KR102275476B1 - 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 provides an adhesive composition for a belt comprising a salt of lysine and citric acid and a thickener, and a belt paper and a belt comprising the same.

Description

Adhesive composition for a sheet, a method for manufacturing the same, and a sheet and a sheet including the same, {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 an adhesive composition for a paper sheet, a method for preparing the same, and a sheet and paper sheet including the same.

The belt is used for moisture-proof packaging of sugar, milling, feed, cement, etc.

Conventional pressure-sensitive adhesives generally include a polymer as a main component in order to impart adhesiveness. The pressure-sensitive adhesive containing a polymer as a main component provides excellent adhesion required in various environments by controlling the structure and molecular weight of the polymer.

However, since polymers are manufactured through complex processes such as synthesis and purification, they cause various environmental pollution. For example, a monomer derived from fossil raw materials is used as a raw material for a polymer, an excessive amount of an organic solvent is used in the process of refining the polymer, and a long time is required for decomposition of the produced polymer. Therefore, it is difficult to recycle the land.

Therefore, there is a need for a pressure-sensitive adhesive that uses renewable raw materials and provides excellent adhesion without using a polymer as a main component, so that the paper can be easily recycled.

One aspect of the present application is to provide an adhesive composition for a zone having excellent peel strength.

Another aspect of the present application is to provide a method for preparing an adhesive composition for a zone.

Another aspect of the present application is to provide a paper sheet including the pressure-sensitive adhesive composition for the sheet.

Another aspect of the present application is to provide a zone comprising a zone sheet.

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

According to another aspect, the step of mixing lysine, citric acid, a thickener and water; And the step of stirring the mixture at 80 ℃ or less; is provided a method for producing a pressure-sensitive adhesive composition for a zone comprising a.

According to another aspect, a first substrate comprising paper; a second substrate disposed on one surface of the first substrate and including a polymer; and an adhesive layer disposed between the first substrate and the second substrate, wherein the adhesive layer is provided with a paper sheet comprising the adhesive composition for a sheet according to any one of claims 1 to 15.

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

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

^{1 shows a 1} H nuclear magnetic resonance spectrum (NMR) analysis result according to Reference Example 7.

Hereinafter, the pressure-sensitive adhesive composition for a belt according to an embodiment, a method for manufacturing the same, and a sheet and a belt including the same will be described in more detail.

As used herein, the term “adhesion” refers to a phenomenon in which two different objects (except for a gas) come into contact with or approach each other, and then attract each other. In other words, adhesion refers to a phenomenon that requires some force (or work) to separate two different objects (except gas) after they come into contact with or approach each other.

As used herein, the term “viscoelasticity” refers to a phenomenon in which, when a force is applied to an object, a flow without a restoring force against the deformation and an elastic deformation having a restoring force appear at the same time. A material having viscoelasticity has both solid and liquid properties.

As used herein, “viscosity” refers to a property that attempts to obstruct the flow of a substance as a result of internal friction between molecules. Friction is a force that tries to prevent a difference in the distribution of flow velocity. Tackiness and viscosity are separate properties. A material having a high viscosity may have little tackiness, and a material having a low viscosity may have a high tackiness.

The composition having adhesion (adhesion) may have viscoelasticity (viscoelasticity). After the composition having viscoelasticity is applied to the substrate, when it is separated from the substrate, deformation by a force of a certain magnitude is required. The composition having viscoelasticity is capable of reversible attachment and detachment from the substrate. When the composition having viscoelasticity is applied to the substrate and dried, an adhesive layer containing the composition having viscoelasticity is formed on the substrate. The composition having viscoelasticity is stored and distributed through a general processing form before being applied to the substrate, and its adhesion is maintained even after a certain period of time has elapsed. The adhesive article obtained by applying and drying the adhesive composition on the substrate is, for example, a label, an Oriented Polypropylene (OPP) tape, and the like. In addition, the composition having adhesion (adhesion) may not have viscoelasticity. After the composition having adhesiveness is applied to the substrate, it may be solidified after a certain time has elapsed and the viscoelasticity may be lost. When the solidified material without such viscoelasticity is to be separated from the substrate, it may be accompanied by an irreversible physical destruction phenomenon.

The pressure-sensitive adhesive composition for paper includes a salt of lysine and citric acid and a thickener.

A salt of lysine and citric acid is a low molecular weight substance, but provides tack. Thickeners provide additional tack. In addition, the thickener controls the solubility in water of the adhesive composition for paper. Therefore, the adhesive composition for the paper provides excellent peel strength by including a salt of lysine and citric acid and a thickener. The pressure-sensitive adhesive composition for a tissue contains a salt of lysine and citric acid as main components. As used herein, the term “main component” refers to a component having the highest content among components excluding a solvent. It is possible to adjust the adhesive strength and peel strength according to the content and type of the thickener in the adhesive composition for paper. In addition, the adhesive composition for paper is environmentally friendly because it is dissociated by water and the dissociated component is also harmless to living things and the environment.

