KR20180106738A - A composition and preparing method thereof - Google Patents

Abstract

Disclosed is a composition containing at least one selected among a mixture of a dicarboxylic acid having a keto group represented by chemical formula 1 and a diamine represented by chemical formula 2 and a salt thereof. Moreover, disclosed is a production method thereof. In the chemical formula 1, x and y are each independently 0 or an integer of 1 to 13, provided that x and y are not simultaneously 0. In the chemical formula 2, A_1 and A_2, L, a, and b are the same as defined in the detailed description. According to an embodiment of the present invention, the composition can be useful as a water-repellent adhesive.

Description

[0001] The present invention relates to a composition and a preparing method thereof,

The present invention relates to a novel composition and a process for producing the same.

When an aliphatic diamine is reacted with an aliphatic dicarboxylic acid, an amide salt is obtained. These amide salts generally form a polyamide resin through continuous polycondensation reaction at a high temperature.

The amide salt remains dissolved in the solvent depending on the kind of the solvent, and when the solvent is removed, the amide salt precipitates in a solid powder state. The amide salt having such a state is limited in application to the pressure-sensitive adhesive.

SUMMARY OF THE INVENTION The present invention provides a novel composition capable of naturally decomposing.

Another object of the present invention is to provide a method for producing the above-mentioned composition.

In order to accomplish the object of the present invention, there is provided a composition comprising at least one selected from a salt of a mixture of a dicarboxylic acid containing a keto group represented by the following formula (1) and a diamine represented by the following formula (2) .

[Chemical Formula 1]

In Formula (1), x and y are each independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,

(2)

In Formula 2, A ₁ and A ₂ independently represent a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 C20 heteroarylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,

L is a linker, which represents a chemical bond or represents an alkylene group of C1 to C10 or an arylene group of C6 to C10, -O-, S (= O) _2- ,

a and b are independently 0 or an integer of 1 to 20,

The composition is a water-soluble pressure-sensitive adhesive.

Another aspect of the present invention is to provide a method for preparing a composition comprising the diester of the formula (1) and the diamine of the formula (2).

[Chemical Formula 1]

In Formula (1), x and y are each independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,

(2)

In Formula 2, A ₁ and A ₂ independently represent a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 C20 heteroarylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,

L is a linker and represents a chemical bond or represents an alkylene group of C1 to C10 or an arylene group of C6 to C10, or a group represented by -O-, -N-, -S-, S (= O) _2- ,

a and b are independently 0 or an integer of 1 to 20;

The composition according to one embodiment is useful as a water-soluble pressure-sensitive adhesive. Can be easily removed from the adherend or substrate by dissociating it from the adherend or substrate according to one embodiment. Therefore, such a pressure-sensitive adhesive is environmentally friendly as a hydrolysis-resistant substance.

Hereinafter, a composition according to one embodiment and a method for producing the same will be described in detail.

There is provided a composition comprising at least one selected from the group consisting of a mixture of a keto group-containing dicarboxylic acid represented by the following formula (1) and a diamine represented by the following formula (2) and salts thereof.

[Chemical Formula 1]

In Formula (1), x and y are each independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,

(2)

In Formula 2, A ₁ and A ₂ independently represent a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 C20 heteroarylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,

L is a linker (linker), to indicate a chemical bond or, -O-, -N-, -S-, -S (= O) 2 - and, C1 to C10 alkyl group or a C6 to C10 arylene group,

a and b are independently 0 or an integer of 1 to 20;

In the present specification, the term "at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the following formula (2) and a salt thereof is a compound represented by the following formula (1) At least one selected from the group consisting of a mixture of compounds and salts thereof is at least one selected from a mixture of a compound represented by the following formula (1) and a compound represented by the following formula (2) and salts thereof; Or ii) a mixture of a compound represented by the following formula (1) and a compound represented by the following formula (2) and salts thereof.

