KR20070094976A - Solid adhesive and its raw material composition - Google Patents

Abstract

This invention relates to the solid adhesive which improved initial stage adhesiveness, and a raw material liquid composition for adjusting this solid adhesive. The solid adhesive of the present invention is obtained by blending an adhesive polymer having a glass transition temperature (Tg) of 40 to 45 ° C with a gelling agent.

Description

Solid adhesive and its raw material composition {SOLID ADHESIVE AGENT AND RAW MATERIAL COMPOSITION FOR THE SAME}

The present invention relates to a solid adhesive having excellent adhesiveness and coating property to an adherend, and a raw material liquid composition for preparing the solid adhesive.

BACKGROUND ART So-called stick glue formed by filling a lipstick-shaped container with a gel-supporting agent such as a long chain fatty acid salt and a solid adhesive mainly composed of various adhesive polymers such as polyvinylpyrrolidone is known. However, as the adhesive polymer for a solid adhesive, polyvinylpyrrolidone, which has been most frequently used in the past, is expensive, and therefore, an inexpensive adhesive polymer for a solid adhesive is substituted for polyvinylpyrrolidone.

In such a solid adhesive, it is required to be excellent in initial adhesiveness such as a short time after applying to one of a pair of adherends and exhibiting the required adhesive force when adhering with the other adherend.

For example, a solid adhesive using a polyacrylate aqueous dispersion containing a free acid group or an alkali-soluble polyacrylate as an adhesive polymer has been proposed (see WO 03/029376).

However, it has been found by the inventors that the solid adhesive proposed here is insufficient in terms of initial adhesiveness.

An object of the present invention is to provide a solid adhesive having improved initial adhesiveness while maintaining good applicability to an adherend, and a raw material liquid composition for preparing the solid adhesive.

The present invention relates to a solid adhesive obtained by blending an adhesive polymer having a glass transition temperature (Tg) of 40 to 55 ° C and a gelling agent.

MEANS TO SOLVE THE PROBLEM In the solid adhesive which uses an adhesive polymer as a main component of an adhesive component, the inventors mix | blended the adhesive polymer whose glass transition temperature (Tg) is 40-55 degreeC, and does not impair the applicability | paintability to a to-be-adhered body. It discovered that adhesiveness could be improved and came to complete this invention. Hereinafter, the structure of the solid adhesive of this invention is demonstrated in detail.

The adhesive polymer used by this invention requires that a glass transition temperature (Tg) is 40-55 degreeC. When Tg is out of this range, the initial stage adhesiveness of a solid adhesive may fall.

Tg of an adhesive polymer becomes like this. Preferably it is 42 degreeC or more, More preferably, it is 44 degreeC or more, Preferably it is 50 degrees C or less, More preferably, it is 48 degrees C or less.

Tg in this invention shows the value measured by the method shown below.

(Tg measurement method)

Differential scanning calorimetry (DSC) measurement is performed according to JIS K-7121 using DSC220 manufactured by Seiko Corporation.

10 mg of the dried adhesive polymer is placed in the measuring container, capped and fixed, and then placed in a container holder. The other container holder shall be fitted with an empty measuring container with the lid fixed. While nitrogen is introduced at 10 ml per minute, the temperature is raised to 20 deg. C every minute to 150 deg. After holding this state for 20 minutes, it cools to 10 degreeC every minute, and is set to -20 degreeC. After holding this state for 10 minutes, it heated up again at 20 degreeC to 150 degreeC every minute, and draws a DSC curve. Tg is determined in accordance with JIS K-7121 9.3 "Calculation method of glass transition temperature" in the obtained DSC curve.

Such an adhesive polymer is preferably one containing an ethylenically unsaturated monomer having no acid group (hereinafter sometimes referred to simply as an "ethylenically unsaturated monomer") as a component, and more preferably, not having an acid group. Polymers comprising ethylenically unsaturated monomers and acidic monomers as components are recommended.