Thickeners are, for example, water-soluble polymers. The thickener includes, for example, at least one selected from water-soluble natural polymers and water-soluble synthetic polymers. Since the pressure-sensitive adhesive composition for paper includes a water-soluble polymer as a thickener, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for paper can be removed by water. That is, the adhesive layer may be peeled off from the base by water.

Water-soluble natural polymers include, for example, xanthan gum, guar gum, gum arabic, gum tragacanth, galactan, carob gum, karaya gum, carrageenan, acacia gum, pectin, cannan, quince seed ( quince), algecolloid (brown 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, dextran, succino Glucan, bluelan, tragacanthin, hyaluronic acid, pectin, alginic acid, agar, galactomannans, beta-cyclodextrin, amylose ( amylase), casein, and one or more selected from chitosan (chitosan), but is not necessarily limited thereto, and any water-soluble natural polymer that can be used in the art is possible.

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 At least one selected from sodium sulfate, methylcellulose, methylethylcellulose, ethylcellulose, and carboxymethylcellulose (CMC) is not necessarily limited thereto, and any water-soluble synthetic polymer that can be used in the art may be used.

In the pressure-sensitive adhesive composition for a belt, 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. If the content of the thickener is too high, precipitation may occur. In the pressure-sensitive adhesive composition for a zone, 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 7 parts by weight, based on 100 parts by weight of the adhesive composition for a zone. 5 parts by weight.

The adhesive composition for a zone further comprises, for example, a stabilizer. Stabilizers, for example, improve the phase stability of the adhesive composition for paper. The stabilizer includes, for example, one or more selected from monohydric alcohol, polyhydric alcohols, and polyamines. Stabilizers include, for example, glycerol, alkylene glycol, dialkylene glycol, benzenediol, benzene triol, dial alcohol amine, trial alcohol amine, arabitol, mannitol, isomalt, xylitol, sorbitol, maltitol, erythritol, Ribitol, dulcitol, lactitol, threitol, iditol, polyglycitol, methanol, ethanol, propan-2-ol, butan-1-ol, pentan-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-hexol hexane-1,2,3,4,5,6-hexol) , heptane-1,2,3,4,5,6,7-heptane-1,2,3,4,5,6,7-heptol, pro-2-en-1-ol (Prop- 2-ene-1-ol), 3,7-dimethylocta-2,6-dien-1-ol (3,7-Dimethylocta-2,6-dien-1-ol), pro-2-yn-1- Ol (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-methylcyclohexan-1-ol (2-(2-propyl)-5-methyl-cyclohexane-1-ol), C2-C10 alkylenediamine, C2-C10 alkenylenediamine, phenylene At least one selected from diamine and n-amino(C1-C5)alkyl (C1-C5)alkanediamine is not necessarily limited thereto, and any stabilizer used in the art may be used.

In the adhesive composition for a belt, the stabilizer content 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, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight based on 100 parts by weight of the composition. parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. By including the stabilizer in this range of the adhesive composition for a zone, it is possible to provide more improved dust adhesion and/or peel strength.

In the adhesive composition for a belt, 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 adhesive composition for a zone. In the adhesive composition for a belt, the content of a salt 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 adhesive composition for a zone. 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 adhesive composition for a belt, the content of a salt 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 adhesive composition for a zone , 10 to 50 wt%, 20 to 50 wt%, or 30 to 50 wt%.

In the adhesive composition for a belt, the content of salt of lysine and citric acid is 10 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, based on the total weight of organic solids. , 70 wt% or more, 80 wt% or more, or 90 wt% or more. In the adhesive composition for a belt, the content of the salt 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 99wt%, 50wt% to 99wt%, 60wt% to 99wt%, 70wt% to 99wt%, 80wt% to 99wt%, or 90wt% to 99wt%. For example, based on 100 parts by weight of the solid content of the adhesive composition for paper, the sum of the citric acid and lysine contents 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. By having the content of the salt of lysine and citric acid in this range, the adhesion and/or peel strength is further improved. Organic solids include, for example, salts of lysine and citric acid and thickeners.

In the adhesive composition for a zone, for example, it is free of precipitates in the composition. Since the adhesive composition for paper does not contain sediment, it provides more improved adhesion and/or peel strength.

The precipitates may be one or more precipitates selected from lysine, citric acid and a thickener. For example, as shown in Scheme 1 below, an insoluble salt (AB(s)) is obtained by a chemical change of an aqueous lysine solution (A(aq)) and an aqueous citric acid solution (B(aq)), as shown in Scheme 2 below Lysine solid (A(s)) or citric acid solid (B(s)) is precipitated from lysine aqueous solution (A(aq)) or citric acid aqueous solution (B(aq)), or lysine solid (A(s)) or citric acid solid (B(s)) does not dissolve in the solvent and thus remains in an insoluble state. In addition, it includes cases in which the thickener is precipitated in the pressure-sensitive adhesive composition for a zone or the thickener is not dissolved in the solvent and thus remains in an insoluble state.

