KR102677695B1 - Adhesive composition and adhesive processed article comprising same - Google Patents

Abstract

The present invention relates to an adhesive composition comprising a first monomer represented by Chemical Formula 1, an acrylic second monomer, acrylic acid, and a crosslinking agent, and an adhesive processed product containing the adhesive composition.

Description

Adhesive composition and adhesive processed product containing the same {ADHESIVE COMPOSITION AND ADHESIVE PROCESSED ARTICLE COMPRISING SAME}

The present invention relates to an adhesive composition and an adhesive processed product containing the same.

An adhesive is a substance that attaches two or more products with completely different physical properties and whose composition does not change unless it is artificially moved. The adhesive is used in various fields such as wood, medical, electrical and electronic industries, etc. for interior/exterior materials of buildings, interior materials, advertising materials, various films, non-wovens, and labels. Conventionally, polyethylene glycol and the like were used as materials for the adhesive.

However, the adhesive materials used conventionally do not have the property of being dissociated or decomposed by water, and have the disadvantage of being difficult to use in environments with high temperature and high humidity. Accordingly, it is not suitable as an eco-friendly material and its use in environments with high temperature and high humidity is limited, so there is a need for an adhesive that is excellent as an eco-friendly material and is not significantly affected by the environment in which the adhesive is used.

In order to solve the above problems, there have been attempts to develop new adhesive compositions such as in Korean Patent Publication No. 10-2010-0086716, etc., but they have excellent water dissociation properties, can be used even in high temperature and high humidity environments, and have excellent adhesive properties compared to existing adhesives. , adhesives with cohesive force and vortex, etc. were not provided.

Therefore, there is a need to develop adhesives that solve the above-mentioned problems and adhesive processed products containing the same.

Korean Patent Publication No. 10-2010-0086716

The present invention is intended to solve the above problems, and its purpose is to provide an adhesive composition containing an acrylic polymer and excellent water dissociability, and an adhesive processed product containing the same.

One embodiment of the present invention includes a first monomer represented by the following formula (1); second monomer; acrylic acid; And a cross-linking agent,

The second monomer provides an adhesive composition wherein the second monomer is an acrylic monomer.

[Formula 1]

In Formula 1,

R1 is a six-membered ring containing substituted or unsubstituted N and O.

Another embodiment of the present invention provides an adhesive processed product containing the above-described adhesive composition.

The adhesive composition according to the present invention has the advantage of excellent water dissociability and environmentally friendly properties.

The adhesive composition according to the present invention has excellent adhesion, cohesion and/or vortex.

The adhesive composition according to the present invention has the advantage of excellent product stability and easy storage and distribution.

Figure 1 shows an adhesive processed product according to an exemplary embodiment of the present invention.
Figure 2 shows an adhesive processed product according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

In the present invention, “curing” or “crosslinking” may mean crosslinking caused by heat treatment and/or light exposure, or crosslinking caused between compounds, etc. The crosslinking may be created by connecting radicals generated when a carbon-carbon multiple bond or cyclic structure is decomposed by heat treatment or light irradiation.

In the present invention, the term "combination thereof" included in the Markushi format expression means a mixture or combination of one or more components selected from the group consisting of the components described in the Markushi format expression. It means including one or more selected from the group consisting of.

Examples of substituents in the present invention are described below, but are not limited thereto.

In the present invention, the term "substitution" means changing the hydrogen atom bonded to the carbon atom of the compound to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted. When two or more substituents are substituted, the two or more substituents may be the same or different from each other.

In the present invention, the term “substituted or unsubstituted” refers to deuterium; halogen group; Alkyl group; Alkoxy group; Aryl group; It means that it is substituted with one or more substituents selected from the group consisting of heteroaryl groups, is substituted with a substituent where two or more of the above-exemplified substituents are linked, or does not have any substituents.

In the present invention, the halogen group is a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br), or an iodo group (-I).

In the present invention, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group. , but is not limited to these.

In the present invention, the alkoxy group may be straight chain or branched chain. The number of carbon atoms of the alkoxy group is not particularly limited, but may have 1 to 20 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, and n-no. It may be a nyloxy group, n-decyloxy group, etc., but is not limited thereto.

