9: 1, 1.8: 1, 1.7: 1, 1.6: 1, 1.5: 1. Then (50 parts by weight of solid content), the stability, viscosity, and initial adhesion were evaluated in the same manner.

The evaluation results are shown in Table 5 below.

No.	Lysine: aKG (molar ratio)	Solid content (wt%)	Viscosity (mPa.s)	Initial Adhesion (mJ)	Shape check
3-10	2.0: 1	50	39.70	-	Sedimentation
3-11	1.9: 1		37.74	-	Sedimentation
3-12	1.8: 1		35.59	-	Sedimentation
3-13	1.7: 1		35.11	0.341	Liquid maintenance
3-14	1.6: 1		35.02	0.326	Liquid maintenance
3-15	1.5: 1		35.30	0.322	Liquid maintenance

Referring to Table 5, precipitation was formed when the molar ratio of lysine and alpha ketoglutaric acid was 2: 1 to 1.8: 1, while the molar ratio of lysine and alpha ketoglutaric acid was 1.7: 1 to 1.5: 1. In the case of no precipitation was formed.

[ Example  4] shape, viscosity and adhesion composition of the adhesive composition according to the solid content Initial adhesion  analysis

The shape, viscosity and initial adhesion of the composition according to the solid content in the adhesive composition of the present application were analyzed.

1) Evaluation according to the solid content when the molar ratio of lysine and alpha ketoglutaric acid is 1: 1

According to the preparation method described in Example 1, an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared. However, the adhesive composition was prepared so that the solids content in the adhesive composition was 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, and 75% by weight, respectively. (The molar ratio of lysine and alpha ketoglutaric acid is 1: 1.) The solid content was adjusted to the content of water.

The shape, viscosity, and initial adhesion of the composition were evaluated in the same manner as described in Example 3. The evaluation results are shown in Table 6 below.

No.	Lysine: aKG (mol ratio)	Solid content (wt%)	Viscosity (mPa.s)	Initial Adhesion (mJ)	Shape check
4-1	1: 1	10	17.93	0.2315	Liquid maintenance
4-2	1: 1	20	19.70	0.268	Liquid maintenance
4-3	1: 1	30	20.56	0.274	Liquid maintenance
4-4	1: 1	40	26.75	0.275	Liquid maintenance
4-5	1: 1	50	32.95	0.3145	Liquid maintenance
4-6	1: 1	60	64.92	0.3385	Liquid maintenance
4-7	1: 1	70	286.10	0.635	Liquid maintenance
4-8	1: 1	75	1264.67	-	Sedimentation

Referring to Table 6, when the content of the solid content in the adhesive composition is 10 to 70% by weight, it could be confirmed that the precipitate is formed without dissolution.

In order to identify more specific thresholds, the solids content in the composition may be 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, After further subdividing into 74 wt%, 75 wt% and 76 wt% to prepare an adhesive composition (molar ratio of lysine and alpha ketoglutaric acid is 1: 1), the same method was used to evaluate the stability, viscosity, and initial adhesion. It was. The evaluation results are shown in Table 7 below.

No.	Lysine: aKG (mol ratio)	Solid content (wt%)	Viscosity (mPa.s)	Initial Adhesion (mJ)	Shape check
4-9	1: 1	65	111.5	0.624	Liquid maintenance
4-10	1: 1	66	133.0	0.629	Liquid maintenance
4-11	1: 1	67	157.1	0.689	Liquid maintenance
4-12	1: 1	68	189.4	0.736	Liquid maintenance
4-13	1: 1	69	226.6	0.751	Liquid maintenance
4-14	1: 1	70	287.9	0.781	Liquid maintenance
4-15	1: 1	71	363.9	-	Sedimentation
4-16	1: 1	72	487.2	-	Sedimentation
4-17	1: 1	73	629.9	-	Sedimentation
4-18	1: 1	74	897.3	-	Sedimentation
4-19	1: 1	75	1268.3	-	Sedimentation
4-20	1: 1	76	1731.0	-	Sedimentation

Referring to Table 7, the content of the solid content in the adhesive composition was maintained from 65% to 70% by weight, but when the solid content in the adhesive composition is 71% by weight or more, it is confirmed that a precipitate is formed within 2 weeks. Could.

 2) Evaluation according to the solid content when the molar ratio of lysine and alpha ketoglutaric acid is 1: 2, 1: 3 or 2: 1

When the molar ratio of lysine and alpha ketoglutaric acid was changed, it was evaluated whether precipitates were formed according to the solid content.