The keto-containing dicarboxylic acid represented by the above-mentioned formula (1) is, for example, selected from the group consisting of mesoxalic acid, oxaloacetic acid, alpha-keto glutaric acid, Ketoadipic acid, oxoheptanedioic acid, 2-oxo-pentanedioic acid, 2-oxooctanedioic acid, 5-oxononanedioic acid, at least one member selected from the group consisting of 4-oxo-undecanoic acid, 4-oxosebacic acid, 5-oxo undecanedioic acid and 4-oxododecanedioic acid. . As described above, a monomer such as alpha-keto glutaric acid derived from the above-mentioned bio is introduced as a dicarboxylic acid containing a keto group and is environmentally friendly.

The dicarboxylic acid containing a keto group of the formula (1) may include, for example, at least one selected from compounds represented by the following formula (1a).

[Formula 1a]

 The diamine represented by Formula 2 may be, for example, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-hexanediamine, 1,7-diaminoheptane, 1,8-diaminooctane (1, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,11- diaminodecane, 1,12-diamino dodecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,1-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,10-diaminoheptadecane, 1,8-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, and 1,8-diaminoheptadecane. methyl 1-pentane diamine, 3-methyl-1,5-pentane diamine, 2-methyl-1,5-pentane diamine, Octane diamine, 5-methyl-1,9-nonanediamine, 2,2,4-trimethyl-1,6-octanediamine, 2,2,4-trimethyl-1,6-hexane diamine, cyclohexane diamine, methyl cyclohexane diamine, cycloaliphatic diamine, bis- (4- (4-aminohexyl) methane, isophorone diamine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine p-xylylenediamine, m-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone. (4,4'-diaminodiphenyl ether), and the like.

The diamine compound represented by the general formula (2) contains at least one selected from a primary amino group and a secondary amino group. The diamine compound represented by the formula (2) according to one embodiment includes, for example, at least one selected from compounds represented by the following formula (2a).

(2a)

In the composition according to one embodiment, the mixing ratio of the keto group-containing dicarboxylic acid of formula (1) and the diamine of formula (2) is controlled so that the mixture of the dicarboxylic acid-containing dicarboxylic acid and the diamine can be maintained in a solid state.

According to one embodiment, the mixing ratio can be controlled such that the number of carbonyl groups corresponds to the number of amino groups of the diamine compound of formula (2). For example, when the content of the keto-containing dicarboxylic acid of formula (1) having three carbonyl groups in the composition is 2 moles, the content of the diamine compound of formula (2) having two amino groups can be used in the range of 3 moles.

The composition has a liquid state or a gel state at room temperature (25 DEG C) and is excellent in adhesive property. Such a composition is usable as a water-soluble pressure-sensitive adhesive. When the composition is used as a pressure-sensitive adhesive, it is easy to remove since the pressure-sensitive adhesive is dissociated by water when the pressure-sensitive adhesive is separated or removed from the applied base material or the applied material.

The effect of the composition according to one embodiment exhibiting adhesiveness as described above will be described below. These and other effects are not intended to be construed in a limiting sense only and are not to be construed as limiting the scope of the present invention.

The keto-containing dicarboxylic acid represented by the formula (1) contained in the composition has three carbonyl groups, and the diamine represented by the formula (2) has two or more amino groups. The non-covalent electron pair of the carbonyl group of the dicarboxylic acid-containing dicarboxylic acid and the hydrogen of the amino group of the diamine compound form an ionic bond such as a hydrogen bond to form a network structure between these compounds. As a result, it is possible to exhibit excellent adhesive properties while maintaining a liquid or gel state without being precipitated in a solid state.

The content of the keto-containing dicarboxylic acid represented by the formula (1) in the composition according to one embodiment is 0.5 to 1.2 moles based on 1 mole of the diamine represented by the formula (2).

When the composition is a salt, the salt may be a compound represented by the following general formula (3).

