KR102593925B1 - Adhesive composition and manufacturing method for same - Google Patents

Abstract

The present specification includes an acrylic monomer containing a functional group; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; and an unsaturated carboxylic acid-based monomer, wherein the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 15 parts by weight or more based on 100 parts by weight of the acrylic monomer containing the functional group, and the same. Manufacturing method is provided.

Description

Adhesive composition and manufacturing method thereof {ADHESIVE COMPOSITION AND MANUFACTURING METHOD FOR SAME}

This specification claims the benefit of the filing date of application No. 10-2021-0061358 filed with the Korean Intellectual Property Office on May 12, 2021, the contents of which are incorporated into this specification.

This specification relates to an adhesive composition and a method for producing the same.

Water-dissociable adhesive is an environmentally friendly adhesive that uses a water-soluble polymer that can dissolve in water at room temperature and has the property of being completely decomposed and dissociated in water. In general, water-dissociable adhesives (neutralized type) are very sensitive to humidity due to the characteristic of dissociation and decomposition by water, so when exposed to moisture, the adhesive properties such as irregular deformation of the adhesive surface or rapid changes in heat resistance and adhesive strength may occur. Had a problem with deterioration.

Republic of Korea Patent Publication No. 10-2010-0086716 (2010.08.02)

One embodiment of the present invention provides an adhesive composition with improved adhesion and water dissociability and a method for manufacturing the same.

One embodiment of the present invention includes an acrylic monomer containing a functional group;

(meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; and

Contains unsaturated carboxylic acid monomers,

Provided is an adhesive composition in which the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 15 parts by weight or more based on 100 parts by weight of the acrylic monomer containing the functional group.

In addition, other embodiments of the present specification include an acrylic monomer containing a functional group; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; And preparing an acrylic monomer composition containing an unsaturated carboxylic acid monomer,

A method for producing the above-described adhesive composition is provided, wherein the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 15 parts by weight or more based on 100 parts by weight of the acrylic monomer containing the functional group.

The pressure-sensitive adhesive composition prepared by the manufacturing method according to an exemplary embodiment of the present invention has the effect of maintaining excellent water dissociation properties without being significantly affected by temperature changes.

The adhesive composition manufactured by the manufacturing method according to an exemplary embodiment of the present invention has the effect of maintaining excellent adhesive performance without being significantly affected by temperature changes.

Hereinafter, this specification will be described in detail.

One embodiment of the present invention includes an acrylic monomer containing a functional group; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; and an unsaturated carboxylic acid monomer, and the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 15 parts by weight or more based on 100 parts by weight of the acrylic monomer containing the functional group. do.

The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention includes an acrylic monomer containing a functional group; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; And by including an unsaturated carboxylic acid monomer, there is an effect of improving adhesive properties and water dissociability.

In addition, the adhesive composition according to an exemplary embodiment of the present invention has the effect of improving adhesive properties and water dissociability by adjusting the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton within the above range.

In the present specification, the acrylic monomer composition is a composition containing an acrylic monomer and may refer to a state before neutralization.

In the present specification, the (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton may mean a polyalkylene glycol copolymer ester copolymer containing a polyalkylene glycol skeleton.

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, and water dissociation characteristics and adhesion characteristics 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.

Examples of the polyalkylene glycol component include polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMG), and polyhexamethylene ether glycol (PHMG).

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).

In one embodiment of the present invention, the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton may be 15 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the acrylic monomer containing the functional group. Alternatively, it may be 20 parts by weight or more and 400 parts by weight or less, or 20 parts by weight or more and 300 parts by weight or less, based on 100 parts by weight of the acrylic monomer containing the functional group. When the above numerical range is satisfied, reactivity or reaction stability is excellent when preparing the composition, and water dissociation characteristics and adhesion characteristics can be improved.

In one embodiment of the present invention, the unsaturated carboxylic acid-based monomer controls the softness and hardness by controlling the degree of internal crosslinking of the polymer, allowing the adhesive composition to achieve appropriate viscoelastic properties.

