KR20200026100A - An adhesive composition for paper bag, preparation method thereof, a sheet for paper bag comprising adhesive composition, and a paper bag comprising sheet for paper bag - Google Patents

Abstract

The present invention relates to an adhesive composition for a paper bag, comprising salt of lysine and citric acid and a thickener, and having excellent peeling strength, to a paper for a paper bag, and to a paper bag.

Description

An adhesive composition for paper bag, preparation method thereof, a sheet for paper bag comprising adhesive composition, and a paper bag comprising sheet for paper bag

The present application relates to a pressure-sensitive adhesive composition, a method of manufacturing the same, a zone paper and a zone including the same.

Zones are used for moisture-proof packaging of sugar, milling, feed, cement, etc.

Conventional rent adhesives generally contain a polymer as a main component to impart tackiness. The pressure sensitive adhesive containing the polymer as a main component provides excellent adhesion required for various environments by controlling the structure and molecular weight of the polymer.

However, since the polymer is manufactured through a complex process such as synthesis and purification, it causes various environmental pollution. For example, a monomer derived from a fossil raw material is used as a raw material of the polymer, an excess of an organic solvent is used in the purification of the polymer, and a long time is required for decomposition of the produced polymer. Therefore, recycling of the zone is difficult.

Therefore, there is a need for a pressure-sensitive adhesive that uses renewable raw materials and provides excellent adhesiveness without using a polymer as a main component, thereby making it easier to recycle the zone.

One aspect of the present application is to provide a pressure-sensitive adhesive composition having excellent peel strength.

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

Another aspect of the present application is to provide a zone paper comprising a zone adhesive composition.

Another aspect of the present application is to provide a zone including zone paper.

According to one aspect, there is provided a tacky adhesive composition comprising a salt of lysine and citric acid and a thickener.

According to another aspect, mixing lysine, citric acid, thickener and water; And stirring the mixture at 80 ° C. or less.

According to another aspect, a first substrate comprising a paper; A second substrate disposed on one surface of the first substrate and including a polymer; And a pressure-sensitive adhesive layer disposed between the first base material and the second base material, wherein the pressure-sensitive adhesive layer comprises a zone paper including the pressure-sensitive adhesive composition according to any one of claims 1 to 15.

According to another aspect, a zone is provided comprising the zone sheet according to the above.

The adhesive composition for rent according to one embodiment provides an excellent peel strength by having a new composition containing a water-soluble low molecular material as a main component.

Figure 1 shows the results of the ¹ H nuclear magnetic resonance spectrum (NMR) analysis according to Reference Example 7.

Hereinafter, the adhesive composition for a rent according to one embodiment, a manufacturing method thereof, a paper sheet including the same and a rent will be described in more detail.

As used herein, the term "adhesion" means a tendency in which two different objects (but not gases) come into close proximity or contact with each other and then pull each other. That is, tackiness refers to a phenomenon in which two different objects (except gas) are required to have a certain force (or work) after they are brought into close proximity or contact with each other.

As used herein, the term "viscoelasticity" refers to a phenomenon in which, when a force is applied to an object, a flow having no restoring force against deformation and an elastic deformation having restoring force simultaneously appear. Viscoelastic materials have both solid and liquid properties.

As used herein, "viscosity" refers to a property that is intended to hinder the flow of a substance as a result of internal friction between molecules. Friction is the force that tries to prevent a difference in the distribution of flow velocity. Tackiness and viscosity are separate properties. The material with high viscosity may have little adhesiveness, and the material with low viscosity may have high adhesiveness.

Compositions with adhesion may have viscoelasticity. After applying the composition having a viscoelasticity to the substrate, deformation by force of a certain size is required when separating from the substrate. Compositions having viscoelastic properties can be reversibly attached and detached from a substrate. When the composition having a viscoelasticity is applied to a substrate and dried, an adhesive layer containing the composition having a viscoelasticity is formed on the substrate. The viscoelastic composition is stored and distributed through a general processing form prior to application to the substrate and maintains its adhesion even after a certain time. The adhesive article obtained by apply | coating and drying such an adhesive composition on a base material is a label, Oriented Polypropylene (OPP) tape, etc., for example. In addition, compositions with adhesion may not have viscoelasticity. After the adhesive composition is applied to the substrate, it may be solidified after a period of time to disappear viscoelasticity. The desire to separate such viscoelastic solidified material from the substrate can involve irreversible physical destruction.

Zone adhesive compositions include salts and thickeners of lysine and citric acid.

Salts of lysine and citric acid are low molecular weight materials, but provide tack. Thickeners provide additional tack. Thickeners also control the solubility of the adhesive composition for water in water. Thus, the adhesive composition for rent provides excellent peel strength by including salts and thickeners of lysine and citric acid. The pressure-sensitive adhesive composition contains a salt of lysine and citric acid as a main component. As used herein, the term "main component" means a component having the highest content among components except for a solvent. It is possible to control the adhesive strength and peel strength according to the content and type of thickener in the adhesive composition for rent. In addition, the adhesive composition for the zone is dissociated by water, and the dissociated components are also environmentally friendly because they are harmless to life and the environment.

Thickeners are, for example, water soluble polymers. Thickeners include, for example, one or more selected from water soluble natural polymers, and water soluble synthetic polymers. The adhesive layer formed from the adhesive composition for rent can be removed by water, since the adhesive composition for rent is water-soluble as a thickener. That is, the adhesive layer can be peeled from the zone by water.

Water soluble natural polymers include, for example, xanthan gum, guar gum, gum arabic, tragacanth gum, galactan, carab gum, karaya gum, carrageenan, acacia gum, pectin, cannan, queens seed ( Quince), algocolloid (algae extract), starch (derived from rice, corn, potatoes, wheat, etc.), glycyrrhizin, alginin, sodium alginate, collagen, alginate ), Gelatin, furcellaran, carrageenan, casein, locust bean gum, pectin, chitosan, albumin, dextran, succino Glucan, blueran, tragacanthin, hyaluronic acid, pectin, alginic acid, agar, galactomannans, beta-cyclodextrin, amylose ( amylase), casein, and chitosan; It not limited to those so long as it can all be used as water-soluble natural polymers in the art.