 (3)

In Formula 3, x and y are independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,

A ₁ and A ₂ are each independently a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 hetero An arylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,

L is a linker (linker), to indicate a chemical bond or, -O-, -N-, -S-, -S (= O) 2 - and, C1 to C10 alkyl group or a C6 to C10 arylene group,

a and b are independently 0 or an integer of 1 to 20;

In the above formula (3), when a and b are 0, and when x and y are 0, they represent a chemical bond.

은 상술한 케토기 함유 화합물의 구체적인 예시 화합물로부터 파생된 음이온일 수 있다. 그리고 화학식 3에서

는 상술한 디아민의 구체적인 예시 화합물로부터 파생된 음이온일 수 있다.In the above formula (3)

May be an anion derived from a specific exemplified compound of the above-mentioned keto group-containing compound. In formula (3)

May be an anion derived from the specific exemplified compounds of diamines described above.

The compound represented by the formula (3) may be at least one selected from compounds represented by the following formulas (4) to (17).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

According to one embodiment, the compound represented by the general formula (3) may have two or more kinds of cations or two or more kinds of anions. When the compound represented by the general formula (1) has two kinds of cations, the content of the anion is stoichiometrically controlled so as to have a charge balance and have a neutral state. When the compound of formula (2) has two kinds of anions described above, the cation can be stoichiometrically adjusted so that the overall charge state is maintained as neutral. When the charge balance is achieved by neutralizing the charge, the yield of the salt can be maximized and the excess acid and base molecules not forming ionic bonds can be minimized.

The compound represented by the formula (3) is, for example, selected from the compounds represented by the above formulas (3a) to (3c).

[Chemical Formula 3]

In Formula (3), x and y are independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time, b is an integer of 1 to 10.

 (3b)

In formula (3b), m and n are selected differently from each other and are an integer of 1 to 10,

x and y are independently 0, an integer of 1 to 10,

[Chemical Formula 3c]

In formula (3c), a and b are selected differently from x and y, 0, an integer from 1 to 10, and n is an integer from 1 to 10.

The composition according to one embodiment can be used as a water-soluble pressure-sensitive adhesive. The water-dispersible pressure-sensitive adhesive may further contain at least one additive selected from a crosslinking agent, a tackifying resin and a solvent, depending on the intended properties.

The pressure-sensitive adhesive can be completely removed from the substrate to which the pressure-sensitive adhesive is applied upon contact with water.

The composition according to one embodiment can be prepared by mixing the keto group-containing dicarboxylic acid represented by the formula (1) and the diamine represented by the formula (2). The mixing is carried out at room temperature (25 캜).

When the keto group-containing dicarboxylic acid represented by the formula (1) and the diamine represented by the formula (2) are mixed, the acid-amine neutralization reaction proceeds to prepare the compound represented by the formula (3).

The content of the diamine represented by the formula (2) has a molar ratio of 0.9 to 1.2 mol based on 1 mol of the keto-containing dicarboxylic acid represented by the formula (1).

In the formula (3), the anion is a region derived from the keto-containing dicarboxylic acid represented by the formula (1), and the cation is a region derived from the diamine represented by the formula (2). The characteristics of the compound of Chemical Formula 3 vary depending on the structure and the carbon number length of the keto group-containing dicarboxylic acid represented by Chemical Formula 1 and the diamine represented by Chemical Formula 2. For example, when the carbon chain length of the keto group-containing dicarboxylic acid represented by the formula (1) and the diamine represented by the formula (2) is long, the fluidity of the compound of the formula (3) becomes high.

The step of reacting the keto-group-containing dicarboxylic acid with the diamine is carried out by simultaneously mixing a keto-containing dicarboxylic acid, a diamine and a solvent.

The step of reacting the keto group-containing dicarboxylic acid with the diamine includes, for example, a step of preparing a keto-containing dicarboxylic acid solution by mixing a keto group-containing dicarboxylic acid with a solvent, mixing the diamine with a solvent, And a step of mixing and reacting a solution of a dicarboxylic acid-containing dicarboxylic acid and a diamine.

The solvent is at least one selected from deionized water and alcohol. The content of the solvent is 100 to 4000 parts by weight based on 100 parts by weight of the dicarboxylic acid-containing dicarboxylic acid and diamine.