[Scheme 1]

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

[Scheme 2]

A(aq)->A(s)

As used herein, the term "sediment" is a precipitate generated during storage and distribution before application of a substrate or an adhesive.

As used herein, the term "lysine" is one of the basic α-amino acids, lysine is biosynthesized from oxalacetic acid through a lysine biosynthetic pathway, or chemically synthesized.

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 thereof, or combinations thereof. These lysine salts can be converted into lysine free form.

Conversion of lysine salts to lysine preforms is known to those of ordinary skill in the art. In addition, commercially available lysine raw materials can be used. 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 comprising them are also the same or similar, the present invention may belong to the category of

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

[Formula 3]

The salt of lysine and citric acid in the adhesive composition for a belt is present, for example, in the form of a salt solution. When lysine, citric acid, water and a thickener are mixed, lysine and citric acid do not form a covalent compound or an insoluble salt, for example, in the form of an aqueous salt solution.

The content of lysine, citric acid, water, and a thickener in the adhesive composition for a belt can be controlled so that lysine and citric acid are not precipitated as crystals or precipitation is not formed. When the pressure-sensitive adhesive composition for paper is maintained in a liquid state without forming crystals or precipitation, it has excellent adhesion and is easy to apply uniformly to a substrate.

The mixing molar ratio of lysine and citric acid may be 1.5:1 to 1:3. Specifically, the mixing molar ratio of the 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. When the content of lysine with respect to citric acid is more or less than the above-mentioned range, a precipitate may be formed in the composition to decrease adhesion, or storage stability or storage stability of the pressure-sensitive adhesive composition may be reduced.

The content of solids including a salt of lysine and citric acid and a thickening agent in the adhesive composition for a belt 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 paper on the substrate, and when the content of the solid content is 70 parts by weight or more, it may be difficult to use the adhesive composition as a precipitate is formed. Even if the content of the solid content is reduced, precipitation in the composition is not formed or the adhesive strength is not lost, so the content of the solid content may be adjusted to a level of 0.1 to 10 parts by weight depending on the field to be applied.

In the adhesive composition for a belt, citric acid and lysine may be contained in the form of a condensate containing citric acid and lysine as units. For example, the condensate may be a dimer, trimer, or oligomer, and the content of the condensate is 20 parts by weight or less, 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 contents. and may contain 0. When the condensate is included in more than the above range, the adhesive strength of the pressure-sensitive adhesive composition may decrease or the liquid state may not be maintained.

The reason why the adhesive composition for a belt exhibits the adhesiveness as described above will be described in more detail. This description of the adhesiveness is merely to aid understanding, and is not intended to limit the scope of the present application to the scope of this interpretation. Adhesion may be explained by other reasons within the scope of scientific contradiction. The salts of lysine and citric acid provide tack to the composition by forming a kind of network within the composition, for example by strong interaction between lysine and citric acid or lysine and citric acid, water, or lysine and citric acid, water, a thickener do. Lysine has two amino groups and citric acid has three carbonyl groups. The unshared electron pair of the 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, the unshared electron pair of oxygen of the carbonyl group of citric acid, hydrogen of the amino group of lysine, and water interact strongly through an ionic hydrogen bond. When the components of the pressure-sensitive adhesive composition for paper are analyzed by liquid chromatography or the like, lysine and citric acid can be identified as raw materials. From this, lysine and citric acid in the adhesive composition for a belt are combined through ionic hydrogen bonding, and exist in the form of a salt of lysine and citric acid, that is, a salt solution of lysine and citric acid. The salt of lysine and citric acid in the pressure-sensitive adhesive composition for paper provides excellent adhesive properties while maintaining a liquid state without precipitating in the form of crystals (solid state) or precipitate at room temperature (25° C.). Since the adhesive composition for the paper has adhesiveness, it can have excellent peel strength.

The solvent of the pressure-sensitive adhesive composition for paper is an aqueous solvent. The aqueous solvent includes, for example, at least one selected from water and alcohol. The aqueous solvent contains, for example, water as a main component and alcohol as an auxiliary component.

The aqueous solvent includes, 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 for a zone, a mixing 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. The alcohol solvent is, for example, monohydric alcohol, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, or mixtures thereof. The monohydric alcohol is, for example, at least one selected from methanol, ethanol, propan-2-ol, butan-1-ol, pentan-1ol and hexadecan-1-ol. The polyhydric alcohol is, 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-1,3-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-hexol ( hexane-1,2,3,4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptane-1,2,3,4,5,6,7 -heptol) is at least one selected from Unsaturated aliphatic alcohols are, for example, prop-2-ene-1-ol, 3,7-dimethylocta-2,6-dien1-ol (3,7-Dimethylocta- 2,6-dien-1-ol), pro-2-yn-1-ol (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-methylcyclohexan-1-ol (2-(2-propyl)-5-methyl-cyclohexane-1- ol) is at least one selected from The alicyclic alcohol is, for example, at least one selected from among cyclopentanol, cyclohexanol and cycloheptanol.