The water-soluble synthetic polymer is, for example, polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), N- (2-hydroxypropyl) Methacrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA), polyphosphate, polyphosphazene, methyl cellulose, methyl ethyl cellulose, ethyl cellulose, microcrystalline cellulose, hydroxyethyl cellulose, hydroxybutyl methyl Cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose stearoxy ether, carboxymethyl hydroxyethyl cellulose, alkyl hydroxyethyl cellulose, nonoxynyl hydroxyethyl cellulose, cellulose Sodium sulfate, methylcellulose, methylethylcellulose, ethylcellulose, and car One or more selected from carboxymethyl cellulose (CMC), but not necessarily limited to any of these can be used as a water-soluble synthetic polymer in the art.

In the pressure-sensitive adhesive composition, the thickener content in the composition is for example 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the composition. Too much thickener may cause precipitation. In the zoned adhesive composition, the thickener content in the composition is, for example, 1 to 10 parts by weight, 1 to 9 parts by weight, 1 to 8 parts by weight, 1 to 7 parts by weight, or 1 to 1 based on 100 parts by weight of the zoned adhesive composition. 5 parts by weight.

The adhesive composition for abutment further contains a stabilizer, for example. Stabilizers, for example, improve the phase stability of the zoned adhesive composition. Stabilizers include, for example, one or more selected from alcohols (monohydric alcohols), polyhydric alcohols, and polyhydric amines. Stabilizers include, for example, glycerol, alkylene glycol, dialkylene glycol, benzenediol, benzenetriol, dialcoalamine, trialcoholamine, arabitol, mannitol, isomalt, xylitol, sorbitol, maltitol, erythritol, Ribitol, dulcitol, lactitol, traceritol, iditol, polyglycitol, methanol, ethanol, propan-2-ol, butan-1-ol, pentane-1ol, ethane-1,2-diol -1,2-diol), propane-1,2-diol, propane-1,2,3-triol, butane-1 , 3-diol (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-hexolhexane-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), pro-2-en-1-ol (Prop- 2-ene-1-ol), 3,7-dimethylocta-2,6-diene1-ol (3,7-Dimethylocta-2,6-dien-1-ol), pro-2-yn-1- Prop-2-yn-1-ol, cyclohexane-1,2,3,4,5,6-hexol (cyclohexane-1,2,3,4,5,6-hexol), 2- ( 2-propyl) -5- Butylcyclohexane-1-ol (2- (2-propyl) -5-methyl-cyclohexane-1-ol), C2-C10 alkylenediamine, C2-C10 alkenylenediamine, phenylenediamine and n-amino (C1 And one or more selected from -C 5) alkyl (C 1 -C 5) alkanediamines, but are not necessarily limited to any of these and may be used as stabilizers in the art.

In the zoned adhesive composition, the stabilizer content is, for example, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight based on 100 parts by weight of the composition. 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. The zoned adhesive composition can provide improved dust adhesion and / or peel strength by including a stabilizer in this range.

In the fat adhesive composition, the content of a salt of lysine and citric acid in the composition is, for example, 70 parts by weight or less, 60 parts by weight or less, or 50 parts by weight or less based on 100 parts by weight of the fat adhesive composition. In the zoned adhesive composition, the content of salts of lysine and citric acid in the composition is, for example, 1 to 70 parts by weight, 5 to 70 parts by weight, 10 to 70 parts by weight, 10 based on 100 parts by weight of the zoned adhesive composition. To 60 parts by weight, 10 to 50 parts by weight, 20 to 50 parts by weight, or 30 to 50 parts by weight. In the zoned adhesive composition, the salt content of lysine and citric acid in the composition is, for example, 1 to 70 wt%, 5 to 70 wt%, 10 to 70 wt%, 10 to 60 wt% based on the total weight of the zoned adhesive composition. , 10 to 50 wt%, 20 to 50 wt%, or 30 to 50 wt%.

In the pressure-sensitive adhesive composition, the salt content of lysine and citric acid is 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt% or more based on the total weight of organic solids. At least 70 wt%, at least 80 wt%, or at least 90 wt%. In the zoned adhesive composition, the salt content of lysine and citric acid is, for example, 10wt% to 99wt%, 20wt% to 99wt%, 30wt% to 99wt%, 40wt% based on the total weight of organic solids. To 99 wt%, 50 wt% to 99 wt%, 60 wt% to 99 wt%, 70 wt% to 99 wt%, 80 wt% to 99 wt%, or 90 wt% to 99 wt%. For example, the sum of citric acid and lysine content based on 100 parts by weight of the adhesive composition for rent is 10 to 99 parts by weight, 20 to 99 parts by weight, 30 to 99 parts by weight, 40 to 99 parts by weight, 50 to 99 parts by weight. Parts, 60 to 99 parts by weight, 70 to 99 parts by weight, 80 to 98 parts by weight, or 85 to 97 parts by weight. The salts of lysine and citric acid have a content in this range so that the tack and / or peel strength is further improved. Organic solids include, for example, salts and thickeners of lysine and citric acid.

In the zoned adhesive composition, for example, precipitates are free in the composition. The zoned adhesive composition does not contain precipitates to provide further improved tack and / or peel strength.

Precipitates may be one or more precipitates selected from lysine, citric acid and thickeners. For example, as shown in Scheme 1 below, an insoluble salt (AB (s)) is obtained by chemical change of an aqueous solution of lysine (A (aq)) and an aqueous solution of citric acid (B (aq)), as shown in Scheme 2 below. Lysine solid (A (s)) or citric acid solid (B (s)) is precipitated from aqueous lysine solution (A (aq)) or citric acid solution (B (aq)) or lysine solid (A (s)) or citric acid solid It includes all cases in which (B (s)) is not dissolved in a solvent and remains in an insoluble state. In addition, the thickening agent may be precipitated in the adhesive composition for rent, or the thickener may not be dissolved in a solvent, thereby leaving an insoluble state.

Scheme 1

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

Scheme 2

A (aq)-> A (s)

As used herein, “precipitate” is a precipitate produced during storage, distribution, and prior to the application of a substrate or adhesive.

As used herein, the term “lysine” is one of the basic α-amino acids, where lysine is biosynthesized or chemically synthesized from oxalacetic acid via the lysine biosynthetic pathway.