According to the preparation method described in Example 1, an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared. However, lysine and alpha ketoglutaric acid were mixed so that the molar ratio of lysine and alpha ketoglutaric acid was 1: 2, 1: 3, and 2: 1, respectively. For the compositions having respective molar ratios, the water content was adjusted so that the solids content in the composition was 10%, 20%, 30%, 40%, 50%, 60%, 70% by weight, respectively. . For each composition, the stability of the composition was evaluated in the same manner as described in Example 1. The evaluation results are shown in Table 8.

No.	Lysine: aKG (mol ratio)	Solid content (wt%)	Viscosity (mPa.s)	Initial Adhesion (mJ)	shape
4-21	1: 2	10	17.84	0.179	Liquid maintenance
4-22		20	20.03	0.187	Liquid maintenance
4-23		30	23.35	0.273	Liquid maintenance
4-24		40	24.73	0.344	Liquid maintenance
4-25		50	29.38	0.399	Liquid maintenance
4-26		60	44.67	0.827	Liquid maintenance
4-27		70	138.80	0.857	Liquid maintenance
4-28	1: 3	10	19.09	0.081	Liquid maintenance
4-29		20	21.12	0.094	Liquid maintenance
4-30		30	23.82	0.139	Liquid maintenance
4-31		40	26.72	0.235	Liquid maintenance
4-32		50	30.29	0.292	Liquid maintenance
4-33		60	41.68	0.411	Liquid maintenance
4-34		70	105.47	0.618	Liquid maintenance
4-35	2: 1	10	25.40	-	Sedimentation
4-36		20	25.86	-	Sedimentation
4-37		30	27.32	-	Sedimentation
4-38		40	31.30	-	Sedimentation
4-39		50	40.10	-	Sedimentation
4-40		60	118.40	-	Sedimentation
4-41		70	584.00	-	Sedimentation

Referring to Table 8, when the molar ratio of lysine and alpha ketoglutaric acid is 1: 2 and 1: 3, no precipitation was formed even when the solid content was changed to 10 wt% to 70 wt%. On the other hand, when the molar ratio of lysine and alpha ketoglutaric acid is 2: 1, precipitation was formed at any solid content.

In other words, the stability and adhesion of the pressure-sensitive adhesive composition of the present application is determined to have the greatest effect according to the molar ratio of lysine and alpha ketoglutaric acid. It was confirmed that it is large.

Example 5 Comparison of Initial Adhesion and Water Separability

The adhesive force and water separation property of the conventional adhesive and the adhesive composition of the present application were compared.

According to the preparation method described in Example 1, an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared. However, the content of water was adjusted so that the content of solids in the adhesive composition was 10% by weight. (Molar ratio of lysine and alpha ketoglutaric acid = 1: 1)

After preparing a commercially available polyvinyl alcohol based adhesive (PVA 088-50, Qingdao Sanhuan Colorchem CO., LTD), by adjusting the content of water so that the solid content is 10% by weight of the adhesive composition (hereinafter, Control 1) was prepared.

Using the same method as described in Example 3, the viscosity and initial adhesive strength of the pressure-sensitive adhesive composition (solid content of 10% by weight) of the present application and the control 1 was evaluated.

In addition, the water separability of the pressure-sensitive adhesive composition (solid content of 10% by weight) of the present application and the control 1 was evaluated. The method for evaluating water separability is as follows.

The adhesive composition of the present application was applied to a thickness of 50 ~ 60㎛ on the PET film and then dried for 30 minutes at 40 ℃. The dried resultant was cut to a size of 25 mm × 25 mm, attached to stainless steel (SUS304), and pressed by bonding 5 times at a pressure of 2 kgf using a hand roller to prepare a specimen. PVA pressure-sensitive adhesive was applied on the PET film with a thickness of 50 ~ 60㎛, cut into 25mmX25mm size and attached to stainless steel (SUS304), and pressed by 5 times at a pressure of 2kgf using a hand roller to prepare a specimen. .

After the specimens were completely immersed in distilled water (DIW) at room temperature, atmospheric pressure and pH neutral conditions, the specimens were checked after i) one hour or ii) 24 hours at 200 rpm using a stirrer. Thereafter, the time from the specimen until the adhesive composition or the adhesive was completely removed from the substrate was measured to evaluate the water separability of the specimen.

The evaluation results are shown in Table 9 below.

	Solid content (wt%)	Viscosity (mPa.s)	Initial Adhesion (mJ)	Water separation
5-1	10	17.93	0.2315	Detached within 1 hour
Control group 1 (PVA system)	10	43.49	0.201	At 200 rpm i) only partially soluble in water after 1 hour or ii) soluble in water after 24 hours

Referring to Table 9, the pressure-sensitive adhesive composition according to the present application exhibited an equivalent level of initial adhesive force as compared to the polyvinyl alcohol-based pressure-sensitive adhesive composition (Control 1), and was separated in water in a short time. On the other hand, the polyvinyl alcohol-based adhesive composition was dissolved in water after 24 hours after immersion in water, but only partially dissolved in water after 1 hour.