As ethylenically unsaturated monomer which does not have an acidic radical, (meth) acrylic acid and carbon number, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate (Meth) acrylic acid ester polymerizable monomer which is ester with 1-18 alcohols (except cyclic alcohol); Styrene-based polymerizable monomers such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, chloromethylstyrene, and ethylvinylbenzene; Cyclohexyl group-containing polymerizable monomers such as cyclohexyl (meth) acrylate; Unsaturated esters such as methyl crotonate, vinyl acetate and vinyl propionate; Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene and 2-chloro-1,3-butadiene; Allyls, such as (meth) allyl alcohol and glycidyl (meth) allyl ether; Unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile; Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and monoester of (meth) acrylic acid and polypropylene glycol; Polyethylene glycol chain-containing polymerizable monomers such as polyethylene glycol (meth) acrylic ester; Alkyl polyalkylene glycol obtained by adding 1 to 300 moles of oxyalkylene having 2 to 4 carbon atoms to an alcohol or an amine such as methoxy polyethylene glycol mono (meth) acrylate and methoxy polyalkylene glycol mono (meth) acrylate; Esters or amides with unsaturated monocarboxylic acids; Allyl which added 1 to 300 moles of oxyalkylene having 2 to 4 carbon atoms to (meth) allyl alcohol; Dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, (meth) acrylamide, N-monomethyl (meth) acrylamide, (meth) acrylalkylamide, N-monoethyl (meth) acrylamide (Meth) acrylamides and derivatives thereof such as N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and methylene (meth) acrylamide; Diamides of unsaturated dicarboxylic acids such as maleic acid and fumaric acid with amines having 1 to 22 carbon atoms; N-vinylpyrrolidone; Basic polymerizable monomers such as methyl aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine and vinylimidazole; Phenolic monomers such as vinylphenol; Aziridine group containing monomers, such as 2-aziridinyl ethyl (meth) acrylate and (meth) acryloyl aziridine; Oxazoline group-containing polymerizable monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl oxazoline; Epoxy group-containing polymerizable monomers such as glycidyl (meth) acrylate and acryl glycidyl ether; Direct bonding to silicon atoms such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloylpropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane and allyltriethoxysilane Hydrolyzable silicon group-containing polymerizable monomers; Halogen-containing polymerizable monomers such as vinyl fluoride, vinylidene fluoride, vinyl chloride and vinylidene chloride; Bifunctional (meth), such as (poly) ethylene glycol di (meth) acrylate, (poly) alkylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and trimethylol propane di (meth) acrylate Acrylates; (Meth) acrylic acid, ethylene glycol, 1,3-butylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylol propane, pentaerythritol, Polyfunctional (meth) acrylic acid esters having two or more polymerizable unsaturated groups in a molecule such as an ester with a polyhydric alcohol such as dipentaerythritol; Polyfunctional allyl compounds having two or more polymerizable unsaturated groups in a molecule such as diallyl phthalate, diallyl maleate, and diallyl fumalate; Allyl (meth) acrylate; Divinyl aromatics such as divinylbenzene; Polymerizable polyfunctional monomers such as allyl (meth) acrylate; Cyanurates such as triallyl cyanurate; Associative monomers such as esterified products of poly (ethylene glycol) alkyl ether and (meth) acrylic acid, and the like, and one or two or more of these may be used.

Preferable ethylenically unsaturated monomers include at least one monomer selected from (meth) acrylic acid ester polymerizable monomers and unsaturated esters, and (meth) acrylic acid ester polymerizable monomers are particularly preferred.

As an acidic monomer, Carboxylic acid group containing polymeric monomers, such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride; Sulfonic acid group-containing polymerizable monomers such as vinylsulfonic acid, styrenesulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, and sulfoethyl (meth) acrylate; Mono (2-methacryloyloxyethyl) phosphate, mono (2-acryloyloxyethyl) phosphate, 2- (meth) acryloyloxypropyl phosphate, 2- (meth) acryloyloxy-3-chloro Phosphoric acid group-containing polymerizable monomers such as propyl phosphate and 2- (meth) acryloyloxyethylphenyl phosphate; And inorganic salts such as sodium salts and potassium salts of these polymerizable monomers, or ammonium salts and organic amine salts, and one or two or more thereof can be used.

Preferred acidic monomers include carboxylic acid group-containing polymerizable monomers and sulfonic acid group-containing polymerizable monomers, and among them, carboxylic acid group-containing polymerizable monomers are preferable.

Among the adhesive polymers containing the above ethylenically unsaturated monomers and acidic monomers as constituents, the ethylenically unsaturated monomers have good adhesiveness to paper, which is one of the main adherends of the solid adhesive of the present invention. As a (meth) acrylic acid ester type polymerizable monomer and an acidic monomer, the polymer which contains (meth) acrylic acid or its salt as a component is preferable.

In order to make Tg of the adhesive polymer according to the present invention fall within the above range, for example, when the adhesive polymer comprises ethyl acrylate as an ethylenically unsaturated monomer and methacrylic acid as an acidic monomer, the sum thereof is When it is 100 mass parts, it is recommended to mix | blend ethyl acrylate at 61.5 mass parts or more, 68 mass parts or less, and methacrylic acid in the ratio of 32 mass parts or more and 38.5 mass parts or less.