Lysine includes one lysine or a mixture of one or more lysines.

Lysine is at least one selected from L-lysine represented by the following formula (1), D-lysine represented by the following formula (2) and salts thereof.

[Formula 1]

[Formula 2]

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.

Conversion of lysine salts to lysine preforms is known to those of ordinary skill 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.

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

[Formula 3]

The salts of lysine and citric acid are present in the form of salt solutions, for example, in the adhesive composition for rent. In the case of mixing lysine, citric acid, water and thickeners, lysine and citric acid do not form covalent compounds or insoluble salts, for example in the form of aqueous salt solutions.

The content of lysine, citric acid, water and thickener in the adhesive composition for rent can be controlled so that lysine and citric acid do not precipitate or form precipitates. When the adhesive composition for a zone maintains a liquid state without forming crystal | crystallization or precipitation, it is excellent in adhesiveness and it is easy to apply | coat uniformly to a base material.

The mixing molar ratio of lysine and citric acid may be 1.5: 1 to 1: 3. Specifically, the mixed molar ratio of lysine and citric acid may be 1.5: 1 to 1: 2, 1.5: 1 to 1: 1.5, 1.5: 1 to 1: 1.5 or 1.5: 1 to 1: 1. If the content of lysine to citric acid is more or less than the above-mentioned range, precipitation in the composition may be formed, thereby lowering the adhesiveness or lowering the storage stability or storage stability of the adhesive composition.

The content of solids, including salts and tackifiers of lysine and citric acid, in the adhesive composition for rent is 70 parts by weight or less, for example, 0.1 to 70 parts by weight, 1 to 70 parts by weight, based on 100 parts by weight of the composition. Parts, or 10 to 70 parts by weight. When the content of the solid content is within this range, it is easy to apply the adhesive composition for rent on the substrate, and when the content of the solid content is 70 parts by weight or more, precipitation may be formed and thus it may be difficult to use 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.

In the adhesive composition for rent, citric acid and lysine may be contained in the form of a condensate containing citric 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, 10 parts by weight or less, 1 part by weight or less based on 100 parts by weight of the sum of citric acid and lysine content. And may include zero. 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.

The reason why the pressure-sensitive adhesive composition exhibits the adhesiveness as described above will be described more specifically. This description of tack is merely to aid understanding and is not intended to limit the scope of the present application to the scope of this interpretation. Tackiness may be explained for other reasons as long as there is no scientific contradiction. Salts of lysine and citric acid provide adhesion to the composition by, for example, forming a kind of network in the composition by strong interactions between lysine and citric acid or lysine and citric acid, water, or lysine and citric acid, water, thickeners. do. Lysine has two amino groups and citric acid has three carbonyl groups. The unshared electron pair of oxygen of the carbonyl group of citric acid and the hydrogen of the amino group of lysine have a strong interaction through an ionic hydrogen bond. In addition, a non-covalent electron pair of oxygen of the carbonyl group of citric acid, hydrogen of the amino group of lysine, and water have a strong interaction through an ionic hydrogen bond. When the adhesive composition for a rent is analyzed by liquid chromatography etc., lysine and a citric acid can be confirmed as a raw material. From this, the lysine and citric acid in the pressure-sensitive adhesive composition is bonded through an ionic hydrogen bond, and present in the form of a salt solution of lysine and citric acid, that is, a salt solution of lysine and citric acid. Salts of lysine and citric acid in the adhesive composition for rent provides excellent adhesion properties while maintaining a liquid state without precipitation in crystalline form (solid state) or precipitate form at room temperature (25 ℃). The adhesive composition for rent can have excellent peel strength by having adhesiveness.

The solvent of the pressure-sensitive adhesive composition is an aqueous solvent. The aqueous solvent includes, for example, one or more selected from water and alcohols. Aqueous solvents include, for example, water as a main component and alcohol as a secondary component.

Aqueous solvents include, for example, one or more alcohol solvents selected from the group consisting of deionized water, primary alcohols, polyhydric alcohols, diols and triols. In the pressure-sensitive adhesive composition, the mixed weight ratio of deionized water and alcohol is, for example, 1: 1 to 10: 0, 1: 1 to 10: 1, 1: 1 to 5: 1 or 1: 1 to 3: 2. Alcohol solvents are, for example, monohydric alcohols, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols or mixtures thereof. The monohydric alcohol is at least one selected from, for example, methanol, ethanol, propan-2-ol, butan-1-ol, pentane-1ol and hexadecan-1-ol. Polyhydric alcohols are for example 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-diene1-ol (3,7-Dimethylocta- 2,6-dien-1-ol), pro-2-yn-1-ol, cyclohexane-1,2,3,4,5,6-hexol -1,2,3,4,5,6-hexol), 2- (2-propyl) -5-methylcyclohexane-1-ol (2- (2-propyl) -5-methyl-cyclohexane-1- ol) at least one selected from. The cycloaliphatic alcohol is, for example, at least one selected from cyclopentanol, cyclohexanol and cycloheptanol.

The pH of the zoned adhesive composition is 2 to 11, 2 to 9.5, or 2 to 8.5. By the zone adhesive composition having such a range of pH range, the storage stability and storage stability of the zone adhesive composition is improved, and the long-term storage property is improved. The adhesive composition for a zone is excellent in adhesiveness even after long-term storage other than immediately after manufacture, and no precipitation is formed. For example, the adhesive composition for rent is for example 14 days or more, 2 months or more, 4 months or more, 6 months or more, 8 months or more, 10 months or more, 12 months or more, or 24 months or more, stored or distributed Even after the composition is stable, no precipitation is formed and the physical properties are kept intact. In addition, the temperature of the environment where the adhesive composition for the zone is stored is -18 ℃ to 80 ℃, specifically -18 ℃ to 45 ℃, 0 ℃ to 60 ℃, 0 ℃ to 45 ℃, 0 ℃ to 40 ℃, or 20 ℃ To 40 ° C. Even if stored outside this temperature range, if the temperature of the environment in which the pressure-sensitive adhesive composition is used is within the above temperature range 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.