The reaction between the keto group-containing dicarboxylic acid and the diamine generates heat by the neutralization reaction between the acid and the base. When the temperature of the reaction product reaches room temperature, the reaction of these compounds is terminated.

When the reaction is terminated, the reaction product is evaporated under reduced pressure to remove the solvent to obtain an aqueous separable pressure-sensitive adhesive containing the compound of formula (1). Deionized water is added to the water-repellent pressure-sensitive adhesive and stirred at room temperature to obtain a pressure-sensitive adhesive. The pH of the pressure-sensitive adhesive is 7 to 8, and has a pH value of, for example, 7.16 to 7.8. The content of the solid content in the pressure-sensitive adhesive may optionally be adjusted to 1 to 100% by weight, for example, 40 to 70% by weight. When the content of the solid content is in the above range, it is easy to apply the pressure-sensitive adhesive on the substrate.

Alcohols include, but are not limited to, monohydric alcohols, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, or mixtures thereof.

The monohydric alcohol includes at least one selected from methanol, ethanol, propan-2-ol, butan-1-ol, pentan-1ol and hexadecan-1-ol. The polyhydric alcohols include ethane-1,2-diol, propane-1,2-diol, propane-1,2,3-triol propane-1,2,3-triol), butane-1,3-diol, butane-1,2,3,4-tetraol -tetraol), pentane-1,2,3,4,5-pentol, hexane-1,2,3,4,5,6-hexol -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). < / RTI >

Unsaturated aliphatic alcohols include, for example, prop-2-ene-1-ol, 3,7-dimethylocta- 2,6-dien-1-ol, prop-2-yn-1-ol, cyclohexane- 2- (2-propyl) -5-methyl-cyclohexane-1-ol, ol) may be mentioned.

When the water-decomposable pressure-sensitive adhesive according to one embodiment is used as a pressure-sensitive adhesive tape, a label sheet, a spray-type pressure-sensitive adhesive, a dust remover, etc., water can be easily removed without damaging the adherend. Therefore, the packaging material can be easily recycled. In addition, when it is expanded to the field of agrochemicals and seeds, it can be easily removed with water after using a composition containing a pressure-sensitive adhesive, so that the application range can be broadened.

As a starting material to be used in the production of the pressure-sensitive adhesive according to the present invention, a monomer derived from bio-origin can be selected. Since it is a monomer which can be utilized in vivo, when a pressure-sensitive adhesive is separated by water, a monomer, polymer or oligomer It is possible to prevent the environmental pollution caused by the dust.

Structures such as an adhesive tape and a sheet for labels formed using the water-decomposable pressure-sensitive adhesive described above have improved mechanical strength such as tensile shear strength and peel strength.

As used herein, " alkyl " refers to fully saturated branched or unbranched (or linear or linear) hydrocarbons.

Non-limiting examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n- pentyl, isopentyl, neopentyl, isoamyl, -Methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl and the like.

"Alkyl" at least one hydrogen atom of an alkyl group of a halogen atom, halogen-substituted C1-C20 (for _{example: CCF 3, CHCF 2, CH} 2 F, CCl 3 , etc.), an alkoxy of C1-C20 alkoxy, C2-C20 of A sulfamoyl group, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C20 alkyl group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, C20 alkenyl, C2-C20 alkynyl, C1-C20 heteroalkyl, C6-C20 aryl, C6-C20 arylalkyl, C6-C20 heteroaryl, C7-C20 heteroaryl An alkyl group, a C6-C20 heteroaryloxy group, a C6-C20 heteroaryloxyalkyl group or a C6-C20 heteroarylalkyl group.

The term " halogen atom " includes fluorine, bromine, chlorine, iodine and the like.

&Quot; Alkenyl " refers to branched or unbranched hydrocarbons having at least one carbon-carbon double bond. Non-limiting examples of the alkenyl group include vinyl, allyl, butenyl, isopropenyl, isobutenyl and the like, and at least one hydrogen atom of the alkenyl may be substituted with the same substituent as the alkyl group described above .