The pH of the pressure-sensitive adhesive composition for paper is 2 to 11, 2 to 9.5, or 2 to 8.5. By having the pressure-sensitive adhesive composition for the zone in this pH range, the storage stability and storage stability of the adhesive composition for the zone is improved, and long-term storage is improved. The pressure-sensitive adhesive composition for paper has excellent adhesion and no precipitation even after long-term storage in addition to immediately after production. For example, the pressure-sensitive adhesive composition for paper 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 maintained. In addition, the temperature of the environment in which the pressure-sensitive adhesive composition for paper is stored is -18°C to 80°C, specifically -18°C to 45°C, 0°C to 60°C, 0°C to 45°C, 0°C to 40°C, or 20°C. 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, the formulation and quality may not be affected. For example, when stored at a low temperature, it can be used after leaving it at room temperature for a certain period of time before use.

When the solid 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 belt, the adhesive composition for the belt has a viscosity of, for example, 400 mPa at room temperature (eg, 25°C±1°C) s or more, 800 mPa·s or more, 1200 mPa·s or more, 1600 mPa·s or more, 2000 mPa·s or more, 2500 mPa·s or more, 3000 mPa·s or more, 3500 mPa·s or more, 4000 mPa·s or more or more, 4500 mPa-s or more, 5000 mPa-s or more, 6000 mPa-s or more, 7000 mPa-s or more, 8000 mPa-s or more, 9000 mPa-s or more, or 10000 mPa-s or more.

When the solid 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 a belt, the peel strength measured by ASTM D1876 "Method for measuring T peel strength" of the adhesive composition for a belt is an example 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.

By including the thickener, the adhesive composition for a zone may have improved viscosity, adhesion and/or peel strength compared to a composition including only a salt of lysine and citric acid. At room temperature (eg, 25°C±1°C), the pressure-sensitive adhesive composition has, for example, a viscosity of 1000 mPa·s or more, 1500 mPa·s or more, 2000 mPa·s or more, 2500 mPa·s or more, 3000 mPa·s or more , 3500 mPa·s or more, 4000 mPa·s or more, 4500 mPa·s or more, 5000 mPa·s or more, 6000 mPa·s or more, 7000 mPa·s or more, 8000 mPa·s or more, 9000 mPa·s or more, or It may be 10000 mPa·s or more.

The peel strength measured according to ASTM D1876 "Method for measuring T peel strength" of the adhesive composition for paper 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.

The adhesive composition for paper can optionally contain reactive diluents, emulsifiers, tackifiers, plasticizers, fillers, antioxidants, curing accelerators, flame retardants, coagulants, surfactants, sunscreens, elastomers, pigments, dyes, fragrances, fillers, UV blocker, antistatic agent, antiblocking agent, slip agent, inorganic filler, kneading agent, modified resin, coupling agent, leveling agent, optical brightener, dispersant, heat stabilizer, light stabilizer, UV absorber, wax, wetting agent, flame retardant, antioxidant , and one or more additives selected from the group consisting of preservatives and lubricants. The total content of the additives is not particularly limited, and various additives are included in various weight ranges depending on the intended use. The content of the above-described additives is a level commonly used in the art.

The reactive diluent is a diluent that helps each component of the composition to be evenly applied to the object to which the composition is applied, for example, n-butyl glycidyl ether, aliphatic glycidyl ether, 2-ethylhexyl glycidyl ether. , Phenyl glycidyl ether, O-cresyl glycidyl ether, nonylphenyl glycidyl ether, p-tertbutylphenyl glycidyl ether, 1.4-butanediol diglycidyl ether, 1.6-hexanediol diglycidyl Ether, neopentyl glycidyl ether, 1.4-cyclohexanedimethylol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether Cydyl ether, resorcinol diglycidyl ether, hydrogenate bisphenol aglycidyl ether, trimethylol propene triglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, pentery Tritol polyglycidyl ether, kestol glycidyl ether, serbitol polyglycidyl ether, neokenoxid glycidyl ether, diglycidyl-1.2-cyclohexanedicarboxylate, diglycidyl-O -Phthalate, N,N-diglycidylamine, N,N-diglycidyl-O-toludiene, triglycidyl-p-aminophenol, tetraglycidyl-diaminodiphenylmethane, triglycidyl -It may be at least one selected from the group consisting of isocyanate, 1.4-butanediol diglycidyl ether, 1.6-hexanediol diglycidyl ether, polypropylene glycidyl diglycidyl ether and triethylol propene triglycidyl ether have.

The emulsifier may include, for example, at least one selected from the group consisting of polyoxyethylene, a copolymer of polyoxypropylene, a copolymer of polyoxyethylene and polyoctylphenyl ether, and sodium dodecylbenzenesulfide.

Tackifiers include, 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 resin) (eg terpene resin, terpene-phenol resin, terpene-styrene resin, terpene-phenolic resin), petroleum resin (eg 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 modified phenolic resin), rubber, resin emulsion (eg rosin emulsion, TPR water based resin, 2402 resin emulsion, petroleum resin emulsion), and coumaronindene resin.