When the solids content of the salt of lysine and citric acid is 10 parts by weight or more based on 100 parts by weight of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition has a viscosity of 400 mPa at room temperature (eg, 25 ° C. ± 1 ° C.). At least 800 mPa · s, at least 1200 mPa · s, at least 1600 mPa · s, at least 2000 mPa · s, at least 2500 mPa · s, at least 3000 mPa · s, at least 3500 mPa · s, at least 4000 mPa · s At least 4500 mPa · s, at least 5000 mPa · s, at least 6000 mPa · s, at least 7000 mPa · s, at least 8000 mPa · s, at least 9000 mPa · s, or at least 10000 mPa · s.

When the solids content of the salt of lysine and citric acid is 10 parts by weight or more based on 100 parts by weight of the adhesive composition for the zone, the peel strength measured by ASTM D1876 "Method of measuring T peel strength" of the adhesive composition for zone is For example, the peel strength may be 1 N / 25 mm or more, 1.5 N / 25 mm or more, 2 N / 25 mm or more, 2.5 N / 25 mm or more, 3 N / 25 mm or more, 3.5 N / 25 mm or more, or 4 N / 25 mm or more.

The zoned adhesive composition may have improved viscosity, adhesion and / or peel strength as compared to a composition comprising only salts of lysine and citric acid by including the thickener. The adhesive composition for rent is, for example, at room temperature (eg, 25 ° C. ± 1 ° C.) of viscosity of at least 1000 mPa · s, at least 1500 mPa · s, at least 2000 mPa · s, at least 2500 mPa · s, at least 3000 mPa · s. At least 3500 mPa · s, at least 4000 mPa · s, at least 4500 mPa · s, at least 5000 mPa · s, at least 6000 mPa · s, at least 7000 mPa · s, at least 8000 mPa · s, at least 9000 mPa · s, or It may be 10000 mPa · s or more.

The peel strength measured by ASTM D1876 "Method of measuring T peel strength" of the adhesive composition for a zone is, for example, a peel strength of 2 N / 25 mm or more, 2.5 N / 25 mm or more, 3 N / 25 mm or more, 3.5 N / 25 mm or more Or 4 N / 25 mm or more.

Zone adhesive composition may contain reactive diluents, emulsifiers, tackifiers, plasticizers, fillers, anti-aging agents, curing accelerators, flame retardants, flocculants, surfactants, sunscreens, elastomers, pigments, dyes, paints, fillers, Sunscreen, antistatic agent, antiblocking agent, slip agent, inorganic filler, kneading agent, modifying resin, coupling agent, leveling agent, fluorescent brightener, dispersant, thermal stabilizer, light stabilizer, ultraviolet absorber, wax, wetting agent, flame retardant, antioxidant And at least one additive selected from the group consisting of preservatives and lubricants. The total content of the additives is not particularly limited and includes various additives in various weight ranges depending on the intended use. The content of the above-mentioned additives is at a level conventionally used in the art.

Reactive diluents are diluents that allow each component of the composition to be applied evenly to the object to which the composition is applied, such as n-butylglycidyl ether, aliphatic glycidyl ether, 2-ethylhexyl glycidyl ether , Phenylglycidyl ether, O-cresyl glycidyl ether, nonylphenyl glycidyl ether, p-tert butylphenyl glycidyl ether, 1.4-butanediol diglycidyl ether, 1.6-hexanediol diglycidyl Ether, neopentylglycidyl ether, 1.4-cyclohexanedimethylol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol digly Cidyl ether, resorcinol diglycidyl ether, hydrogenate bisphenol eglycidyl ether, trimethylolpropene triglycidyl ether, glycerol polyglycidyl ether, diglyl Roll polyglycidyl ether, penterritritol polyglycidyl ether, castol glycidyl ether, servitol polyglycidyl ether, neokenoxyacid glycidyl ether, diglycidyl-1.2-cyclohexanedica Carboxylate, diglycidyl-O-phthalate, N, N-diglycidylamine, N, N-diglycidyl-O-toludiene, triglycidyl-p-aminophenol, tetraglycidyl- Diaminodiphenylmethane, triglycidyl-isocyanate, 1.4-butanediol diglycidyl ether, 1.6-hexanediol diglycidyl ether, polypropylene glycidyl diglycidyl ether, and triethylolpropene triglycidyl ether It may be one or more selected from the group consisting of.

Emulsifiers include, for example, at least one member selected from the group consisting of polyoxyethylene, copolymers of polyoxypropylene, copolymers of polyoxyethylene and polyoctylphenyl ether, and sodium dodecylbenzene sulfide.

Tackifiers are for example rosin and its modified products (e.g. rosin, hydrogenated rosin, polymerized rosin, male rosin, rosin glycerin, rosin modified phenolic resin, etc.), 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 ronadiene 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.

Plasticizers can play a role in improving processing flow or stretching. 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.

Plasticizers specifically include dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (DnOP), diisooctyl phthalate (DIOP), diddecyl phthalate DDP, diisodecyl phthalate (DIDP), C8 ~ C10 mixed higher alcohol phthalate, butylbenzyl phthalate (BBP), dioctyl adipate (DOA), dioctyl azelate (DOZ), dioctyl sebacate (DOS), Tricresyl Phosphate (TCP), Trikisilenyl Phosphate (TXP), Monooctyl Diphenyl Phosphate (Santicizer141), Monobutyl-Dikisilenyl Phosphate, Trioctyl Phosphate (TOF), Aromatic Oil, Poly Bedene, paraffin and the like can be used.

The surfactant may be used as long as it is commonly used in the art. For example alkyl sulfates having a chain length of C8 to C18, alkyl ether sulfates or alkyl arylether sulfates having 8 to 18 C atoms and up to 40 ethylene oxide or propylene oxide units in a hydrophobic group, C8 to C18 Alkyl sulfonates, alkylaryl sulfonates, esters and semiesters of sulfosuccinic acids with 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.

Fillers are added to improve the strength, durability, and workability of the composition, such as calcium carbonate, talc, suspended solids, ceramics, silica, dolomite, cray, titanium bags, galvanized, talc, 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 accelerator 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 (e.g., 3M's HQ-115), alkali metal salt ( For example, 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) imide [TBM A] [NTf ₂ ], and the like, and these may be used alone or in combination of two or more thereof.