In one embodiment of the present invention, the unsaturated carboxylic acid monomer is acrylic acid, fumaric acid, maleic acid, itaconic acid, and citraconic acid. , mesaconic acid, glutaconic acid, and allylmalonic acid, and preferably acrylic acid.

In one embodiment of the present invention, the content of the unsaturated carboxylic acid monomer can be adjusted by considering the content of the acrylic monomer containing the above-mentioned functional group and the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton, If too much is used, the aging peeling strength may increase even when stored at high temperatures for a long time, and if too little is used, the adhesive strength may decrease.

In one embodiment of the present invention, the acrylic monomer containing the functional group may include a (meth)acrylic acid ester monomer having an alkyl group. At this time, the (meth)acrylic acid ester monomer having the alkyl group may be referred to as the first (meth)acrylic acid ester monomer, and the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton may be referred to as the second (meth)acrylic acid ester. It can be referred to as a monomer.

In one embodiment of the present invention, the acrylic monomer containing the functional group may include a (meth)acrylic acid ester monomer having a C1 to C14 alkyl group.

In one embodiment of the present invention, the (meth)acrylic acid ester monomer is methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n- Butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate , isooctyl (meth)acrylate, isononyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate. The above mixture can be used, but is not necessarily limited thereto.

In one embodiment of the present invention, the acrylic monomer containing the functional group is not particularly limited as long as it can crosslink the acrylic polymer, and can be appropriately selected as needed. The functional group is preferably one or two or more selected from the group consisting of an epoxy group, carboxyl group, hydroxyl group, and amide.

Acrylic monomers containing the functional group include hydroxyalkyl (meth)acrylate, hydroxyalkylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, and 2-hydroxypropylene glycol Any one or two or more selected from the group consisting of (meth)acrylates may be used, but are not limited thereto.

In one embodiment of the present invention, the adhesive composition may further include an organic solvent. The organic solvent is preferably selected from ketone, ester, alcohol, and aromatic solvents, and more preferably acetone, ethanol, or a mixture thereof. For example, ethyl acetate, ethyl alcohol, isopropyl alcohol, or mixtures thereof can be used.

In one embodiment of the present invention, the organic solvent may have a lower freezing point than water.

In one embodiment of the present invention, the adhesive composition may further include one or more additives selected from the group consisting of molecular weight regulators, crosslinking agents, initiators, thickeners, dispersants, ultraviolet stabilizers, antioxidants, anti-corruption agents, buffers, and fillers. You can.

The molecular weight regulator acts as a chain transfer agent (CTA) during the polymerization reaction of the resin, and specifically attaches to the end of the molecule to transfer the radical to another location and create a termination reaction. The molecular weight regulator is, for example, alcohol, ether, thioether, dithiocarbonate, natroxide, mercaptan, TEMPO, lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mer Consisting of n-octyl mercaptan, glycidyl mercaptan, mercapto acetic acid, 2-mercapto ethanol, thioglycolic acid, 2-ethylhexyl thioglycolic acid, and 2,3-dimercapto-1-propanol. It may be one or more types selected from the group.

The crosslinking agent may be an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, or a metal chelate crosslinking agent, but is not limited thereto. Isocyanate crosslinking agents include polyfunctional isocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate, or naphthalene diisocyanate, or the above polyfunctional Examples include compounds obtained by reacting an isocyanate compound with a polyol compound such as trimethylol propane, and epoxy crosslinking agents include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, One or more selected from the group consisting of N',N'-tetraglycidyl ethylenediamine and glycerin diglycidyl ether may be exemplified, and the aziridine crosslinking agent is N,N'-toluene-2,4-bis ( 1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1-(2-methyl One or more selected from the group consisting of aziridine) and tri-1-aziridinylphosphine oxide may be exemplified, but are not limited thereto. In addition, examples of the metal chelate-based crosslinking agent include compounds in which a multivalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and/or vanadium is coordinated with acetylacetone or ethyl acetoacetate, etc. It is not limited.