In the present invention, an aryl group refers to a monovalent group of a monovalent aromatic hydrocarbon or an aromatic hydrocarbon derivative. In the present invention, an aromatic hydrocarbon refers to a compound containing a planar ring in which pi electrons are completely conjugated, and a group derived from an aromatic hydrocarbon refers to a structure in which an aromatic hydrocarbon or a cyclic aliphatic hydrocarbon is condensed with an aromatic hydrocarbon. . Additionally, in the present invention, the aryl group is intended to include a monovalent group in which two or more aromatic hydrocarbons or derivatives of aromatic hydrocarbons are linked together. The aryl group is not particularly limited, but has 6 to 60 carbon atoms; 6 to 50; 6 to 30; 6 to 25; 6 to 20; 6 to 18; 6 to 15; 6 to 13; Or preferably 6 to 12, and may be a monocyclic aryl group or a polycyclic aryl group.

In the present invention, the heteroaryl group is an aromatic ring group containing one or more of N, O, P, S, Si, and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but may have 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 2 to 30 carbon atoms. Examples of the heteroaryl group include pyridine group, pyrrole group, pyrimidine group, pyridazine group, furan group, thiophene group, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, etc. However, it is not limited to these.

In the present invention, the ring is a hydrocarbon ring; Or it means a heterocycle. The hydrocarbon ring may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic. The description of the heteroaryl group above may be applied to the hetero ring.

In the present invention, room temperature may be 10°C to 30°C. As a specific example, room temperature may be 20°C.

In the present invention, the solid content of the composition means components excluding the solvent.

<Adhesive composition>

One embodiment of the present invention includes a first monomer represented by the following formula (1); second monomer; acrylic acid; and a crosslinking agent, wherein the second monomer is an acrylic monomer.

[Formula 1]

In Formula 1,

R1 is a six-membered ring containing substituted or unsubstituted N and O.

<First monomer>

According to one embodiment of the present invention, R1 is a six-membered ring containing substituted or unsubstituted N and O.

According to one embodiment of the present invention, the six-membered ring containing substituted or unsubstituted N and O is a substituted or unsubstituted morpholine group.

According to a preferred embodiment of the present invention, the six-membered ring containing substituted or unsubstituted N and O is substituted or unsubstituted acryloylmorpholine.

According to a preferred embodiment of the present invention, the six-membered ring containing substituted or unsubstituted N and O is acryloylmorpholine.

According to one embodiment of the present invention, the first monomer is substituted or unsubstituted acryloylmorpholine.

According to a preferred embodiment of the present invention, the first monomer is acryloylmorpholine.

<Second monomer>

According to one embodiment of the present invention, the second monomer is represented by the following formula (2).

[Formula 2]

In Formula 2,

R2 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; Or it is a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms.

According to one embodiment of the present invention, R2 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; Or it is a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms.

According to one embodiment of the present invention, R2 is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; Or it is a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms.

According to one embodiment of the present invention, R2 is an alkyl group having 1 to 10 carbon atoms; Or it is an alkoxy group having 1 to 2 carbon atoms substituted with an alkyl group.

According to one embodiment of the present invention, R2 is an alkyl group with 8 carbon atoms or an alkoxy group with 1 to 2 carbon atoms substituted with a methyl group.

According to one embodiment of the present invention, R2 is an ethoxy group substituted with a 2-ethylhexyl group or a methyl group.

According to one embodiment of the present invention, the second monomer is n-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n -Pentyl (meth)acrylate, isopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, It is any one or a mixture of two or more selected from the group consisting of isononyl (meth)acrylate and 2-methoxyethyl acrylate.

According to one embodiment of the present invention, the second monomer is any one or a mixture of two or more selected from the group consisting of 2-ethylhexyl acrylate and 2-methoxyethyl acrylate.

According to a preferred embodiment of the present invention, the adhesive composition may include a (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton. The (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton may refer to a polyalkylene glycol copolymer ester copolymer containing a polyalkylene glycol skeleton.

According to a preferred embodiment of the present invention, the polyalkylene glycol skeleton may be represented by Formula 1 below.

[Formula 1]

HO-[(CH ₂ )nO-]mH

In Formula 1,

m can be 2 to 20,

The n is the repeating number of the alkylene group in Formula 1, and may be 2 to 4.