Elastomers refer to polymers 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, etc. can be used.

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

Pigments may be natural or synthetic pigments, which may be inorganic or organic pigments in another class.

Perfume, for example, but is not limited to peppermint oil, spearmint oil, carbon or menthol may be used alone or in combination.

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 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 the adhesion and the 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 antioxidant may be N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.

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

UV absorbers include ethylhexyl methoxycinnamate (eg 2-Ethylhexyl 4-methoxycinnamate), ethylhexyl salicylate, 4-methylbenzylidene camphor, isoamyl p-methoxycinnamate, octocrylene, phenylbenz Imidazolesulphonic acid, homosalate, synoxate, ethylhexyltrizone, polysilicone-15, tie-salicylate, popba (PABA), ethylhexyldimethylpava, glyceryl pava and the like. These may be used alone or in combination of two or more.

In addition to the additives described above, the pressure-sensitive adhesive compositions or pressure-sensitive adhesive products herein are described in US4959412, CA1278132, US6777465, WO2007-120653, US2003-0064178, US7306844, US 7939145, WO 2011-136568, WO 2010-071298, Korean Patent Publication No. 2016-0095132, The additives disclosed in Japanese Patent Laid-Open No. 5959867 and Korean Patent No. 989942 are incorporated by reference in their entirety.

According to another embodiment, a method for preparing a tacky adhesive composition includes mixing lysine, citric acid, a thickener, and water; And stirring the mixture at 80 ° C. or less.

First, the lysine, citric acid, thickener, and water are mixed to prepare a mixture, and the prepared adhesive composition is prepared by stirring the prepared mixture at 80 ° C or lower.

When the step of stirring the prepared mixture at 80 ° C. or less is performed outside the temperature range, side reaction materials, impurities, and the like may be formed, and in some cases, it may be difficult to obtain a pressure-sensitive adhesive composition having a desired stickiness. Stirring at 80 ° C. or lower is performed at 0 ° C. to 80 ° C., 0 ° C. to 75 ° C., 0 ° C. to 70 ° C., 0 ° C. to 65 ° C., or 0 ° C. to 60 ° C., for example. Stirring at 80 ° C. or less includes, for example, i) a first step of mixing and stirring at 0 ° C. to 80 ° C., 0 ° C. to 75 ° C., 0 ° C. to 70 ° C., or 0 to 60 ° C., and ii) room temperature (20). To 30 ° C.). When the lysine, citric acid, thickener and water are mixed, citric acid and the thickener may be added to the aqueous solution of lysine, or the lysine, citric acid, thickener and water may be mixed. Thickeners are used, for example, in the form of thickener solutions dissolved in water. Zone adhesive composition may further include the step of removing the water and the solvent by concentration under reduced pressure in order to control the solid content in a predetermined range. Stabilizers may be added during the manufacturing process.

In the step of preparing a mixture by mixing lysine, citric acid, thickener and water, the mixing molar ratio of lysine and citric acid may be 1.5: 1 to 1: 3. The mixing molar ratio of lysine and citric acid may be, for example, 1.5: 1 to 1: 2, 1.5: 1 to 1: 1.5, 1.5: 1 to 1: 1.5 or 1.5: 1 to 1: 1. If the content of lysine to citric acid is more or less than the above-mentioned range, precipitation in the composition may be formed, thereby lowering the adhesiveness or lowering the storage stability or storage stability of the adhesive composition.

According to another embodiment, a zoned paper includes: a first substrate comprising paper; A second substrate disposed on one surface of the first substrate and comprising a polymer; And an adhesive layer disposed between the first substrate and the second substrate, wherein the adhesive layer includes the above-described adhesive composition for rent.

The paper that the first substrate includes or constitutes the first substrate is one or more selected from kraft paper, crypt tape paper, embossed paper, and corrugated paper, but is not necessarily limited thereto, and any paper used in the art may be used. The polymers contained in or constituting the second substrate are high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene, polyurethane, ethylene-propylene-diene terpolymers. One or more selected from copolymer synthetic rubber, ethylene vinyl acetate, neoprene rubber, styrene-butadiene rubber, and nitrile-butadiene rubber, including but not limited to these, all may be used as a polymer in the art. For example, the first substrate is kraft paper, and the second substrate is a high density polyethylene film. The first substrate is a single layer or a multilayer. The first substrate is, for example, a paper base paper obtained by stacking a plurality of kraft papers. For example, the first substrate includes kraft paper as the first layer, corrugated paper, embossed paper, or creep tape paper as the second layer disposed on the first layer, and kraft paper as the third layer disposed on the second layer. It is a corrugated cardboard having a three-layer structure. The second substrate is a single layer or a multilayer. The second substrate is, for example, a laminate of a plurality of different polymer films. For example, the second substrate is a multilayer polymer film having a three-layer structure including high density polyethylene as the first layer, low density polyethylene as the second layer, and high density polyethylene as the third layer.

A zone (paper bag) according to another embodiment includes the zone paper described above. For example, the above-described zone paper is folded and bonded to prepare the zone. The zone is used as a bag of various powders such as sugar, flour, feed, grains, and cement.

Other articles also include the above-described zone paper. Other articles are not limited to, for example, boxes, cups, packs, and the like, and may be any articles that can be manufactured using zoned paper.

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] Preparation of a pressure-sensitive adhesive composition containing a salt of lysine and citric acid, a thickener and a stabilizer

Composition a-1

47.59 g of DIW (distilled water) was added to 100 g of an aqueous 54% by weight L-lysine free form solution and diluted with stirring at room temperature (25 ° C.) for 30 minutes. 23.66 g of citric acid (citric acid: CA) and xanthan gum were slowly added to the diluted lysine at room temperature (25 ° C.) and stirred for 1 hour, followed by stirring at 60 ° C. for 3 hours. Subsequently, after the reaction mixture reached room temperature (25 ° C.), the reaction was terminated to obtain 172.58 g of an adhesive composition. The solids content of lysine and citric acid in this composition was about 45 parts by weight based on 100 parts by weight of the composition, and the mixed molar ratio of lysine and citric acid was 3: 1. The xanthan gum content is 0.77 wt% based on the total weight of the composition and the solvent is deionized water.