The initiator can be used, for example, in the group of azo-based, peroxide-based, hydroperoxide-based and perester-based, specifically, for example, 2,2′-azo-bis(isobutylnitrile), dimethyl 2, the azo series of 2'-azo-bis(isobutylate), azo-bis(diphenylmethane) and 4,4'-azo-bis(4-cyanopentanoic acid); peroxides of hydrogen peroxide, benzoyl peroxide, cumyl peroxide, tert-butyl peroxide, cyclohexanone peroxide, glutaric acid peroxide, lauroyl peroxide and methyl ethyl ketone peroxide; Hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide; peracids of peracetic acid, perbenzoic acid, cannium persulfate and ammonium persulfate; Any one or a mixture of two or more selected from the group of diisopropyl percarbonate peresters can be used, but is not limited thereto. Preferably, 2,2'-azo-bis(isobutylnitrile) can be used.

The surfactant may be used to generate initial particles during a polymerization reaction, control the size of the generated particles, and stabilize the particles. These surfactants are composed of hydrophilic and lipophilic groups, and are divided into anionic, cationic, and nonionic surfactants. Anionic and nonionic surfactants are mainly used, and they are mixed together to improve mechanical and chemical stability. Sometimes it happens. The surfactant is, for example, sodium polyoxyethylene alkyl ether sulfate (varying types depending on the EO group), diphenyl oxide disulfonate, and sodium lauryl sulfate. , sodium alkyldiphenyloxide disulfonate, or sodium methylallyl sulfonate, etc., but is not limited thereto. Additionally, these may be used alone or in combination of two or more types. For example, a surfactant with a phenyl group can easily attract nonpolar monomers, and a surfactant with a methyl allyl group can accommodate many monomers because its molecules are not large.

In one embodiment of the present invention, the content of the additive can be adjusted appropriately as needed, and for example, it can be used in an amount of 0.1 to 5% by weight based on the total weight of the composition.

In one embodiment of the present invention, the Probe tack test result of the adhesive composition after immersing it in water at 80°C and drying may be 1 gf or less. Specifically, it may be 0.5gf or less and 0.1gf or less. A low ProbeTack adhesion test result means that the adhesive composition has excellent water dissociability, and the lower the result, the better, so the lower limit is not particularly limited.

In one embodiment of the present invention, the adhesive composition may have a viscosity of 1,000 to 9,000 cPs at 25°C. When the above range is satisfied, fairness is improved and storage stability is excellent.

In one embodiment of the present invention, the adhesive composition may have a solid content of 30% to 80%, or 40% to 60%. When the above range is satisfied, fairness is improved and storage stability is excellent.

The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention has excellent water dissociation properties at room temperature and high temperature water dissociation properties. The high temperature may mean higher than 25°C or higher than 80°C. The room temperature may be 25°C, and the high temperature may be 80°C. For the room temperature water dissociability and high temperature water dissociability tests, adhesive composition specimens can be prepared and tested. Specifically, it was applied to a thickness of 20-100㎛ on a non-woven fabric and dried at about 40°C for 24 hours. The manufactured specimen is cut into a size of 10mm x 10mm and then placed in 500cc of water. After stirring for 10 minutes at a speed of about 10,000 rpm using a homomixer, wash the impeller three times with 50 cc of water. After filtering through a 300 mesh filter, apply evenly to paper (A4 paper) and laminate. Afterwards, it is dried at 120°C for 20 minutes and then peeled to check the presence or absence of transfer and adhesive.

The adhesive composition according to an exemplary embodiment of the present invention has the effect of not significantly changing adhesive strength at low and high temperatures. A SUS substrate can be used as the substrate for measuring the adhesive force, and the adhesive force can be measured and compared at different temperatures. The adhesive strength is measured by placing a 1 After tensioning at a speed of 300 mm/min, the adhesive force required to peel the adhesive tape from the adherend can be measured using a tensile tester.

The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention has excellent heat-resistant cohesion. The heat-resistant cohesion was determined by placing 1 × 1 inch cut pieces of adhesive tape on each adherend (SUS board and PE board) and pressing them using a 2 kg roller. The adhesive tape pressed to the adherend can be placed vertically, a 1 kg weight is applied to the bottom of the sample, and the length measured after 1 hour in an 80°C environment can be compared.