It is preferable that it is 100,000 or more as a weight average molecular weight of an adhesive polymer.

The acid value of the adhesive polymer is preferably 170 mgKOH / g or more, more preferably 180 mgKOH / g or more, preferably 250 mgKOH / g or less, and more preferably 240 mgKOH / g. Less than or equal to g is recommended.

The property of the adhesive polymer is not particularly limited as long as it is water-soluble or water-dispersible. Among them, in an acidic condition (pH 3 or lower), an emulsion state using water as a medium is taken, and an alkali that is water-soluble under neutralization conditions (pH 7 or higher) is used. Soluble emulsions are preferred.

When preparing the adhesive polymer by emulsion polymerization, it is preferable to use an emulsifier. The emulsifier is not particularly limited, and anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants and the like that are generally used in emulsion polymerization can be given. Moreover, reactive surfactant which has unsaturated groups, such as a polyoxyethylene alkenyl aryl sulfate salt and (alpha)-sulfonato- (omega) -1- (allyloxymethyl) alkyloxy polyoxyethylene salt, can also be used. Moreover, it is preferable that the non volatile matter in the aqueous dispersion obtained after an emulsion polymerization reaction is 60% or less. If the nonvolatile content exceeds 60%, the viscosity of the water dispersion becomes too high, dispersion stability is not maintained, and tends to aggregate easily.

Moreover, the average particle diameter of the polymer particle of the adhesive polymer obtained by the said emulsion polymerization becomes like this. Preferably it is 70 nm or less, More preferably, it is recommended that it is 60 nm or less. In the solid adhesive of the present invention, it is essential that the adhesive polymer is mixed and heated with fatty acids, polyhydric alcohols and other additives, and then neutralized with an alkaline solution (preferably an aqueous sodium hydroxide solution) to form a uniform liquid. When the average particle diameter of a polymer particle exceeds the said range, aggregation of a polymer particle will be easy to occur at the time of neutralization in alkaline solution (sodium hydroxide aqueous solution), and there exists a tendency for uniformity to take a long time.

In addition, the adhesive polymer is a pH: 7, an aqueous solution of 1% by weight of concentration, the viscosity obtained by measuring at 25 ℃ using a k-type viscometer (spindle No. 2) is preferably 70 mPa · s or more More preferably, it is 80 mPa * s or more, Preferably it is 500 mPa * s or less, More preferably, it is recommended to set it to 400 mPa * s or less. When the viscosity of aqueous solution is less than the said range, the adhesive force of a solid adhesive may not fully be obtained.

Moreover, although the solid adhesive of this invention is obtained by mixing and heating each raw material to the viscous liquid substance, for example, filling this into a container (lipstick shape etc.) and cooling and solidifying, it is an adhesive polymer When the aqueous solution viscosity exceeds the above range, the viscosity of the liquid before filling the container increases, and the discharge operation from the container or filling into a container of relatively small diameter (for example, lipstick shape) of 1 cm to several cm is performed. There may be a problem that it takes a long time.

In the solid adhesive of the present invention, in order to ensure shape retention, the gelling agent is also a component. The said gelling agent is not specifically limited, The well-known gelling agent conventionally used for a solid adhesive conventionally can be used.

For example, Metal salt or ammonium salt of C8-C36 fatty acid, such as laurate, myristic acid salt, palmitate salt, stearic acid salt, and ricinoleate salt; Sorbitol benzaldehyde condensates, and the like, and these may be used alone or in combination of two or more thereof. Especially, the alkali metal salt or ammonium salt of a C8-C36 fatty acid is preferable, and an alkali metal salt is more preferable. Moreover, as alkali metal of the metal salt of a C8-C36 fatty acid, Na, K, etc. are common.

In addition, in the production of the solid adhesive of the present invention, the alkali metal salt or ammonium salt of the C8-C36 fatty acid is mixed with an adhesive polymer or other additives with C8-C36 fatty acid, and then, such as sodium hydroxide or ammonia. The form which neutralizes with alkaline substance may be sufficient.

In the preparation of the solid adhesive, the adhesive polymer, the gelling agent and other additives are dissolved and dispersed in an aqueous solvent and filled into a container for the solid adhesive composition. As the aqueous solvent, water is preferable, but among the aqueous solvents, alcohols such as ethanol and isopropyl alcohol; Ketones such as methyl ethyl ketone; Ester, such as ethyl acetate, can be contained.