&Quot; Alkynyl " refers to branched or unbranched hydrocarbons having at least one carbon-carbon triple bond. Non-limiting examples of the "alkynyl" include ethynyl, butynyl, isobutynyl, isopropynyl, and the like.

Aryl " also includes a group in which an aromatic ring is fused to one or more carbon ring rings. Non-limiting examples of " aryl " include phenyl, naphthyl, tetrahydronaphthyl, and the like.

Also, at least one hydrogen atom in the " aryl " group may be substituted with the same substituent as in the case of the above-mentioned alkyl group.

&Quot; Heteroaryl " means monocyclic or bicyclic organic compounds containing one or more heteroatoms selected from N, O, P, or S and the remaining ring atoms carbon. The heteroaryl group may contain, for example, from 1 to 5 hetero atoms, and may include 5-10 ring members. The S or N may be oxidized to have various oxidation states.

Examples of heteroaryl include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, , 5-oxadiazolyl, 1,3,4-oxadiazolyl group, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, Thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol- Yl, isoxazol-3-yl, 1,2,4-triazol-5-yl, Yl, pyridyl-3-yl, 2-pyrazin-4-yl, 2-yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl or 5-pyrimidin-2-yl.

The term " heteroaryl " includes those where the heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocycle.

The " carbon ring " group used in the formula refers to a saturated or partially unsaturated non-aromatic monocyclic, bicyclic or tricyclic hydrocarbon group.

Examples of monocyclic hydrocarbons include cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. Examples of bicyclic hydrocarbons are bornyl, decahydronaphthyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.1] heptenyl, or bicyclo [2.2.2] octyl. And examples of tricyclic hydrocarbons include adamantly.

  &Quot; Heterocycle " is a cyclic hydrocarbon containing at least one heteroatom and may contain from 5 to 20, for example from 5 to 1, carbon atoms. Wherein the heteroatom is one selected from sulfur, nitrogen, oxygen and boron.

Alkoxy, aryloxy, heteroaryloxy means alkyl, aryl and heteroaryl, respectively, attached to an oxygen atom herein.

Hereinafter, the water-permeable pressure-sensitive adhesive according to the exemplary embodiments and the method for producing the same will be described in more detail.

Example  One

73.02 g of alpha-keto glutaric acid and 380.35 g of ethyl alcohol were stirred together at room temperature (25 ° C) for 1 hour, and 58.28 g of hexamethylene diamine and 58.28 g of ethyl alcohol ethyl alcohol) were stirred together at room temperature for 1 hour to prepare an ethanol solution of alpha-keto glutaric acid and an ethanol solution of hexamethylenediamine. An ethanol solution of hexamethylenediamine was slowly added to the ethanol solution of alpha-keto glutaric acid, and the mixture was stirred at room temperature and neutralized at the same time. And the reaction was terminated when the generated neutralizing heat reached room temperature. The phase-separated ethyl alcohol was recovered from the reaction mixture to obtain the compound represented by the formula (16).

[Chemical Formula 16]

To facilitate evaluation of the physical properties represented by the formula (16), 82.54 g of deionized water (DIW) was added to the compound of the formula (10) and the mixture was stirred at room temperature for dilution. When complete dissolution was completed, The pH and solids content of the composition were measured. As a result, the content of solids in the composition was about 49.07 wt% and the pH was 7.55.

Example  2

73.06 g of alpha-keto glutaric acid and 95.68 g of methanol were stirred together at room temperature for 1 hour to obtain a methanol solution of alpha-keto glutaric acid.

Separately, 57.98 g of hexamethylenediamine and 65.05 g of methanol were mixed and stirred at room temperature for 1 hour to prepare a methanol solution of hexamethylenediamine.

A methanol solution of hexamethylenediamine was slowly added to the methanol solution of alpha-keto glutaric acid, and the mixture was neutralized while stirring at room temperature.