The (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton may be derived from polyalkylene glycol having a number average molecular weight of 100 to 1,000, preferably 200 to 900, and more preferably 200 to 500. If the above numerical range is exceeded, the acrylic acid ester monomer exists in a wax phase, which may reduce water dissociation after polymerization. When the above numerical range is satisfied, reactivity and reaction stability are excellent when preparing the composition, water dissociation characteristics and adhesion characteristics can be improved, and adhesion reliability can be improved.

The (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton can be prepared by copolymerizing a polyalkylene glycol component, a diol component, and a dicarboxylic acid component.

The polyalkylene glycol component includes poly pentamethylene glycol, poly hexamethylene glycol (PHMG), polyephthamethylene glycol, poly octamethylene glycol, and poly decamethylene glycol (PDMG).

The polyalkylene glycol component can be used by mixing two or more of the same or different substances.

The diol components include ethylene glycol, diethylene glycol, polyethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butylene glycol (1, 4-BG), and 1, 5-pentanediol. , linear aliphatic diols such as neopentyl glycol, 1,6-hexanediol, and 1,8-octanediol; Cyclic aliphatic diols such as 1,2-cyclohexane diol, 1,4-cyclohexane diol (1,4-CHDO), and 1,4-cyclohexanedimethanol (1,4-CHDM); aromatic diols such as xylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)sulfone; Diols derived from plant raw materials such as isosorbido, isomannido, isoizetto, and erythritan can be mentioned.

The dicarboxylic acid components include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecarboxylic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid and their ester-forming derivatives; Fatty cyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, and 1,4-cyclohexanedicarboxylic acid, and fats such as dimethyl 1,4-cyclohexanedicarboxylic acid (1,4-DMCD) Ester-forming derivatives of cyclic dicarboxylic acids; Terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylene dioxy dicarboxylic acid, 4, 4'-diphenyldicarboxylic acid, 4, 4'-diphenyl ether dicarboxylic acid, Aromatic dicarboxylic acids such as 4, 4'-diphenyl ketone dicarboxylic acid, 4, 4'-diphenoxyethane dicarboxylic acid, 4, 4'-diphenyl sulfone dicarboxylic acid, and 2, 6-naphthalene dicarboxylic acid. and ester-forming derivatives of aromatic dicarboxylic acids such as carboxylic acid and terephthalic acid methyl ester (DMT).

<Initiator>

The adhesive composition according to an exemplary embodiment of the present invention includes an initiator. The initiator may include a photopolymerization initiator, a thermal polymerization initiator, and the like. Among these, a photopolymerization initiator may be preferable because curing can be easily performed and damage to the adherend is minimal.

According to one embodiment of the present invention, the photopolymerization initiator may be activated, for example, by irradiating ultraviolet rays with a wavelength of 200 nm to 410 nm. Such photopolymerization initiators include, for example, acetophenone derivative compounds, benzoin ether compounds, ketal derivative compounds, phosphine oxide derivative compounds, bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, and Michler. Ketones, chlorothioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenylketone, 2-hydroxymethylphenylpropane, etc. are mentioned. Examples of the acetophenone derivative compound include methoxyacetophenone. Examples of the benzoin ether-based compounds include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivative compounds include benzyl dimethyl ketal, acetophenone diethyl ketal, and the like. These photopolymerization initiators may be used individually, or two or more types may be used together.

According to an exemplary embodiment of the present invention, the thermal polymerization initiator includes one that is decomposed by heat and generates active radicals that initiate polymerization and curing. Specifically, for example, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide. oxide, paramenthan hydroperoxide, and di-t-butyl peroxide. Among these thermal polymerization initiators, commercially available ones are not particularly limited, but for example, Perbutyl D, Perbutyl H, Perbutyl P, and Perpenta H (all manufactured by Nichiyu Corporation) are preferable. These thermal polymerization initiators may be used individually, or two or more types may be used together.

According to one embodiment of the present invention, the initiator is 0.1 to 10 parts by weight based on 100 parts by weight of solid content of the adhesive composition; 0.1 to 5 parts by weight; Or 0.1 to 2 parts by weight. In a preferred example, the initiator is included in an amount of 1 part by weight based on 100 parts by weight of solid content of the adhesive composition.