Plasticizers may serve to improve process flow or elongation. And the plasticizer can improve the functions of electrical insulation, adhesion, cold resistance, light resistance, oil resistance, soap resistance, flame retardancy resistance, thermal stability, easy processing (intramolecular activity), activity (intermolecular activity), non-toxicity of the composition.

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

Plasticizers for improving oil resistance may be phosplex aromatic phosphate esters (trade names: TPP, TCP, 112 (CDP), 179A (TXP)), polyester, NBR, etc., and plasticizers for soap resistance include TCP, ESBO , polyester, and the like.

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

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

The plasticizer for non-toxicity may be BPBG, octyldiphenyl phosphate, ESBO, citric acid ester, NBR, or 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 phthalate Late (DDP), diisodecyl phthalate (DIDP), C8~C10 mixed higher alcohol phthalate, butylbenzylphthalate (BBP), dioctyl adipate (DOA), dioctyl azelate (DOZ), dioctyl sebacate (DOS), tricrezyl phosphate (TCP), trixylenyl phosphate (TXP), monooctyl diphenyl phosphate (Santicizer 141), monobutyl-dicylenyl phosphate, trioctyl phosphate (TOF), aromatic oils, poly Bdenum, paraffin, etc. can be used.

Any 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 aryl ether sulfates having 8 to 18 C atoms and up to 40 ethylene oxide or propylene oxide units in the hydrophobic group, C8 to C18 alkyl sulfonates, alkylaryl sulfonates, esters and semi-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, alkyl polyglycol ethers or alkyl aryl polyglycol ethers having C8 to 40 ethylene oxide units. For example, sodium dodecyl sulfate (SDS), sodium-silicate, etc. may be used.

Fillers are added to improve the strength, durability, and workability of the composition, and include, for example, calcium carbonate, talc, medium, ceramic, silica, dolomite, clay, titanium bag, zinc oxide, talc, carbon (anti-shrinkage, anti-blocking), potassium carbonate, titanium oxide, liquid polysulfide polymers, volatile diluents, magnesium oxide, processing oil, and the like.

The curing accelerator includes, for example, dibutyltin dilaurate, JCS-50 (manufactured by Johoku Chemical Co., Ltd.), and formate TK-1 (manufactured by Mitsui Chemicals Polyurethane). And as the antioxidant, for example, dibutylhydroxytoluene (BHT), Irganox (registered trademark) 1010, Irganox (registered trademark) 1035FF, Irganox (registered trademark) 565 (all, Chiba Specialty Chemicals) product of Zusa).

The antistatic agent is not particularly limited, and specifically, 1-hexyl-4-methylpyridinium hexafluorophosphate, dodecylpyridinium hexafluorophosphate, a fluorinated organometallic compound (eg, 3M HQ-115), an 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 salt (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 [TBMA][NTf ₂ ], and the like, and these may be used alone or in combination of two or more.

Elastomer refers to a polymer having rubber or elastomer properties, for example, ethylene-vinyl acetate copolymer, acrylic rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, styrene-ethylene- A butylene-styrene copolymer, an acrylonitrile-butadiene copolymer, etc. can be used.

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

Pigments may be natural or synthetic pigments, and they 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 used alone or in combination.

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

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

The coupling agent may improve adhesion and adhesion reliability between the adhesive composition and the packaging material. When such a coupling agent is added, adhesion reliability can be improved 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-glycidoxypropyl trimethoxy silane, γ-glycidoxypropyl methyldiethoxy silane, γ-glycidoxypropyl triethoxy silane , 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxy silane, γ-aminopropyl tri Methoxy silane, γ-aminopropyl triethoxy silane, 3-isocyanatopropyl triethoxy silane, γ-acetoacetatepropyl trimethoxysilane, γ-acetoacetatepropyl triethoxy silane, β-cyanoacetyl A silane compound 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 wetting agent may be, for example, sugar, glycerin, an aqueous sorbitol solution or an amorphous sorbitol aqueous solution alone or in combination.

UV absorbers include ethylhexyl methoxycinnamate (eg, 2-Ethylhexyl 4-methoxycinnamate), ethylhexyl salicylate, 4-methylbenzylidene camphor, isoamyl p-methoxycinnamate, octocrylene, phenylbenz imidazole sulfonic acid, homosalate, cinoxate, ethylhexyltriazone, polysilicon-15, TA-salicylate, popba (PABA), ethylhexyldimethylfaba, glyceryl paba, and the like. These may be used alone or in combination of two or more.

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

A method for preparing an adhesive composition for a zone according to another embodiment comprises the steps of mixing lysine, citric acid, a thickener and water; and stirring the mixture at 80° C. or less.

First, a mixture is prepared by mixing lysine, citric acid, a thickener and water, and by stirring the prepared mixture at 80° C. or less, an adhesive composition for a belt is prepared.