An exemplary embodiment of the present specification includes an acrylic monomer containing a functional group; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; And preparing an acrylic monomer composition containing an unsaturated carboxylic acid monomer,

A method for producing the above-described adhesive composition is provided, wherein the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 15 parts by weight or more based on 100 parts by weight of the acrylic monomer containing the functional group.

In one embodiment of the present invention, the method for producing the adhesive composition includes neutralizing the acrylic monomer composition; And it may include the step of aging the neutralized acrylic monomer composition.

In one embodiment of the present invention, the method for producing the adhesive composition may further include polymerizing the acrylic monomer composition under temperature conditions of 50°C to 100°C, preferably at temperature conditions of 60°C to 95°C. there is. When the above range is satisfied, there is an advantage that reactivity is not reduced.

In one embodiment of the present invention, known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization can be used for the polymerization.

In one embodiment of the invention, the step of neutralizing the acrylic monomer composition may include adjusting the pH of the acrylic monomer composition to 6 or more, 6 to 10, or 7 to 9.

In one embodiment of the present invention, the step of neutralizing the acrylic monomer composition may be using an alkali neutralizing agent. The alkaline neutralizing agent may be one or more selected from the group consisting of hydroxides, chlorides, carbonates, aqueous ammonia, and organic amines of divalent metals, and may be specifically aqueous ammonia or KOH.

The concentration or amount of the alkaline neutralizer is not greatly limited as long as it satisfies the pH range, but KOH with a concentration of 50 wt% diluted with KOH and distilled water at a weight ratio of 1:1 can be used.

In one embodiment of the present invention, the aging step may be performed for 30 minutes to 120 hours at a temperature of 30 to 95 ° C. When the above range is satisfied, stability over time is improved and productivity is excellent.

Hereinafter, the present invention will be described through examples, but the scope of the present invention is not limited to the examples described below.

<Example 1>

2-Ethylhexyl acrylate as an acrylic monomer containing a functional group in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas introduction pipe, and dropping lot, and (meta) containing a polyalkylene glycol skeleton. A material with a number average molecular weight of 200 of polyalkylene glycol in the skeleton was used as an acrylic acid ester monomer, and acrylic acid (AA) was added as an unsaturated carboxylic acid monomer.

As a polymerization solvent, 60 parts by weight of ethyl acetate, 55 parts by weight of ethyl alcohol, and 5 parts by weight of isopropyl alcohol were added, and nitrogen gas was introduced for 2 hours. Based on 100 parts by weight of polymerization solvent, 0.2 parts by weight of polymerization initiator {2.2-Azobisisobutyronitrile (AIBN)} was added and solution polymerized at 70°C for 8 to 10 hours to obtain a solution with a solid content of 49.5% and a viscosity of 6,000cps (@25°C). An adhesive composition was prepared.

<Examples 2 to 21 and Comparative Examples 1 to 4>

An adhesive composition was prepared in the same manner as in Example 1, except that the content of each material was changed as shown in Tables 1 to 4 below.

<Experiment method>

<Experimental Example 1: Probe Tack Test>

① The adhesive composition of the example was applied to a thickness of 50 to 60 μm on PET with a thickness of 25 to 30 μm and aged at 43°C for 1 day to prepare a film.

② Cut the specimen into 20mm wide x 20mm long and place the specimen in 300g of water at 80℃.

③ Stir at 300 rpm for 60 minutes and then take out the specimen.

④ Dry the specimen sufficiently in an oven at 120℃ for more than 5 minutes and then measure it using Probe Tack equipment.

⑤ Probe tack is measured 5 times and the average is calculated.

<Experimental Example 2: Ball Tack Test>

① The adhesive composition of the example was applied to a thickness of 50 to 60 μm on PET with a thickness of 25 to 30 μm and aged at 43°C for 1 day to prepare a film.

② Measure ball tack using the J. Dow method.

③ The size of the ball that rolls and stops is indicated as tack.

<Experimental Example 3: Adhesion test>

① The adhesive composition of the example was applied to a thickness of 50 to 60 μm on PET with a thickness of 25 to 30 μm and aged at 43°C for 1 day to prepare a film.

② Cut into pieces measuring 25mm wide x 110mm tall.

③ Peel strength test is performed according to the regulations of GM-A-1001.