<Cross-linking agent>

The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention includes a crosslinking agent. Examples of the crosslinking agent include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol. Epoxy-based compounds including diglycidyl ether and resorcin diglycidyl ether, tetramethylene diisocyanate, hexamethylene diisocyanate, and toluene diisocyanate of trimethylolpropane. Isocyanate-based compounds including triadducts and polyisocyanates, trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylprop Cypionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), Aziridine-based compounds, epoxy, including N,N'-toluene-2,4-bis(1-aziridinecarboxyamide), trimethylolpropane-tri-β-(2-methylaziridine)propionate, etc. These include melamine-based compounds including hexamethoxymethylolmelamine, metal chelate-based compounds, and the like. One type of crosslinking agent may be used individually, or multiple types may be used in combination.

According to one embodiment of the present invention, the crosslinking agent is a metal chelate-based compound.

According to a preferred embodiment of the present invention, the crosslinking agent is an aluminum chelate-based compound. As an example, the crosslinking agent is CAS No. 13963-57-0 can be used.

The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention can improve cohesion, peeling performance, adhesion, etc. of the pressure-sensitive adhesive component by including the crosslinking agent.

According to one embodiment of the present invention, the crosslinking agent is 0.1 to 10 parts by weight based on 100 parts by weight of solid content of the adhesive composition; 0.1 to 5 parts by weight; Or 0.1 to 2 parts by weight. In a preferred example, the crosslinking agent is included in an amount of 1 part by weight based on 100 parts by weight of solid content of the adhesive composition.

<Neutralizer>

The adhesive composition according to an exemplary embodiment of the present invention further includes a neutralizing agent. The neutralizing agent includes metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; Carbonates such as sodium carbonate and potassium carbonate; Hydrogencarbonate salts such as sodium hydrogencarbonate and potassium hydrogencarbonate; Metal alkoxides such as sodium methoxide and potassium butoxide; organic metals such as butyllithium; potassium silanolate; These include ammonia gas, ammonia water, and nitrogen compounds such as methylamine, trimethylamine, and triethylamine.

According to a preferred embodiment of the present invention, the neutralizing agent is an aqueous potassium hydroxide solution. As a specific example, the neutralizing agent is a 20% to 80% aqueous potassium hydroxide solution. In a more specific example, the neutralizing agent is a 50% aqueous potassium hydroxide solution.

According to one embodiment of the present invention, the neutralizer is included in an amount of 1 to 10 parts by weight based on 100 parts by weight of solid content of the adhesive composition. In a preferred example, the crosslinking agent is included in an amount of 1 to 5 parts by weight based on 100 parts by weight of solid content of the adhesive composition.

<Adhesive composition>

According to one embodiment of the present invention, the solvent may be one or more mixed solvents selected from methyl acetate, ethyl acetate, butylacetate, toluene, xylene, benzene, acetone, and methyl ethyl ketone (MEK), but is limited thereto. It doesn't work. At this time, the weight part of the solvent is not particularly limited, and may be used in an amount that can sufficiently dissolve or contain the substance to be dissolved or the substance to be added to the solvent.

According to one embodiment of the present invention, the weight ratio of the first monomer and the second monomer is 1:99 to 25:75. When the first monomer is included in excess of 25 parts by weight based on the total weight ratio of the first monomer and the second monomer, which is 100 parts by weight, there is a disadvantage in that water dissociability is not achieved because the required adhesive strength is greatly exceeded.

According to an exemplary embodiment of the present invention, the acrylic acid is included in an amount of 2 to 40 parts by weight based on 100 parts by weight of the first monomer.

According to a preferred embodiment of the present invention, the acrylic acid is included in an amount of 2 to 15 parts by weight based on 100 parts by weight of the first monomer.

According to another embodiment of the present invention, the acrylic acid is included in an amount of 2 to 40 parts by weight based on the total weight of the first monomer and the second monomer.

According to another embodiment of the present invention, the adhesive composition further includes a second monomer represented by Formula 2, and the acrylic acid is present in an amount of 2 to 2 parts by weight based on the total weight of the first monomer and the second monomer. Contains 40 parts by weight.

According to one embodiment of the present invention, the viscosity of the adhesive composition is 2500 cps to 15000 cps.