When the stirring of the prepared mixture at 80° C. or less is performed outside the above temperature range, side reaction materials, impurities, etc. may be formed, and in some cases, it may be difficult to obtain a pressure-sensitive adhesive composition having a desired adhesiveness. Stirring at 80°C or lower is performed, for example, 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. The step of stirring at 80° C. or less includes, for example, i) the 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.) and a second step of cooling. When lysine, citric acid, a thickener and water are mixed, citric acid and a thickener are added to an aqueous solution of lysine, or lysine, citric acid, a thickener and water are mixed simultaneously. Thickeners are used, for example, in the form of thickener solutions dissolved in water. The pressure-sensitive adhesive composition for a zone may further include a process of removing the water and the solvent by concentration under reduced pressure to control the solid content within a predetermined range. Stabilizers may be added during manufacturing.

In the step of preparing a mixture by mixing lysine, citric acid, a 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 the 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. When the content of lysine with respect to citric acid is more or less than the above-mentioned range, precipitation may be formed in the composition to decrease adhesion, or storage stability or storage stability of the adhesive composition may be reduced.

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

The paper included in the first substrate or constituting the first substrate is at least one selected from kraft paper, clip tape paper, embossing paper, and corrugated paper, but is not necessarily limited thereto, and any paper used in the art is possible. Polymers included in or constituting the second substrate include high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene, polyurethane, ethylene-propylene-diene ternary At least one selected from copolymer synthetic rubber, ethylene vinyl acetate, neoprene rubber, styrene-butadiene rubber, and nitrile-butadiene rubber is not necessarily limited thereto, and any polymer used in the art is possible. 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 base material is, for example, a paper base paper obtained by overlapping a plurality of kraft papers. For example, the first substrate may include kraft paper as a first layer, corrugated paper, embossed paper, or creeptape paper as a second layer disposed on the first layer, and kraft paper as a third layer disposed on the second layer. It is 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 belt (paper sack) according to another embodiment includes the above-described belt paper. For example, the sheet is prepared by folding and gluing the above-mentioned sheet paper. The belt is used as a bag for various powders such as sugar, flour, feed, grain, and cement.

In addition, other articles include the rent paper described above. Other articles are, for example, boxes, cups, packs, etc., but are not limited thereto, and may be any article that can be manufactured using the base paper.

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

[Example 1] Preparation of a pressure-sensitive adhesive composition for a zone comprising 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 54 wt% L-lysine free form aqueous solution, and the mixture was diluted with stirring at room temperature (25° C.) for 30 minutes. To the diluted lysine, 23.66 g of citric acid (CA) and xanthan gum were slowly added at room temperature (25° C.) and stirred for 1 hour, followed by stirring at 60° C. for 3 hours. Then, after the reaction mixture reached room temperature (25° C.), the reaction was terminated to obtain 172.58 g of a pressure-sensitive adhesive composition. In this composition, the solid content of lysine and citric acid was about 45 parts by weight based on 100 parts by weight of the composition, and the mixing 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

An 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 each contain xanthan gum, guar gum, and gum arabic) Specific compositions are shown in Tables 1 to 3 below. is initiated.

[Example 2] Precipitation formation, viscosity and peel strength evaluation

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

As Control A, a commercially available polyvinyl alcohol-based pressure-sensitive adhesive (J-POVAL JP-18, Japan VAM & Poval Co., Ltd.) was prepared. For each of the pressure-sensitive adhesive compositions, precipitation formation, viscosity, and peel strength were evaluated according to the following method, and the evaluation results are shown in Tables 1 to 3 below.

1) Whether precipitation is formed

Precipitation formation of the prepared composition 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 Industries). After the film coated with the composition was left for 14 days at room temperature (25° C.) and 60±10% relative humidity, the shape change was evaluated by checking the surface change of the pressure-sensitive adhesive composition present on the OPP film. 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 type spindle, and the viscosity at 60 rpm. The 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 high-density polyethylene (HDPE) film (film size: 120 mm* 25 mm, thickness: 50 um), use the #4 bar coater (bar coater) to coat the adhesive composition on one side of kraft paper to a thickness of 11 um. After drying in an oven at 60°C for 4 minutes, it was laminated with a high-density polyethylene (HDPE) film using a dry laminator equipment (roller speed 1.9 m/min, roller temp. 60°C). The lamination-completed specimen was dried in an oven controlled at 25° C. for 12 hours. The peel strength of the specimen prepared according to ASTM D1876 "Measurement of T peel strength" was measured. Peel strength was measured using a push-pull gauge measuring instrument (manufacturer IMADA), and the maximum load when a 1N load per 1.0 inch (1 inch = 25 mm) of width of the specimen was pulled up to 10 cm was applied. The 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 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 adhesive strength by providing improved peel strength compared to 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 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 adhesive strength by providing improved peel strength compared to Control A in various solid 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 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 adhesive strength by providing improved peel strength compared to Control A in various thickener content ranges.