<Experimental Example 4: Heat-resistant cohesion test>

① The adhesive composition of the example was applied to a thickness of 50 to 60 μm on PET with a thickness of 25 to 30 μm and aged at 43°C for 1 day to prepare a film.

② Cut the film into 1 inch x 1 inch.

③ After attaching the adhesive tape to the SUS, use a roll-down equipment to adhere it back and forth once at a speed of 305 mm/min.

④ Add 0.023T PET to the opposite side of the adhesive surface to be measured.

⑤ After aging the prepared specimen at 25℃/50% for 30 minutes, place a 1kg weight on the triangular ring attached to the end of the specimen in an oven at 60℃.

⑥ Measure the falling time of the weight or the degree to which it is pushed down from the SUS.

<Experimental Example 5: Water dissociation test>

The water dissociability of each adhesive composition was tested using the method below.

① The adhesive composition of the example is applied to a nonwoven fabric with a thickness of 25 to 30 μm to a thickness of 50 to 60 μm and aged at 43° C. for 1 day to prepare a film.

② Cut the sample into 10mm wide x 10mm long and put 15g of the sample into 500cc of room temperature water.

③ Homogenizer Chuck-Type size 1~8mm (HT5) Stir for 10 minutes at 10,000 rpm using a low-viscosity mixer, then wash the impeller with 50 cc of water (3 times).

④ After filtering through a 300mesh filter, apply evenly to A4 paper and laminate.

⑤ After drying at 120°C for 20 minutes, the presence or absence of transfer and adhesive was checked upon peeling and marked with O or X.

Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Acrylic monomer containing a functional group
100 parts by weight 2EHA 2EHA 2EHA 2EHA 2EHA 2EHA 2EHA R-1 100 R-2 100 R-3 100 R-4 100 R-5 100 R-6 100 R-7 100 R-8 AA 40 40 40 40 40 40 40 KOH (50%) 2 One Cross-linking agent (GC-10) 4 4 4 4 4 4 4 Experimental Example 1 0 0 0 0 0 0 0 Experimental Example 2 5 12~15 12~15 14~16 14~16 4 6~8 Experimental Example 3 1300 1100 1100 1200 1100 1000 1000 Experimental Example 4 One One 1~2 1~2 1~2 2 2 Experimental Example 5 O O O O O O O

Example Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Acrylic monomer containing a functional group
100 parts by weight 2EHA 2EHA 2EHA 2EHA 2EHA 2EHA 2EHA 2EHA R-1 R-2 233 150 43 25 R-3 R-4 R-5 R-6 R-7 233 150 43 R-8 100 AA 40 67 50 29 25 67 50 29 KOH (50%) 2 Cross-linking agent (GC-10) 4 4 4 4 4 4 4 4 Experimental Example 1 0 0 0 0 0 0 0 0 Experimental Example 2 10~12 19~22 16~19 4~6 4↓ 12~13 9~11 4↓ Experimental Example 3 1000 1000 1100 1400 1500 900 900 1300 Experimental Example 4 One 2 One One One One One One Experimental Example 5 O O O O O O O O

Example Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Acrylic monomer containing a functional group
100 parts by weight 2EHA 2EHA 2EHA 2EHA B.A. EA R-1 R-2 100 100 100 100 100 R-3 R-4 R-5 R-6 R-7 25 R-8 AA 25 20 30 50 40 40 KOH (50%) 2 2 One Cross-linking agent (GC-10) 4 4 4 4 4 4 Experimental Example 1 0 0 0 0 0 0 Experimental Example 2 4↓ 19 15 8~10 11~13 8~9 Experimental Example 3 1500 500 700 1200 900 1000 Experimental Example 4 One One One One One One Experimental Example 5 O O O O O O

Comparative example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Acrylic monomer containing a functional group
100 parts by weight B.A. 2EHA 2EHA 2EHA R-1 R-2 10 R-3 R-4 R-5 R-6 R-7 10 R-8 AA 20 20 22 22 KOH (50%) Cross-linking agent (GC-10) 4 4 4 4 Experimental Example 1 100 150 30 30 Experimental Example 2 4↓ 4↓ 4↓ 4↓ Experimental Example 3 1400 1600 1500 1600 Experimental Example 4 One One One 2 Experimental Example 5 × × × ×