According to a preferred embodiment of the present invention, the viscosity of the adhesive composition is 2500 cps to 12000 cps.

<Measurement of SUS adhesion, heat-resistant cohesion and vortex>

In the present invention, SUS adhesion (g/inch) was measured by the following method. A 1 Х 1 inch cut piece of the adhesive tape was placed on each of the adherends (SUS board and PE board) and pressed back and forth once using a 2 kg roller. The adhesive tape pressed to the adherend was stretched in a 180° direction for 24 hours after 20 minutes, and the adhesive force required to peel the adhesive tape from the adherend was measured using a tensile tester.

According to one embodiment of the present invention, the SUS adhesive strength of the adhesive composition or the adhesive processed product to be described later is 50 g/inch to 1,500 g/inch.

In the present invention, heat-resistant cohesion (mm) was measured by the following method. A 1 Х 1 inch cut piece of the adhesive tape was placed on each adherend (SUS board and PE board) and pressed using a 2 kg roller. The adhesive tape pressed to the adherend was placed vertically, a load of 1 kg was applied to the bottom of the sample, and the length was measured after 1 hour in an 80°C environment.

In the present invention, vortex (No) was measured by applying 30° to the J.dow method.

According to one embodiment of the present invention, the vortices of the adhesive composition or the adhesive processed product to be described later are #1 to #19.

<Water dissociation>

According to one embodiment of the present invention, the water dissociability of the adhesive composition is evaluated according to whether the adhesive remains when peeling off the bonded paper using the adhesive composition applied to one side of the nonwoven, aged, washed and filtered. can be

According to one embodiment of the present invention, the water dissociability of the adhesive composition is measured by applying the adhesive composition to one side of the nonwoven, aging it, washing and filtering, and measuring the weight (g) of the adhesive when peeling the bonded paper. am.

According to one embodiment of the present invention, the thickness of the nonwoven is 20 ㎛ to 40 ㎛.

According to a preferred embodiment of the present invention, the thickness of the nonwoven is 30 ㎛.

According to one embodiment of the present invention, the adhesive composition is applied to one surface of the nonwoven to a thickness of 40 ㎛ to 70 ㎛.

According to a preferred embodiment of the present invention, the adhesive composition is applied to one surface of the nonwoven to a thickness of 60 ㎛.

According to one embodiment of the present invention, the adhesive composition is applied to one surface of the nonwoven and aged at a temperature of 30°C to 50°C.

According to a preferred embodiment of the present invention, the adhesive composition is applied to one surface of the nonwoven and aged at a temperature of 40°C.

According to one embodiment of the present invention, the adhesive composition is applied to one surface of the nonwoven and aged for 12 to 48 hours.

According to a preferred embodiment of the present invention, the adhesive composition is applied to one surface of the nonwoven and aged for 24 hours.

According to one embodiment of the present invention, the aged film is cut and then put into water. At this time, the temperature of the water may be room temperature.

According to one embodiment of the present invention, the aged film can be cut into sizes of 5 x 5 mm ² to 20 x 20 mm ² .

According to a preferred embodiment of the present invention, the aged film can be cut into a size of 10 x 10 mm ² .

According to one embodiment of the present invention, 5 g to 20 g of the cut film is added to water.

According to a preferred embodiment of the present invention, 10 g of the cut film is added to water.

According to one embodiment of the present invention, the cut film is put into 300 cc to 1000 cc of water.

According to a preferred embodiment of the present invention, the cut film is put into 500 cc of water.

According to one embodiment of the present invention, the film added to the water is stirred through a mixer.

According to a preferred embodiment of the present invention, the film added to the water is stirred through a Homogenizer Chuck-Type size 1 mm to 8 mm (HT5) low viscosity mixer. At this time, the stirring may be performed for (5,000 rpm to 50,000 rpm)* (5 to 60 minutes). Preferably, it may be performed at 10,000 rpm * 10 minutes.

According to one embodiment of the present invention, the stirred material can be impeller washed with water. The washing may be performed 2 to 10 times. Preferably, it can be carried out three times.

According to one embodiment of the present invention, the washed material can be filtered.

According to a specific embodiment of the present invention, the finely chopped material can be filtered through a 300 mesh filter net.