[ Reference example One] lysine and stability evaluation of a 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 54 wt% L-lysine free form aqueous solution, and the mixture was diluted with stirring at room temperature (25° C.) for 30 minutes. 70.97 g of 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. Then, after the reaction mixture reached room temperature (25° C.), the reaction was terminated to obtain 249.93 g of a pressure-sensitive adhesive composition. The content of the 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 acids = 1:1 molar ratio composition)

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

In the same manner as in Example 1, except that acetic acid, glutamic acid, glutaric acid, tartaric acid, aspartic acid, fumaric acid, glyoxylic acid, 4-ketopimelic acid, pyruvic acid, and 1,3-acetonedicarboxylic acid were used instead of citric acid, respectively. The composition was prepared by carrying out according to the same method.

(Evaluation of precipitation)

Precipitation formation of the prepared composition 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 Industries). After the composition-coated film was left for 14 days at room temperature (25° C.) and 60±10% relative humidity, the shape change was evaluated by checking the surface change of the pressure-sensitive adhesive composition present on the OPP film.

The composition containing lysine and citric acid did not form a precipitate, whereas the composition containing other organic acids and lysine formed a precipitate, and adhesion could not be evaluated.

When the composition was prepared by mixing lysine and various organic acids, it was confirmed that all compositions did not form a precipitation and did not exhibit adhesion.

[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 comprising lysine and citric acid was prepared. (Mole ratio of lysine and citric acid = 1:1, solid content 50 parts by weight) 25 g of the following additional solvent was added to 50 g of the prepared pressure-sensitive adhesive composition, and stirred 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), 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, an alcohol, was used as an additional solvent, but was not dissolved and precipitated in the other additional organic solvents described above.

[Reference Example 3] Analysis of the shape, viscosity and initial adhesive force of the adhesive composition according to the solid content

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

1) Stability evaluation

A specific method for evaluating the stability of each adhesive composition having various molar ratios is as follows. About 1 g of each adhesive composition was measured in an aluminum dish having a diameter of 5 cm. After that, it was observed whether a precipitate was formed in the pressure-sensitive adhesive composition for 14 days at room temperature (25° C.) and relative humidity of 60±10%.

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 type spindle, and the viscosity at 60 rpm.

3) Initial adhesion evaluation

In the stability evaluation, the initial adhesive strength was evaluated for the composition in which no precipitation was formed. The initial adhesive strength was measured using Anton Paar's rheometer measuring equipment, and the initial adhesive strength of the adhesive composition was compared through this equipment. A SUS material probe having a diameter of 25 mm is brought into contact 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 is measured to measure the instantaneous initial adhesive force. Quantitative evaluation was made. The evaluation results are shown in Table 4 below.

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

[Reference Example 4] Comparison of initial adhesive strength

The adhesive strength of the conventional adhesive and the adhesive composition of the present application was compared.

According to the manufacturing method described in Reference Example 1, an adhesive composition comprising lysine and citric acid was prepared. However, the content of water was adjusted so that the content of solids in the pressure-sensitive adhesive composition was 10% by weight. (Mole 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), the content of water is adjusted so that the solid content is 10% by weight to obtain an adhesive composition (hereinafter, Control 1) was prepared.

By using the same method as described in Reference Example 3, the viscosity and initial adhesive strength of the pressure-sensitive adhesive composition of the present application (solid content 10% by weight) and the control 1 were 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 1
(PVA system) 10 43.49 0.201

Referring to Table 5, the adhesive composition according to the present application exhibited an equivalent level of initial adhesive strength compared to the polyvinyl alcohol-based adhesive composition (control group 1).

[ Reference example 5] Evaluation of peel strength according to solvent

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

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

According to the manufacturing method described in Reference Example 1, an adhesive composition comprising lysine and citric acid was prepared (below 5-7 to 5-8). However, methanol was added in addition to deionized water, and the weight ratio of deionized water and methanol was set to 6:4 and 4:6. (Mole 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, Control 2) (solid content 59% by weight) was prepared. Peel strength for each of the adhesive compositions was evaluated according to the following method, and the evaluation results are shown in Table 6 below.

1) Peel strength

After preparing the PET film (film size: 120mm*25mm, thickness: 38um or 50um), the sample was coated on the surface of the PET film (50um thickness) to a thickness of 11 um using a bar coater. After drying in an oven at 60℃ for 4 minutes, lamination was performed with PET film (38um thickness) using dry laminatior equipment (roller speed 1.9m/min, roller temp. 60℃). After the lamination was completed, the specimen was dried in an oven controlled at 30° C. for 72 hours. The peel strength of the dried specimen was measured according to ASTM D1876 "Measurement of 180°T Peel Strength". 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 (6:4 wt ratio) 6.28 5-8 1:1 DIW and methanol (4:6 wt ratio) - Control 2
(Acrylic) - 59 6.61

Referring to Table 6, the PET film adhered to the stainless steel by the pressure-sensitive adhesive composition according to the present application was separated within 1 hour, and provided similar peel strength even with a lower solid content than that of Control 2.