Compositions a-2 to c-12

A pressure-sensitive adhesive composition was prepared in the same manner as in composition a-1, except that the solid content of lysine and citric acid, the molar ratio of lysine and citric acid, the thickener content or the stabilizer content were changed. (Compositions a-1 to a-6, Compositions b-1 to b-5, and Compositions c-1 to c-8 include xanthan gum, guar gum, and arabic gum, respectively) Specific compositions are shown in Tables 1 to 3 below. Is initiated.

Example 2 Evaluation of Precipitation Formation, Viscosity, and Peel Strength

According to the production method described in Example 1, an adhesive composition was prepared (compositions a-1 to a-6, compositions b-1 to b-5, and compositions c-1 to c-8).

As a control A, a commercially available polyvinyl alcohol-based adhesive (J-POVAL JP-18, Japan VAM & Poval Co., Ltd.) was prepared. For each of the pressure-sensitive adhesive composition was evaluated whether or not precipitate formation, viscosity and peel strength according to the following method, the evaluation results are shown in Tables 1 to 3 below.

1) Precipitation Formation

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

2) viscosity evaluation

Viscosity was measured using a rotary viscometer (manufacturer: LAMYRHEOLOGY, trade name: RM200 TOUCH CP400 or RM200 TOUCH) at 25 ± 1 ° C., LV-1 spindle, 60 rpm. Evaluation results are shown in Tables 2 to 3 below.

3) Peel strength

After preparing kraft paper (kraft paper size: 120 mm * 25 mm, thickness: 40 um) and HDPE film (film size: 120 mm * 25 mm, thickness: 50 um), # 4 bar coater (bar coater) was coated on one side of the kraft paper with a thickness of 11 um. After drying for 4 minutes at 60 ℃ in an oven using a dry laminator (dry laminatior) equipment was laminated with a high density polyethylene (HDPE) film (roller speed 1.9 m / min, roller temp. 60 ℃). Laminated specimens were dried for 12 hours in an oven controlled at 25 ℃. The peel strength of the specimens prepared according to ASTM D1876 "Measurement of T Peel Strength" was measured. Peel strength measurements were measured using a push-pull gauge (manufacturer IMADA), and the maximum load was applied when the specimen was pulled up to 10 cm of 1 N load per 1.0 inch (1 inch = 25 mm) of width. Evaluation results are shown in Tables 1 to 3 below.

Solid content of lysine and citric acid
(wt%) Lysine: CA
(mol ratio) Thickener
content
[wt%] Peel strength
[N / 25mm] Viscosity
[mPa.s] a-1 45 3: 1 0.77 2.41 3240 a-2 45 2: 1 0.77 3.18 2750 a-3 45 1.5: 1 0.77 4.66 1850 a-4 45 1: 1 0.77 4.08 1072 a-5 45 1: 2 0.77 3.92 420 a-6 45 1: 3 0.77 3.92 420 Control group A
(PVA system) - - - 1.96 1757

As shown in Table 1, the adhesive compositions of a-1 to a-6 prepared in Example 1 showed excellent adhesion by providing improved peel strength over Control A in various molar ratio ranges.

Solid content of lysine and citric acid
(wt%) Lysine: CA
(mol ratio) Thickener content
[wt%] Peel strength
[N / 25mm] Viscosity
[mPa.s] b-1 65 1.5: 1 1.25 4.41 19525 b-2 50 1.5: 1 1.25 4.18 9693 b-3 40 1.5: 1 1.25 3.77 6816 b-4 60 1.5: 1 0.77 4.08 3621 b-5 50 1.5: 1 0.77 3.92 2523 Control group A
(PVA system) - - - 1.96 1757

As shown in Table 2, the adhesive compositions of b-1 to b-5 prepared in Example 1 showed excellent adhesion by providing improved peel strength as compared to Control A in various solids content ranges.

Solid content of lysine and citric acid
(wt%) Lysine: CA
(mol ratio) Thickener
content
[wt%] Peel strength
[N / 25mm] Viscosity
[mPa.s] c-1 45 1.5: 1 1.25 3.77 7816 c-2 45 1.5: 1 1.00 3.84 4620 c-3 45 1.5: 1 0.75 3.92 1620 c-4 45 1.5: 1 0.50 3.58 854 c-5 50 1.5: 1 1.25 4.25 9693 c-6 50 1.5: 1 1.00 4.02 5523 c-7 50 1.5: 1 0.75 3.92 2523 c-8 50 1.5: 1 0.50 3.58 1453 Control group A
(PVA system) - - - 1.96 1757

As shown in Table 3, the c-1 to c-8 adhesive compositions prepared in Example 1 showed excellent adhesion by providing improved peel strength over Control A in various thickener content ranges.

[ Reference Example  One] Lysine  And stability evaluation of the composition comprising an organic acid

(Lysine and citric acid = 1: 1 molar ratio composition)

79 g of DIW (distilled water) was added to 100 g of an aqueous 54% by weight L-lysine free form solution and diluted with stirring at room temperature (25 ° C.) for 30 minutes. 70.97 g of citric acid (citric acid: CA) was slowly added to the diluted lysine at room temperature (25 ° C.) and stirred for 1 hour, followed by stirring at 60 ° C. for 1 hour. Subsequently, after the reaction mixture reached room temperature (25 ° C.), the reaction was terminated to obtain 249.93 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 citric acid is 1: 1 and the solvent is deionized water.

(Lysine and other organic acid = 1: 1 molar ratio composition)

In the same manner as the above method, the composition was prepared by changing only the type of organic acid.

Example 1 except that acetic acid, glutamic acid, glutaric acid, tartaric acid, aspartic acid, fumaric acid, glyoxylic acid, 4-ketopimelic acid, pyruvic acid, 1,3-acetonedicarboxylic acid were used instead of citric acid. The same procedure was followed to prepare a composition.

(Evaluation of sedimentation)

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

Compositions containing lysine and citric acid did not form precipitates, whereas compositions containing other organic acids and lysine could form precipitates and could not evaluate tack.

When the composition was prepared by mixing lysine with various organic acids, it was confirmed that not all compositions exhibit stickiness without forming a precipitate.