According to one embodiment of the present invention, paper can be laminated using the filtered material. Specifically, the filtered material can be applied to one side of paper and laminated with other paper.

According to one embodiment of the present invention, the paper may be A4 paper or the like.

According to an exemplary embodiment of the present invention, the laminated papers may be the same or different from each other.

According to one embodiment of the present invention, the laminated paper can be dried.

According to a specific embodiment of the present invention, the laminated paper can be dried at a temperature of 80°C to 200°C.

According to a preferred embodiment of the present invention, the laminated paper can be dried at a temperature of 120°C.

According to one specific embodiment of the present invention, the laminated paper can be dried for 10 to 60 minutes.

According to a preferred embodiment of the present invention, the laminated paper can be dried for 20 minutes.

According to one embodiment of the present invention, the weight of the adhesive can be measured when peeling off the dried laminated paper (can be called a sample, etc.). The measured weight of the adhesive can be used to evaluate water dissociability.

According to one embodiment of the present invention, the water dissociability of the adhesive composition is achieved by applying 60 ㎛ of the adhesive composition to one side of the 30 ㎛ nonwoven, aging it at a temperature of 43 ° C. for 24 hours, then washing and filtering. It can be evaluated based on whether adhesive remains when peeling off the paper. Specifically, if no or almost no adhesive remains, the water dissociability can be evaluated as very good or excellent, if a small amount of the adhesive remains, the water dissociability can be evaluated as average, and if a large amount of the adhesive remains, the water dissociability can be evaluated as average. It can be evaluated as defective.

According to another embodiment of the present invention, the Probe Tack value of the dried laminated paper (can be called a sample, etc.) can be measured and used to quantify the water dissociability. Specifically, if the Probe Tack value is 0 to 5 g, the water dissociability can be considered excellent (o), if it is 6 to 30 g, it can be said to be average (△), and if it is more than 30 g, it can be said to be poor (x). For reference, the method for evaluating the water dissociability of the adhesive composition may be a water dissociation measurement method used in the market or subjective data, and may be less accurate.

According to one embodiment of the present invention, the Probe Tack value is measured by the following method, but is not limited thereto. The following Probe Tack measurement method refers to the information described in standard ASTM D2979.

[Probe Tack measurement method]

A film is prepared by applying the adhesive composition (or the sample, etc.) to a thickness of 50 to 60 μm on a 25 to 30 μm PET and aging it for 24 hours at 40 to 45 ° C. (preferably 43 ° C.). After cutting into 20 x 20mm sizes, 3 to 5 specimens are placed in 300g of water at 80°C. After stirring at 300 rpm for 15 minutes, 30 minutes, 60 minutes, and 90 minutes, respectively, take out the specimen. After sufficiently drying the specimen in an oven at 120°C for more than 5 minutes, it is measured using Probe Tack equipment. The Probe Tack is measured 5 times and the average is calculated.

According to an exemplary embodiment of the present invention, the adhesive composition has excellent heat-resistant cohesion, and thus has the effect of preventing freezing in winter.

As a specific example, the heat-resistant cohesion is measured by the following method, but is not limited thereto.

[Method for measuring heat-resistant cohesion]

A 1 Х 1 inch cut piece of the adhesive composition or an adhesive processed product (e.g. tape) containing the same is placed on an adherend (SUS plate and PE plate) and pressed using a 2 kg roller. The adhesive tape pressed to the adherend is placed vertically, a load of 1 kg is applied to the bottom of the sample, and the length is measured after 1 hour in an 80°C environment. At this time, the longer the measured length, the greater the heat-resistant cohesion.

<Adhesive processed products>

One embodiment of the present invention provides an adhesive processed product containing the above-described adhesive composition.

According to one embodiment of the present invention, the adhesive processed product may be a tape, label, sheet, double-sided tape, etc., but is not limited thereto, and includes all those used for various purposes requiring adhesiveness.

According to an exemplary embodiment of the present invention, Figure 1 shows an adhesive processed product according to an exemplary embodiment of the present invention. Specifically, Figure 1 shows an adhesive tape 100 according to an exemplary embodiment of the present invention, and an adhesive layer 120 is formed on one surface of the base layer 110.