In addition, when water and alcohol were used as solvents, the peel strength was further improved. It is judged that the improved peel strength is because the adhesive composition using the mixed solvent has a lower contact angle compared to the adhesive composition containing only deionized water, and as a result, has better coating properties on the substrate. However, when the content of deionized water and alcohol was in a 4:6 weight ratio, phase separation occurred in the pressure-sensitive adhesive composition, and thus it could not be used.

[ Reference example 6] Analysis of the composition in the adhesive composition according to the reaction temperature conditions

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

1) Preparation at 0 ° C. (low temperature): 79 g of DIW (distilled water) was added to 100 g of 54 wt% lysine aqueous solution and stirred at 0 ° C. (T1) for 30 minutes. To the diluted result, 70.97 g of citric acid was slowly added at 0° C. (T2) and stirred for 1.5 hours to prepare an adhesive composition. (Solid content: 50% by weight, mixing 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 wt% lysine aqueous solution and stirred at room temperature 25° C. (T1) for 30 minutes. To the diluted resultant, 70.97 g of citric acid was slowly added at 25° C. (T2) and stirred for 1.5 hours to prepare a pressure-sensitive adhesive composition. (solid content: 50 wt %, molar ratio of lysine and citric acid = 1:1). A temperature controller was used to maintain the same temperature while the pressure-sensitive adhesive composition was stirred (hereinafter the same).

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

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

5) Preparation at 240°C: A composition was prepared in the same manner as in 2) above, 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., so that the pressure-sensitive adhesive composition could not be prepared. Therefore, component analysis was performed using ¹ H NMR for the compositions prepared at 0 ℃, 25 ℃, 60 ℃ and 80 ℃.

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

Superconducting Fourier Transform Nuclear Magnetic Resonance Spectrometer (400MHz) Model: 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 the compositions prepared at 0° C. (Sample 1), 25° C. (Sample 2), and 80° C. (Sample 3). The results of NMR analysis are shown in FIG. 1 . Referring to Figure 1, the compositions prepared at 0 ℃, 25 ℃, and 80 ℃ all of the ¹ H NMR peak appeared at the same position, chemical shift (chemical shift) did not occur, they all have the same composition It can be seen that there is That is, the pressure-sensitive adhesive composition prepared at 0° C., 25° C., and 80° C. has lysine and citric acid in a mixture state and there is no formation of a condensate of lysine and citric acid, or even if a condensate is generated, it is contained in a very small amount it can be seen that

Claims (14)

A pressure-sensitive adhesive composition for a zone comprising a salt of lysine and citric acid and a thickener. According to claim 1, wherein the thickener is a water-soluble natural polymer, and water-soluble synthetic polymer comprising at least one selected from the adhesive composition for the zone. According to claim 2, wherein the water-soluble natural polymer is xanthan gum (xanthan gum), guar gum (guar gum), gum arabic, gum tragacanth, galactan, gum carab, karaya gum, carrageenan, gum acacia, pectin, cannan , Queen's seed (quince), algae colloid (brown 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 Trans, succinoglucan, bluelan, tragacanthin, hyaluronic acid, pectin, alginic acid, agar, galactomannans, beta-cyclodextrin , Amylase (amylase), casein, and chitosan (chitosan), the adhesive composition for the zone comprising at least one selected from the group consisting of. According to claim 2, wherein the water-soluble synthetic polymer is polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinyl pyrrolidone (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, Hydroxybutylmethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose stearoxyether, carboxymethylhydroxyethylcellulose, alkylhydroxyethylcellulose, nonoxynylhydroxy Ethyl cellulose, sodium cellulose sulfate, methyl cellulose, methyl ethyl cellulose, ethyl cellulose, and carboxymethyl cellulose (CMC) adhesive composition comprising at least one selected from the group consisting of. According to claim 1, wherein the content of the thickener is 1 to 10 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive composition for a zone. According to claim 1, wherein the mixing molar ratio of the lysine and citric acid is 1.5:1 to 1:3 adhesive composition for a zone. According to claim 1, wherein the solid content in the composition is 0.1 to 70 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive composition for a zone. According to claim 1, wherein the adhesive composition for the zone, the peel strength measured according to ASTM D1876 "Method for measuring T peel strength" is 1 N/25mm or more of the adhesive composition for the zone. According to claim 1, wherein the pressure-sensitive adhesive composition for the zone is not formed during storage at -18 to 45 ℃ for 14 days or more, the pressure-sensitive adhesive composition for the zone. mixing lysine, citric acid, a thickener and water; and
A method for preparing a pressure-sensitive adhesive composition for a zone comprising; stirring the mixture at 0° C. to 80° C. The method of claim 10, wherein the mixing molar ratio of the 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
and an adhesive layer disposed between the first and second substrates,
The sheet paper for the sheet comprising the pressure-sensitive adhesive layer according to any one of claims 1 to 9, the pressure-sensitive adhesive composition for a sheet. The method of claim 12, wherein the first substrate comprises at least one selected from kraft paper, clip tape paper, embossing 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, A belt paper comprising at least one selected from neoprene rubber, styrene-butadiene rubber, and nitrile-butadiene rubber. A zone comprising the zone paper according to claim 12 .

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