That is, the pressure-sensitive adhesive composition according to the present invention is compared to the conventional pressure-sensitive adhesive strength or more than the equivalent level or water separation is very excellent, it is expected that it can be utilized in various fields.

Example 6 Evaluation of Initial Adhesive Force and Water Separability According to Solvent

According to the preparation method described in Example 1, a pressure-sensitive adhesive composition containing lysine and alpha ketoglutaric acid was prepared (following 6-1 to 6-3). However, an adhesive composition was prepared using a molar ratio of lysine and alpha ketoglutaric acid as 1.5: 1, 1: 1, and 1: 1.5, respectively. (50 parts by weight of solid content)

In addition, according to the production method described in Example 1, an adhesive composition containing lysine and alpha ketoglutaric acid was prepared (6-4 to 6-6 below). However, the pressure-sensitive adhesive composition was prepared with a molar ratio of lysine and alpha ketoglutaric acid of 1.5: 1, 1: 1, and 1: 1.5, respectively. Used. (50 parts by weight of solid content)

As a control, a commercially available acrylic pressure-sensitive adhesive (K901, Hansung P & I) (hereinafter referred to as control 2) (solid content 59 wt%) was prepared. Peel strength and water separability of each of the adhesive compositions were evaluated according to the following methods, and the evaluation results are shown in Table 10 below.

1) Water Separation

The prepared pressure-sensitive adhesive composition, and the composition of the control 2 were each applied to a thickness of 50 ~ 60㎛ on the PET film and then dried at 40 ℃ for 30 minutes.

The dried resultant was cut into a size of 25 mm × 25 mm, attached to stainless steel (SUS304), and pressed and bonded five times at a pressure of 2 kgf using a hand roller to prepare a specimen.

After the specimens were completely immersed in distilled water (DIW) at room temperature, atmospheric pressure and pH neutral conditions, the specimens were checked after i) one hour or ii) 24 hours at 200 rpm using a stirrer.

No.	Lysine: aKG (molar ratio)	menstruum	Solids (wt%)	Viscosity (mPa.s)	Initial Adhesion (mJ)	shape	Water separation
6-1	1.5: 1	DIW	50	31.2	0.380	Liquid maintenance	Dissolved in water at 200 rpm i) after 1 hour or ii) after 24 hours
6-2	1: 1			28.7	0.317	Liquid maintenance
6-3	1: 1.5			27.3	0.300	Liquid maintenance
6-4	1.5: 1	DIW and Methanol (1: 1 wt ratio)		49.2	0.570	Liquid maintenance
6-5	1: 1			42.8	0.554	Liquid maintenance
6-6	1: 1.5			39.1	0.522	Liquid maintenance
6-7	1: 1	DIW and Methanol (6: 4 wt ratio)		42.5	0.513	Liquid maintenance
6-8	1: 1	DIW and Methanol (4: 6 wt ratio)		47.9	0.614	Liquid maintenance
Control 2 (acrylic)	-		59	248.9	0.292		Insoluble in water

Referring to Table 10, the adhesive product obtained using the adhesive composition according to the present application was separated from water within 1 hour after being immersed in water. In addition, in the case of using water and alcohol as a solvent it was confirmed that the initial adhesion is further improved. This result is because the adhesive composition using the mixed solvent has a lower contact angle than the adhesive composition containing only deionized water, and as a result, the coating property on the substrate is better. The pressure-sensitive adhesive composition according to the present application was confirmed that the initial adhesive strength is comparable level, although the solid content is lower than that of the conventional acrylic pressure-sensitive adhesive (Control 2). However, the acrylic adhesive did not dissolve in water even after 24 hours.

[ Example  7] Analysis of composition in adhesive composition according to reaction time and temperature condition

In preparing the adhesive composition, the composition in the adhesive composition was analyzed according to the reaction time.

1) Prepared at 40 ° C .: DIW (distilled water) in 100 g of 54 wt% lysine preform aqueous solution

61.95 g was added and stirred at room temperature 25 ° C. (T1) for 30 minutes. 53.97 g of alpha keto glutaric acid was slowly added to the diluted product at 40 ° C. (T2), followed by stirring for 12 hours to prepare an adhesive composition. (Solid content: 50% by weight, mixed molar ratio of lysine and alpha ketoglutaric acid = 1: 1) The composition in the adhesive composition was analyzed every 3 hours.

2) Preparation at room temperature (RT): The composition was prepared in the same manner as in 1) above, except that T2 was changed to RT ° C. The composition in the adhesive composition was analyzed every three hours.