According to one embodiment of the present invention, Figure 2 shows an adhesive processed product according to another embodiment of the present invention. Specifically, Figure 2 shows an adhesive tape 101 according to an exemplary embodiment of the present invention, in which an adhesive layer 121 is formed on one side of the base layer 110, and an adhesive layer 121 is formed on the other side of the base layer 110. Another adhesive layer 122 is formed. As a specific example, Figure 2 may illustrate a double-sided tape, but is not limited thereto.

According to an embodiment of the present invention, the adhesive processed product includes a base layer and an adhesive layer, and the adhesive layer includes the adhesive composition according to an embodiment of the present invention or is manufactured using the adhesive composition.

According to one embodiment of the present invention, the thickness of the adhesive layer can be appropriately adjusted by a person skilled in the art in consideration of water decomposability, adhesive strength, productivity, etc. of the adhesive processed product. For example, the thickness of the adhesive layer is 5 μm to 50 μm, preferably 5 μm to 40 μm, and more preferably 10 μm to 30 μm, but is not limited to the above-exampled thickness.

According to one embodiment of the present invention, the material of the base layer is not particularly limited, and considering the purpose of the adhesive processed product, materials such as paper, non-woven, and resin film known to those skilled in the art may be used. For example, in order to expect transparency of adhesive processed products, a transparent resin film (specifically, transparent PET FILM, etc.) can be used as a material for the base layer.

According to an exemplary embodiment of the present invention, the adhesive processed product can be manufactured by applying the adhesive composition according to an exemplary embodiment of the present invention to one side of the base layer. Specifically, the adhesive processed product can be manufactured by applying the adhesive composition to one side of the base layer, drying the applied adhesive composition, and crosslinking each component to form an adhesive layer.

According to one embodiment of the present invention, the application method is not particularly limited, and known methods such as the roll coater method, reverse roll coater method, gravure roll method, bar coating method, comma coater method, and die coater method can be used. there is.

According to one embodiment of the present invention, the drying temperature and drying time are not particularly limited, and may be dried at 80 ℃ to 200 ℃ for 10 seconds to 10 minutes, preferably at 80 ℃ to 170 ℃ for 15 seconds to 10 minutes. Allow to dry for 5 minutes. However, depending on the purpose of the adhesive processed product, the drying temperature and drying time can be appropriately adjusted by a technician in the art.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1-1

The reaction device includes 10 parts by weight and 90 parts by weight of the first monomer (ACMO) and the second monomer (MEA), respectively, and 5 parts by weight of acrylic acid based on 100 parts by weight, which is the sum of parts by weight of the first and second monomers, and an adhesive. Based on 100 parts by weight of solid content of the composition, 0.2 parts by weight of polymerization initiator 2.2-Azobisisobutyronitrile (AIBN) was added and reacted at 65°C for 6 hours. After sufficiently cooling to below 30°C, 1 part by weight of chelate crosslinker GC-10 and 3 parts by weight of 50% potassium hydroxide aqueous solution as a neutralizer were added to 100 parts by weight of solid content of the adhesive composition and stirred for 1 hour to obtain adhesive composition 1. The weight average molecular weight of the acrylic polymer included in the prepared adhesive composition is 700,000 g/mol.

An adhesive processed product was prepared by applying 60 ㎛ of the prepared adhesive composition to a 30 ㎛ nonwoven and aging it for 24 hr at a temperature of 43°C. The adhesive processed product was cut to a size of 10 x 10 mm, and 15 g of the sample was added to 500 cc of room temperature water. Homogenizer Chuck-Type size 1~8 mm (HT5) Using a low-viscosity mixer, the mixture was stirred at 10,000 rpm x 10 minutes, and the impeller was washed three times with 50 cc of water. After filtering through a 300 mesh filter, it was evenly applied to A4 paper and laminated. The water dissociability of samples dried at 120°C for 20 minutes was measured. In order to quantify the water dissociability, 0 to 5 g was indicated as excellent water dissociability (o), 6 to 30 g was indicated as average (△), and the rest were indicated as poor (x) through the Probe Tack value of the sample. The results are listed in Table 1 below. Additionally, the Probe Tack values are listed in Table 2 below.

Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3

The same method as Example 1-1 was performed, except that the composition of Example 1-1 was used as shown in Table 1 below, and the results are shown in Table 1 below.