The reaction was terminated when the neutralization heat occurred at room temperature, and a compound represented by the following formula (16) was prepared. Then, 82.54 g of deionized water (DIW) was added to the compound of Formula 16, and the mixture was stirred at room temperature for dilution. When complete dissolution was completed, stirring was stopped to prepare a composition containing the compound of Formula 16, And the content thereof was measured.

As a result, the solid content was 48.08 wt% and the pH was 7.45.

 [Chemical Formula 16]

Example  3

18.25 g of Alpha-keto glutaric acid was slowly added to 12.90 g of 1,5-Diaminopentane at room temperature (25 ° C) for 1 hour, .

And the reaction was terminated when the generated neutralizing heat reached room temperature. 29.76 g of a compound represented by the following formula (6), which was produced by the reaction termination, was obtained.

[Chemical Formula 6]

The compound was obtained as a viscous material in the form of trapped heat and bubbles generated during the neutralization reaction.

To facilitate the evaluation of the physical properties, 30.31 g of DIW (distilled water) was added to the compound of Formula 6 and diluted by stirring at room temperature. When complete dissolution was completed, stirring was stopped to prepare a composition containing the compound of Formula 6 . The pH and solids content of the composition were measured.

As a result of measurement, the solid content was about 49.03% by weight and the pH was 7.16.

Example  4

73.04 g of alpha-ketoglutaric acid and 344.36 g of ethanol were stirred together at room temperature for 1 hour to obtain an ethanol solution of alpha-keto glutaric acid. Separately, 44 g of 1,4-butanediamine and 196.46 g of ethanol were stirred together at room temperature for 1 hour to obtain an ethanol solution of 1,4-butanediamine.

An ethanol solution of 1,4-butanediamine was slowly added to the ethanol solution of alpha-keto glutaric acid, and the mixture was neutralized while stirring at room temperature. The reaction was terminated when the generated neutralizing heat reached room temperature, and a compound represented by the following formula (12) was obtained.

[Chemical Formula 12]

To the compound of formula (12), 118.31 g of deionized water was added and the mixture was stirred at room temperature to dilute. When complete dissolution was completed, stirring was stopped to obtain a composition containing the compound of formula (12). The pH and solids content of the composition were measured.

As a result of measurement, the solid content was 46.87% by weight and the pH was 7.8.

Example  5

40.01 g of ketoadipic acid and 103.87 g of ethanol were stirred together at room temperature for 1 hour to obtain an ethanol solution of ketoadipic acid.

Separately, 25.66 g of 1,5-diaminopentane and 61 g of ethanol were stirred together at room temperature for 1 hour to obtain an ethanol solution of 1,5-diaminopentane.

An ethanol solution of 1,5-diaminopentane was slowly added to the ethanolic solution of ketoadipic acid, and the neutralization reaction was carried out while stirring at room temperature.

The reaction was terminated when the generated neutralizing heat reached room temperature, and a compound represented by the following general formula (17) was obtained. The phase-separated ethanol was recovered.

[Chemical Formula 17]

To the compound of formula (17), 53.50 g of deionized water was added and the mixture was stirred at room temperature for dilution. When complete dissolution was completed, stirring was stopped to obtain a composition containing the compound of formula (17). The pH and solids content of the composition were measured.

As a result of measurement, the solid content was 46.22% by weight and the pH was 7.65.

Comparative Example  One

Acrylic pressure-sensitive adhesive (K901, Hansung P & I Co., Ltd.) was used.

Comparative Example  2

Rubber-based adhesive (DY5050T, Dongyang Tape Co., Ltd.) was used.

Evaluation example  1: tensile shear strength

Each of the pressure sensitive adhesive prepared according to Examples 1 to 4 and the acrylic pressure sensitive adhesive according to Comparative Example 1 was applied to a PET film having a thickness of 50 to 60 占 퐉 and dried at 40 占 폚 for 30 minutes.

The dried product was cut into a size of 25 * 90 mm and attached to stainless steel (SUS304), and pressed with a hand roller 5 times at a pressure of 1 kgf and adhered to prepare a specimen.