In order to act as a dissolution aid for dissolving the gelling agent in the aqueous solvent and also as a moisturizing agent and a plasticizer, it is preferable to blend the polyhydric alcohol. Dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol; And trihydric or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol. In addition, cyclic alcohols such as ketose (hexloose, heptulose, and the like), aldonic acid, aldaric acid, deoxysaccharide, and inositol sugar can also be used.

It is preferable that the compounding quantity of the said adhesive polymer is 10 mass% or more in 100 mass% of the solid adhesives of this invention, More preferably, it is 12 mass% or more, It is preferable that it is 20 mass% or less, More preferably, 18 mass% % Or less When the compounding quantity of an adhesive polymer is too small, there exists a tendency for the adhesive force of a solid adhesive to fall. Moreover, although the solid adhesive of this invention is obtained by mixing and heating each raw material to the viscous liquid substance, for example, filling this into a container (lipstick shape etc.), and cooling and solidifying, the compounding quantity of an adhesive polymer When there is too much, the viscosity of the liquid substance before filling into a container may increase, and it may take time to discharge | eject from a container, or to fill the container with a comparatively small diameter of 1 cm-several cm.

In the solid adhesive of the present invention, the amount of the gelling agent in the 100 mass% of the solid adhesive is preferably 3 mass% or more, more preferably 4 mass% or more, preferably 12 mass% or less, and more preferably It is recommended to use 10 mass% or less. When the amount of the gelling agent is less than the above range, the shape retainability of the solid adhesive tends to decrease, while when the amount of the gelling agent exceeds the above range, the initial adhesiveness may decrease.

The amount of the aqueous solvent in the solid adhesive is preferably 30 mass% or more, more preferably 40 mass% or more, preferably 80 mass% or less, and more preferably 70 mass% or less in the solid adhesive. It is preferable.

Moreover, when using together the organic solvent as mentioned above in water as an aqueous solvent, it is preferable to make this organic solvent 10 mass% or less in 100 mass% of aqueous solvents, and to make it 5 mass% or less further. desirable. Of course, it is also preferable that the total amount of the aqueous solvent is water.

Moreover, when using the said polyhydric alcohol, in 100 mass% of solid adhesive agents, Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more, Preferably it is 20 mass% or less, More preferably, 15 It is preferable that it is mass% or less.

You may add another additive to the solid adhesive of this invention. Examples of such additives include fats and oils such as linseed oil, lysine, castor oil, soybean oil, palm oil, tall oil, fish oil, oleic acid, linoleic acid and linolenic acid; Polyoxyalkylene ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan (mono, di, tri) fatty acid ester, (poly) glycerin (mono, di, tri) fatty acid ester, sorbitan (mono, di, Surfactants such as tri) stearate; Lubricants such as liquid paraffin; Inorganic extenders such as silica, alumina, titanium dioxide, barium oxide, zinc oxide, talc, bentonite; Antioxidants such as sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate and rongalit; Sugars such as sucrose, sorbitol and glucose; Dextrins, such as dextrin and cyclodextrin, etc. are mentioned, What is necessary is just to use suitably in an appropriate amount.

Moreover, a fragrance, a fluorescent brightener, an antibacterial agent, a coloring agent, etc. can also be mix | blended. For example, it is recommended to add about 0.01 to 0.1 mass% of antimicrobial agent in solid adhesive.

Moreover, the solid adhesive of this invention can use together the said adhesive polymer and the usual polymer employ | adopted in the field of an adhesive agent together. Such polymers include water-soluble polymers such as polyvinylpyrrolidone, polyvinyl alcohol and modified starch; Polymer emulsions, such as a polyvinyl acetate emulsion, etc. are mentioned.

As a specific manufacturing method of a solid adhesive, the following methods can be employ | adopted, for example. The adhesive polymer is mixed with an aqueous solvent (preferably water), and then the mixture is stirred while heating to prepare a uniform dispersion. A gelling agent and a polyhydric alcohol are mixed with this to dissolve uniformly, Furthermore, as needed, various additives are mixed and viscous liquid. This liquid is filled into a container (for example, a lipstick shape), cooled and solidified to obtain a solid adhesive.

Moreover, when using alkali-soluble emulsion as an adhesive polymer of this invention, and an alkali metal salt or ammonium salt of a C8-C36 fatty acid suitable as a gelling agent, the following manufacturing methods are also effective.