[Reference Example 2] Solubility evaluation according to the solvent of the composition

According to the manufacturing method described in Reference Example 1, an adhesive composition containing lysine and citric acid was prepared. (Molar ratio of lysine and citric acid = 1: 1, 50 parts by weight of solid content) 25 g of the following additional solvent was added to 50 g of the prepared pressure-sensitive adhesive composition, followed by stirring for 1 hour. After stirring, additional solvents of the adhesive composition are methanol, toluene, benzene, chloroform, methylene chloride, dichloromethane, tetrahydrofuran (THF), ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and n- Solubility in hexane solvent was evaluated. As a result of the evaluation, the pressure-sensitive adhesive composition prepared in Example 1 was dissolved when methanol as an additional solvent was used, but precipitated without dissolving with respect to the other additional organic solvents described above.

Reference Example 3 Analysis of Shape, Viscosity, and Initial Adhesive Force of Adhesive Composition According to Solid Content

According to the manufacturing method described in Reference Example 1, an adhesive composition containing lysine and citric acid was prepared. However, the solid content in the adhesive composition may be 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 The pressure-sensitive adhesive composition was prepared so as to be wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 75 wt%. (Molar ratio of lysine and citric acid is 1: 1) (Composition 2-1 to 2-19) The solid content was adjusted to the content of water.

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, at room temperature (25 ° C.) and relative humidity of 60 ± 10%, the formation of precipitates in the adhesive composition was observed for 14 days.

2) viscosity evaluation

Viscosity was measured using a rotary viscometer (manufacturer: LAMYRHEOLOGY, trade name: RM200 TOUCH CP400 or RM200 TOUCH) at 25 ± 1 ° C., LV-1 spindle, 60 rpm.

3) Initial adhesive force evaluation

Initial stability was evaluated for the composition where no precipitate was formed in the stability assessment. Initial adhesive strength was used by Anton Paar 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 held in contact with the adhesive composition for 1 minute to maintain 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.

Referring to Table 4, it was confirmed that when the solid content in the composition is 71 wt% or more, precipitation was formed, whereas when the solid content in the composition was 10 wt% to 70 wt%, no precipitation was formed and the liquid phase was maintained.

Reference Example 4 Comparison of Initial Adhesion

The adhesive force of the conventional adhesive and the adhesive composition of this application was compared.

According to the manufacturing method described in Reference Example 1, an adhesive composition containing lysine and citric 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 citric acid = 1: 1) (composition 4-1)

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 group 1) was prepared.

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

The evaluation results are shown in Table 5 below.

Solid content
(wt%) Viscosity
(mPa.s) Initial adhesion
(mJ) 4-1 10 10.1 0.21 Control group 1
(PVA system) 10 43.49 0.201

Referring to Table 5, the pressure-sensitive adhesive composition according to the present application showed the same level of initial adhesive strength compared to the polyvinyl alcohol-based pressure-sensitive adhesive composition (control group 1).

[ Reference Example  5] Peel strength evaluation according to solvent

According to the production method described in Reference Example 1, a pressure-sensitive adhesive composition containing lysine and citric acid was prepared (following 5-1 to 5-3). However, the pressure-sensitive adhesive composition was prepared by setting the molar ratio of lysine and citric acid to 1.5: 1, 1: 1, and 1: 1.5, respectively. (50 parts by weight of solid content)

According to the preparation method described in Reference Example 1, an adhesive composition containing lysine and citric acid was prepared (6-4 to 6-6 below). However, the pressure-sensitive adhesive composition was prepared by setting the molar ratio of lysine and citric acid to 1.5: 1, 1: 1, and 1: 1.5, respectively, and methanol was added as a solvent. The weight ratio of the deionized water and methanol was 1: 1. (50 parts by weight of solid content)

According to the preparation method described in Reference Example 1, an adhesive composition containing lysine and citric acid was prepared (below 5-7 to 5-8). In addition, methanol other than deionized water was added and the weight ratio of deionized water and methanol was set to 6: 4 and 4: 6. (Molar ratio of lysine and citric acid = 1: 1, solid content 50 parts by weight)

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. The peel strength of each adhesive composition was evaluated according to the following method, and the evaluation results are shown in Table 6 below.

1) peeling strength

After preparing the PET film (film size: 120mm * 25mm, thickness: 38um or 50um) using a bar coater, the sample was coated on the surface of the PET film (50um thickness) to a thickness of 11um. After drying for 4 minutes at 60 ℃ in the oven and lamination with PET film (38um thickness) using a dry laminatior equipment (roller speed 1.9m / min, roller temp. 60 ℃). Laminated specimens were dried in an oven controlled at 30 ° C. for 72 hrs. The peel strength of the dried specimen was measured according to the ASTM D1876 "Measure 180 ° T Peel Strength" method. The measurement results are shown in Table 6 below.

No. Lysine: CA
(mol ratio) menstruum Solid content
(wt%) Peel strength
(N / 25mm) 5-1 1.5: 1 DIW 50 5.91 5-2 1: 1 5.45 5-3 1: 1.5 4.92 5-4 1.5: 1 DIW and Methanol (1: 1 wt ratio) 7.11 5-5 1: 1 6.92 5-6 1: 1.5 6.18 5-7 1: 1 DIW and Methanol (6: 4wt ratio) 6.28 5-8 1: 1 DIW and Methanol (4: 6wt ratio) - Control 2
(Acrylic) - 59 6.61

Referring to Table 6, the PET film adhered to the stainless steel by the adhesive composition according to the present application was separated within 1 hour, and provided a similar peel strength even with a lower solids content as compared to the control 2.

In addition, the peel strength was further improved when water and alcohol were used as the solvent. The improved peel strength is judged to be 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. However, when the content of deionized water and alcohol is 4: 6 by weight, phase separation occurred in the adhesive composition, and thus it was not available.

[ Reference Example  6] Analysis of composition in adhesive composition according to reaction temperature

In preparing the pressure-sensitive adhesive composition, the composition in the pressure-sensitive adhesive composition was analyzed according to temperature conditions.