Component analysis was performed on the prepared composition using high performance liquid chromatography (HPLC).

The analysis results are shown in Table 11 below.

Temperature	Response time (hr)	Lysine (wt%)	Alpha ketoglutaric acid (wt%)
40 ℃	0	24.92	24.87
	3	23.68	23.74
	6	23.12	23.02
	9	23.56	21.87
	12	22.41	20.23
RT.	0	24.98	25.06
	3	24.68	24.87
	6	24.57	24.98
	9	24.24	24.63
	12	24.31	24.46

Referring to Table 11, when the composition is prepared at a temperature of 40 ℃, it can be seen that the content of lysine and alpha ketoglutaric acid in the composition gradually decreased as the reaction time gradually increased.

In contrast, when the composition is prepared at room temperature (RT), the content of lysate and alpha ketoglutaric acid decreases as the reaction time is gradually increased, but the decrease is lower than that of the composition prepared at the temperature of 40 ° C. It was found to shrink.

From this, it can be seen that when the composition is prepared at 40 ° C., side reactions may occur and curing may occur.

One embodiment has been described above with reference to the drawings and embodiments, but this is only illustrative, and those skilled in the art may understand that various modifications and equivalent other embodiments are possible therefrom. will be. Therefore, the protection scope of the present application should be defined by the appended claims.

Claims (13)

1. Lysine, alphaketoglutaric acid and water,

   Wherein the lysine and alpha ketoglutaric acid is in the form of a salt solution (salt solution) and does not form precipitates (precipitates) in the adhesive composition.
2. The method of claim 1,

   The precipitate is a pressure-sensitive adhesive composition is a precipitate of lysine and alpha ketoglutaric acid.
3. The method of claim 1,

   The mixing molar ratio of lysine and alpha ketoglutaric acid is controlled such that precipitation of lysine and alpha ketoglutaric acid is not formed in the adhesive composition.
4. The method of claim 3,

   The mixing molar ratio of the lysine and alpha keto glutaric acid is 1.7: 1 to 1: 3 adhesive composition.
5. The method of claim 1,

   Solid content in the pressure-sensitive adhesive composition is 70 parts by weight or less based on the total weight of the composition, pressure-sensitive adhesive composition.
6. The method of claim 1,

   The pressure-sensitive adhesive composition, wherein the sum of the citric acid and the alpha ketoglutaric acid content is 60 to 100 parts by weight based on 100 parts by weight of the solid content in the pressure-sensitive adhesive composition.
7. The method of claim 1,

   The pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition further comprises one or more solvents selected from the group consisting of primary alcohols, polyhydric alcohols, diols and triols.
8. The method of claim 7, wherein

   The solvent is at least one monohydric alcohol selected from methanol, ethanol, propan-2-ol, butan-1-ol, pentan-1-ol and hexadecane-1-ol; Ethane-1,2-diol, propane-1,2-diol, propane-1,2,3-triol , 3-triol), butane-1,3-diol, butane-1,2,3,4-tetraol, butane-1,3-diol -1,2,3,4,5-pentol (pentane-1,2,3,4,5-pentol), hexane-1,2,3,4,5,6-hexol (hexane-1,2, 3,4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptol (heptane-1,2,3,4,5,6,7-heptol) Polyhydric alcohols; Pro-2-en-1-ol, 3,7-dimethylocta-2,6-diene1-ol (3,7-Dimethylocta-2,6-dien-1 -ol), one or more unsaturated aliphatic alcohols selected from Pro-2-yn-1-ol; Cyclohexane-1,2,3,4,5,6-hexol (cyclohexane-1,2,3,4,5,6-hexol), 2- (2-propyl) -5-methylcyclohexane-1- Adhesive composition which is one or more alicyclic alcohols or mixtures thereof selected from all- (2- (2-propyl) -5-methyl-cyclohexane-1-ol).
9. The method of claim 1,

   The pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition is not formed when stored for more than 14 days at less than -18 ℃ to 40 ℃.
10. Mixing lysine, alpha ketoglutaric acid and water; And

    Stirring the mixture at less than 40 ° C .;

    The content of lysine, alpha ketoglutaric acid and water in the pressure-sensitive adhesive composition is adjusted so that no precipitation of lysine and alpha-ketoglutaric acid is formed.
11. The method of claim 10,

    Method for producing a pressure-sensitive adhesive composition in which the mixing molar ratio of the lysine and alpha keto glutaric acid is 1.7: 1 to 1: 3.
12. The method of claim 10,

    The mixture further comprises one or more solvents selected from the group consisting of primary alcohols, polyhydric alcohols, diols and triols.
13. An adhesive product comprising the adhesive composition of any one of claims 1 to 9.