In Tables 1 to 4 above, the description of each material is as shown in Table 5 below.

monomer abbreviation chemical name R-1 Polyethylene glycol(200) monomethyl ether acrylate R-2 Polyethylene glycol(400) monomethyl ether acrylate R-3 Polyethylene glycol(600) monomethyl ether acrylate R-4 Polyethylene glycol(800) monomethyl ether acrylate R-5 Polyethylene glycol(1000) monomethyl ether acrylate R-6 Polyethylene glycol(350) monomethyl ether methacrylate R-7 Polyethylene glycol(400) monomethyl ether methacrylate R-8 Polyethylene glycol(600) monomethyl ether methacrylate B.A. Butyl acrylate 2EHA 2-Ethylhexyl acrylate EA Ethyl acrylate AA Acrylic Acid

From the above results, it was confirmed that when the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton was not included (Comparative Examples 1 and 2), the water dissociability test result was poor. In addition, the polyalkylene glycol skeleton It was confirmed that the water dissociability test results were poor even when the content of the (meth)acrylic acid ester monomer contained was less than 15 parts by weight based on 100 parts by weight of the acrylic monomer containing the functional group.

However, acrylic monomers containing functional groups; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; and an unsaturated carboxylic acid monomer, and an example in which the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is adjusted to 15 parts by weight or less based on 100 parts by weight of the acrylic monomer containing the functional group. It was confirmed that the adhesive compositions of Nos. 1 to 21 had excellent water dissociability test results.

Claims (15)

Acrylic monomer containing a functional group;
(meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; and
Contains unsaturated carboxylic acid monomers,
The content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 20 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the acrylic monomer containing the functional group,
A viscosity at 25° C. of 1,000 to 9,000 cPs,
The polyalkylene glycol skeleton is represented by the formula 1 below,
The (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is derived from polyalkylene glycol with a number average molecular weight of 200 to 900.
An adhesive composition having a Probe tack test result of 1 gf or less after immersion in water at 80° C. and drying:
[Formula 1]
HO-[(CH ₂ )nO-]mH
In Formula 1,
m can be 2 to 20,
The n is the number of repetitions of the alkylene group in Formula 1, and is 2. delete delete delete In claim 1,
The unsaturated carboxylic acid monomers include acrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, An adhesive composition comprising at least one member selected from the group consisting of glutaconic acid and allylmalonic acid. In claim 1,
An adhesive composition wherein the acrylic monomer containing the functional group includes a (meth)acrylic acid ester monomer having an alkyl group. In claim 1,
An adhesive composition wherein the acrylic monomer containing the functional group includes a (meth)acrylic acid ester monomer having a C1 to C14 alkyl group. In claim 1,
An adhesive composition further comprising one or more additives selected from the group consisting of molecular weight regulators, crosslinking agents, initiators, thickeners, dispersants, ultraviolet stabilizers, antioxidants, anti-corruption agents, buffers, and fillers. delete delete Acrylic monomer containing a functional group; (meth)acrylic acid ester monomer containing a polyalkylene glycol skeleton; And preparing an acrylic monomer composition containing an unsaturated carboxylic acid monomer,
Any one of claims 1 and 5 to 8, wherein the content of the (meth)acrylic acid ester monomer containing the polyalkylene glycol skeleton is 20 parts by weight to 300 parts by weight based on 100 parts by weight of the acrylic monomer containing the functional group. Method for producing an adhesive composition according to. In claim 11,
neutralizing the acrylic monomer composition; and
A method of producing an adhesive composition comprising the step of aging the neutralized acrylic monomer composition. In claim 11,
A method for producing an adhesive composition further comprising polymerizing the acrylic monomer composition at a temperature of 50°C to 100°C. In claim 12,
The step of neutralizing the acrylic monomer composition includes adjusting the pH of the acrylic monomer composition to 6 or higher. In claim 12,
A method of producing an adhesive composition, wherein the aging step is performed for 30 minutes to 120 hours under temperature conditions of 30 to 95 ° C.