Example composition MEA
(part by weight) 2-EHA
(part by weight) ACMO
(part by weight) M5300
(part by weight) N.NDMA
(part by weight) AA
(%) water dissociation
(g) 1-1 One 90 - 10 - - 5 o 1-2 2 92.5 - 7.5 - - 5 o 1-3 3 95 - 5 - - 5 o 1-4 4 90 - 10 - - 2 o Comparative example composition MEA
(part by weight) 2-EHA
(part by weight) ACMO
(part by weight) M5300
(part by weight) N.NDMA
(part by weight) AA
(%) water dissociation
(g) 1-1 11 - 90 - 10 - - x 1-2 12 - 80 - 20 - - x 1-3 13 - 70 - 30 - - x

o: Excellent, x: Poor

Example composition Probe Tack (g) 0 minutes 15 minutes 30 minutes 60 minutes 90 minutes 1-1 One 312 0 0 0 0 1-2 2 205 0 0 0 0 1-3 3 190 0 0 0 0 1-4 4 230 0 0 0 0 Comparative example composition Probe Tack figures 0 minutes 15 minutes 30 minutes 60 minutes 90 minutes 1-1 11 180 170 170 160 150 1-2 12 260 255 250 250 245 1-3 13 330 320 310 310 300

In Table 1, MEA is 2-methoxyethyl acrylate, 2-EHA is 2-ethylhexyl acrylate, ACMO is acryloylmorpholine, and M5300 is ω-carboxy-polycaprolactone monoacrylate. (n=2), N.NDMA is N,N-dimethylacrylamide, and AA is acrylic acid.

According to Table 1, Examples 1-1 to 1-4, which contain 2-methoxyethyl acrylate and acrylic acid within the range of each weight part according to the present invention, have excellent water damage compared to Comparative Examples 1-1 to 1-3. It can be confirmed that it has reasonableness. Specifically, Examples 1-1 to 1-4 had very excellent water dissociation properties with Probe Tack values of 0 g over 15 minutes, while Comparative Examples 1-1 to 1-3 had Probe Tack values of 0 g over 15 minutes or more. The values are all over 170 g, and in particular, the Probe Tack values over 90 minutes are all over 150 g, showing that water dissociation is poor. In other words, according to the present invention, when 2-methoxyethyl acrylate and acrylic acid are included within the range of each weight part, water dissociability is excellent and thus has environmentally friendly characteristics, whereas when it is outside the weight range suggested by the present invention, water dissociation property is excellent. Due to this defect, it does not have eco-friendly characteristics, and it is judged that additional processes such as separation and dissolution will be necessary to recycle it.

100: adhesive tape
101: adhesive tape
110: base layer
120, 121, 122: Adhesive layer

Claims (12)

A first monomer represented by the following formula (1); second monomer; acrylic acid; corrector; And a cross-linking agent,
The second monomer is an acrylic monomer represented by the following formula (2),
The weight ratio of the first monomer and the second monomer is 1:99 to 25:75,
An adhesive composition in which the content of the neutralizing agent is 1 to 10 parts by weight based on 100 parts by weight of solid content of the adhesive composition:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R1 is a six-membered ring containing substituted or unsubstituted N and O,
R2 is a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms. In claim 1,
The adhesive composition wherein the first monomer is acryloylmorpholine. delete In claim 1,
An adhesive composition wherein the content of acrylic acid is 2 to 40 parts by weight based on 100 parts by weight of the total of the first monomer and the second monomer. delete In claim 1,
The second monomer is n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, iso Pentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate and 2 -An adhesive composition that is one or a mixture of two or more selected from the group consisting of methoxyethyl acrylate. delete In claim 1,
The neutralizing agent includes lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium methoxide, potassium butoxide, butyllithium, potassium silanolate, ammonia gas, and methylamine. , an adhesive composition that is one or a mixture of two or more selected from the group consisting of trimethylamine, triethylamine, and aqueous solutions thereof. delete In claim 1,
The adhesive composition wherein the crosslinking agent is an aluminum chelate-based compound. In claim 1,
An adhesive composition in which the content of the crosslinking agent is 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of solid content of the adhesive composition. An adhesive processed product comprising the adhesive composition according to any one of claims 1, 2, 4, 6, 8, 10, and 11.