The tensile shear strength was evaluated according to the shear strength KS M ISO 4587: 2008 method. The mechanical properties of the peel strength of the specimen were measured according to the 180 ° pull - off adhesion force KS T 1028: 2009 method. The evaluation results of tensile shear strength and peel strength are shown in Table 1 below.

division Tensile shear strength
(MPa) Peel strength
(N / 25 mm) Example 1 1.92 3.1 Example 2 - 6.9 Example 3 1.10 - Example 4 - 3.85 Comparative Example 1 0.65 - Comparative Example 2 - 5.98

As shown in Table 1, it was found that the tensile shear strength and peel strength of the specimens using the pressure-sensitive adhesive according to Examples 1 to 4 were equivalent or improved as compared with those of Comparative Examples 1 and 2.

Evaluation example  2: Water resistance

Each of the pressure sensitive adhesive prepared according to Examples 1 to 5 and the acrylic pressure sensitive adhesive according to Comparative Example 1 was applied to a PET film having a thickness of 50 to 60 탆 and then dried at 40 캜 for 30 minutes.

The dried product was cut into a size of 25 mm × 25 mm and attached to stainless steel (SUS304), and pressed with a hand roller 5 times at a pressure of 1 kgf and adhered to prepare a test piece.

After the specimens were thoroughly immersed in distilled water (DIW) at normal temperature, normal pressure and pH neutral conditions, the time from when the adhesive was completely removed from the substrate was measured to evaluate the water resistance of the specimen. The evaluation results of the water resistance of the test pieces are shown in Table 2 below.

division Water solubility (sec) Example 1 Within 60 Example 2 Within 60 Example 3 Within 60 Example 4 Within 60 Example 5 Within 60 Comparative Example 1 Not removed Comparative Example 2 Not removed

Referring to Table 2, it was found that the test pieces using the pressure-sensitive adhesives of Comparative Examples 1 and 2 were difficult to be separated from water, but the test pieces using the pressure-sensitive adhesives of Examples 1 to 5 were easy to be separated from water and excellent in water resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the exemplary embodiments or constructions. It will be apparent to those skilled in the art that various modifications and variations are possible in light of the above teachings will be. Accordingly, the scope of protection of the present invention should be determined by the appended claims.

Claims (14)

A composition comprising at least one selected from the group consisting of a mixture of a keto-containing dicarboxylic acid represented by the following formula (1) and a diamine represented by the following formula (2) and salts thereof:
[Chemical Formula 1]

In Formula (1), x and y are each independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,
(2)

In Formula 2, A ₁ and A ₂ independently represent a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 C20 heteroarylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,
L is a linker (linker), to indicate a chemical bond or, -O-, -N-, -S-, -S (= O) 2 - and, C1 to C10 alkyl group or a C6 to C10 arylene group,
a and b are independently 0 or an integer of 1 to 20; The method according to claim 1,
Wherein the keto-containing dicarboxylic acid represented by Formula 1 is selected from the group consisting of mesoxalic acid, oxaloacetic acid, alpha-keto glutaric acid, ketoadipic acid, Oxoheptanedioic acid, 2-oxo-pentanedioic acid, 2-oxooctanedioic acid, 5-oxononanedioic acid, Wherein the composition is at least one selected from the group consisting of 4-oxosebacic acid, 5-oxo undecanedioic acid, and 4-oxododecanedioic acid. 12. The method of claim 11,
When the diamine represented by the above-mentioned general formula (2) is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,8- 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,10-diaminodecane, 1,12-diamino dodecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1, , 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminoheptadecane, 1,1-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1-diaminoheptadecane, , 5-pentanediyl (2-methyl-1,5-pentane diamine), 3-methyl-1,5-pentane diamine, 2- methyl-1,8-octane diamine, 5-methyl-1,9 nonanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 4-trimethyl-1,6-hexane diamine, cyclohexane diamine, methyl cyclohexane diamine, cycloaliphatic diamine, bis- (4-aminohexyl) 4-aminohexyl methane, isophorone diamine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m- Xylylenediamine, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfone, Ether, and 4,4'-diaminodiphenyl ether. The method according to claim 1,
Wherein the salt comprises a compound represented by the following Formula 3:
(3)