1) Preparation at 0 ° C. (low temperature): 79 g of DIW (distilled water) was added to 100 g of 54% by weight lysine aqueous solution and stirred at 0 ° C. (T1) for 30 minutes. 70.97 g of citric acid was slowly added to the diluted product at 0 ° C. (T2) and stirred for 1.5 hours to prepare an adhesive composition. (Solid content: 50% by weight, mixed molar ratio of lysine and citric acid = 1: 1) An ice bath was used to maintain the same temperature while stirring.

2) Preparation at 25 ° C. (room temperature): 79 g of DIW (distilled water) was added to 100 g of 54% by weight lysine aqueous solution, and stirred at room temperature 25 ° C. (T1) for 30 minutes. 70.97 g of citric acid was slowly added to the diluted product at 25 ° C. (T 2) and stirred for 1.5 hours to prepare an adhesive composition. (Solid content: 50% by weight, mixed molar ratio of lysine and citric acid = 1: 1). The temperature controller was used to maintain the same temperature while the adhesive composition was stirred (hereinafter same).

3) Preparation at 60 ° C: The composition was prepared in the same manner as in 2), except that T2 was changed to 60 ° C.

4) Preparation at 80 ° C .: The composition was prepared in the same manner as in 2), except that T2 was changed to 80 ° C.

5) Preparation at 240 ° C: The composition was prepared in the same manner as in 2), except that T2 was changed to 240 ° C.

As a result of preparing the composition according to the above method, carbides were formed at 240 ° C., thus making it impossible to prepare an adhesive composition. Therefore, component analysis was performed using ¹ H NMR on compositions prepared at 0 ° C, 25 ° C, 60 ° C and 80 ° C.

NMR analyzers and conditions used in the present application are as follows.

Superconducting Fourier Transform Nuclear Magnetic Resonance Spectrometer (400MHz) Model Name: AVANCE II 400, Manufacturer: Bruker Biospin (Maget field strength 9.4 Tesla, Field driftrate: 4Hz / hr, Obervable Freguency: 400Mhz 1H, Sensitivity: 220: 1 (1H), Variable Temp.: -70 ~ + 110 ℃), Solvent: D ₂ O

¹ H NMR analysis was performed on compositions prepared at 0 ° C. (Sample 1), 25 ° C. (Sample 2), and 80 ° C. (Sample 3). The NMR analysis results are shown in FIG. 1. Referring to FIG. 1, the compositions prepared at 0 ° C., 25 ° C., and 80 ° C. all showed ¹ H NMR peaks at the same position, and no chemical shift occurred, and they all had the same composition. It can be seen that. That is, the pressure-sensitive adhesive composition prepared at 0 ° C, 25 ° C, and 80 ° C shows that lysine and citric acid are present in a mixture state and there is no condensation formation of lysine and citric acid, or even a very small amount is contained as an impurity even when condensation is produced. It can be seen that.

Claims (14)

Zone adhesive composition comprising a salt of lysine and citric acid and a thickener. The adhesive composition for rent according to claim 1, wherein the thickener comprises at least one selected from a water-soluble natural polymer and a water-soluble synthetic polymer. The method of claim 2, wherein the water-soluble natural polymer is xanthan gum, guar gum, gum arabic, tragacanth gum, galactan, carab gum, karaya gum, carrageenan, acacia gum, pectin, cannan , Queen's seed (quince), alga colloid (algae extract), starch (derived from rice, corn, potato, wheat, etc.), glycyrrhizin, alginin, sodium alginate, collagen, Alginate, gelatin, furcellaran, carrageenan, casein, locust bean gum, pectin, chitosan, albumin, dex Tran, succinoglucan, blueran, tragacanthin, hyaluronic acid, pectin, alginic acid, agar, galactomannans, beta-cyclodextrin And at least one selected from amylase, casein, and chitosan. The adhesive composition for rent. The method of claim 2, wherein the water-soluble synthetic polymer is polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), N- (2- Hydroxypropyl) methacrylamide (HPMA), divinyl ether-maleic hydride (DIVEMA), polyphosphate, polyphosphazene, methyl cellulose, methyl ethyl cellulose, ethyl cellulose, microcrystalline cellulose, hydroxyethyl cellulose, Hydroxybutyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose stearoxy ether, carboxymethyl hydroxyethyl cellulose, alkyl hydroxyethyl cellulose, nonoxynyl hydroxy Ethyl cellulose, sodium cellulose sulfate, methyl cellulose, methyl ethyl cellulose, ethyl cellulose Agarose, and carboxymethyl cellulose pressure-sensitive adhesive composition for a zone comprising at least one selected from the group consisting of (CMC). The adhesive composition for rent according to claim 1, wherein the thickener content is 10 parts by weight or less based on 100 parts by weight of the adhesive composition for rent. The adhesive composition for abutment according to claim 1, wherein the mixing molar ratio of lysine and citric acid is 1.5: 1 to 1: 3. The adhesive composition for rent according to claim 1, wherein the solid content in the composition is 70 parts by weight or less based on 100 parts by weight of the adhesive composition for a label. The adhesive composition for rent according to claim 1, wherein the peel strength measured by ASTM D1876 "Method for measuring T peel strength" of the adhesive composition for rent is 1 N / 25 mm or more. According to claim 1, wherein the pressure-sensitive adhesive composition for the zone is a pressure-sensitive adhesive composition is not formed during storage for at least 14 days at -18 to 45 ℃. Mixing lysine, citric acid, thickener and water; And
Stirring the mixture at 80 ° C or less; Method for producing a pressure-sensitive adhesive composition comprising a. The method of claim 10, wherein the mixing molar ratio of lysine and citric acid is 1.5: 1 to 1: 3. A first substrate comprising paper; a second substrate disposed on one surface of the first substrate and comprising a polymer; And
An adhesive layer disposed between the first substrate and the second substrate,
The paper sheet wherein the adhesive layer comprises the adhesive composition for rent according to any one of claims 1 to 9. The method of claim 12, wherein the first substrate comprises at least one selected from kraft paper, creep tape paper, embossed paper, corrugated paper,
The second substrate is high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene, polyurethane, ethylene-propylene-diene terpolymer synthetic rubber, ethylene vinyl acetate, Zone paper comprising at least one selected from neoprene rubber, styrene-butadiene rubber, and nitrile-butadiene rubber. A zone comprising the zone sheet according to claim 12.

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