In Formula 3, x and y are independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,
A ₁ and A ₂ are each independently a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 hetero An arylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,
L is a linker, which represents a chemical bond or represents an alkylene group of C1 to C10 or an arylene group of C6 to C10, -O-, -S (= O) ₂ -
a and b are independently 0 or an integer of 1 to 20; 5. The method of claim 4,
Wherein the compound represented by Formula 3 is a compound represented by Formula 3a:
[Chemical Formula 3]

In Formula (3), x and y are independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,
and b is an integer of 1 to 10. The method of claim 3,
Wherein the compound represented by Formula 3 is a compound represented by Formula 3b:
(3b)

In formula (3b), m and n are selected differently from each other and are an integer of 1 to 10,
x and y are independently 0 or an integer of 1 to 10; The method of claim 3,
Wherein the compound represented by Formula 3 is a compound represented by Formula 3c:
[Chemical Formula 3c]

In formula (3c), a and b are selected differently from x and y and are 0, an integer from 1 to 10,
n is an integer of 1 to 10; The method according to claim 1,
Wherein the content of the keto group-containing dicarboxylic acid represented by the formula (1) is 0.5 to 1.2 moles based on 1 mole of the diamine represented by the formula (2). The method of claim 3,
The compound represented by the general formula (3) is, for example, at least one compound selected from compounds represented by the following general formulas (4) to (17)
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

The composition of claim 1, wherein the composition is a water-soluble pressure-sensitive adhesive. 10. A process for producing a composition according to any one of claims 1 to 10, comprising mixing a keto-containing dicarboxylic acid represented by the following formula (1) and a diamine represented by the formula (2)
[Chemical Formula 1]

In Formula (1), x and y are each independently 0 or an integer of 1 to 13, provided that when x and y are 0 at the same time,
(2)

In Formula 2, A ₁ and A ₂ independently represent a substituted or unsubstituted C2 to C20 linear or cyclic alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 C20 heteroarylene group, a substituted or unsubstituted C4 to C20 carbon ring group or a substituted or unsubstituted C2 to C20 heterocyclic group,
L is a linker, which represents a chemical bond or represents an alkylene group of C1 to C10 or an arylene group of C6 to C10, -O-, S (= O) _2- ,
a and b are independently 0 or an integer of 1 to 20; 12. The method of claim 11,
Wherein the step of mixing the keto-group-containing dicarboxylic acid and the diamine is carried out by simultaneously mixing the keto-containing dicarboxylic acid represented by the formula (1), the diamine represented by the formula (2) and a solvent. 12. The method of claim 11,
Wherein the solvent is at least one selected from distilled water and alcohol. 14. The method of claim 13,
Wherein the alcohol is at least one monohydric alcohol selected from methanol, ethanol, propan-2-ol, butan-1-ol, pentan-1ol and hexadecan-
Ethane-1,2-diol, propane-1,2-diol, propane-1,2-triol, , 3-triol, butane-1,3-diol, butane-1,2,3,4-tetraol, Pentane-1,2,3,4,5-pentol), hexane-1,2,3,4,5,6-hexyl hexane-1,2,3 , 4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptol (heptane-1,2,3,4,5,6,7-heptol) Polyhydric alcohols;
Prop-2-ene-1-ol, 3,7-dimethylocta-2,6-dien-1 Unsaturated aliphatic alcohols selected from prop-2-yn-1-ol (Prop-2-yn-1-ol);
Cyclohexane-1,2,3,4,5,6-hexol), 2- (2-propyl) -5-methylcyclohexane-1- (Alicyclic alcohols) selected from 2- (2-propyl) -5-methyl-cyclohexane-1-ol or a mixture thereof.