Aqueous solvent (preferably an alkali-soluble emulsion is mixed with water, followed by stirring while heating the mixture to prepare a homogeneous emulsion, which is mixed with a fatty acid having 8 to 36 carbon atoms and a polyhydric alcohol as necessary to make it uniform. Subsequently, a required amount of alkaline substance such as sodium hydroxide is added to the mixture to neutralize it, and further, various additives are mixed to form a viscous liquid, if necessary, to form a viscous liquid. ), Cooled and solidified to obtain a solid adhesive.

Suitable adherends to be subjected to the solid adhesive of the present invention include known papers such as Japanese paper, synthetic paper, fine paper, heavy paper, art paper, coated paper, cast coated paper, foil paper, kraft paper, impregnated paper, and evaporated paper; Polyester films (including sheets) such as polyethylene terephthalate and polybutylene terephthalate; Woven or nonwoven fabrics composed of fibers such as cotton, polyester and nylon; Various floats; Aluminum foil, copper foil and the like.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example. However, the following Examples do not limit the present invention, and all modifications are made within the technical scope of the present invention without departing from the spirit and scope of the present invention. In addition, "part" and "%" used by a present Example are a mass reference | standard unless there is particular notice. In addition, the evaluation method used in the present Example is as follows.

(1) adhesion time

The following experiment is performed in the atmosphere of temperature 25 degreeC and relative humidity 60%. Plain paper (PPC paper) is cut to 3cm × 6cm and used as test paper. A solid adhesive is applied to about half of one surface of one sheet of test paper, and immediately another sheet of test paper is laminated. After a predetermined time has elapsed since the adhesion, the non-bonded portion of the bonded test paper was pulled in different directions to be peeled off. The time from the adhesion of the test paper until the test paper does not tear and cannot be peeled off is referred to as the adhesion time. The shorter the adhesion time, the more the adhesive force is exerted from the adhesion in a short time, that is, the better the initial adhesion.

Polymerization Example 1:

124.5 parts by mass of ion-exchanged water and 1.5 parts by mass of ammonium sulfonic acid salt of polyoxyethylene dodecyl ether were charged into a four-necked separable flask equipped with a stirrer, a thermometer, a cooler, a nitrogen introduction tube, and a dropping funnel. While stirring at the internal temperature of 68 ° C., nitrogen was gently flowed to completely replace the inside of the reaction vessel with nitrogen. Next, 1.5 parts by mass of ammonium sulfonic acid ammonium salt of polyoxyethylene dodecyl ether was dissolved in 93.2 parts by mass of ion-exchanged water, a mixture of 35 parts by mass of methacrylic acid and 65 parts by mass of ethyl acrylate was added thereto, followed by stirring to prepare a preemulsion. Prepared. In addition, 0.23 parts by mass of ammonium persulfate was mixed with 23.2 parts by mass of ion-exchanged water to prepare an aqueous initiator solution. 5% of the pre-emulsion was added to the reaction vessel and stirred for 5 minutes, and then 0.017 parts by mass of sodium hydrogen sulfite was added thereto. Subsequently, 5% of the aqueous initiator solution was added to the reaction vessel, followed by stirring for 20 minutes to perform initial polymerization. The internal temperature of the reaction vessel was maintained at 72 ° C, and the remaining preemulsion and initiator aqueous solution were added dropwise uniformly over 2 hours. After completion of the dropwise addition, the internal temperature was maintained at 72 ° C., and further stirring was continued for 1 hour, followed by cooling to complete the reaction, thereby obtaining an emulsion polymer having a nonvolatile content of 30%. Tg of this polymer was 46 degreeC, the average particle diameter was 54 nm, and the 1% aqueous solution viscosity in pH 7 was 145 mPa * s.

Polymerization Example 2:

An emulsion polymer having a nonvolatile content of 30% was obtained in the same manner as in Polymerization Example 1, except that 33 parts by mass of methacrylic acid and 67 parts by mass of ethyl acrylate were used. Tg of this polymer was 42 degreeC.

Polymerization Example 3:

An emulsion polymer having a nonvolatile content of 30% was obtained in the same manner as in Polymerization Example 1, except that 38 parts by mass of methacrylic acid and 62 parts by mass of ethyl acrylate were used. Tg of this polymer was 54 degreeC.

Polymerization Example 4:

An emulsion polymer having a nonvolatile content of 30% was obtained in the same manner as in Polymerization Example 1, except that 40 parts by mass of methacrylic acid and 60 parts by mass of ethyl acrylate were used. Tg of this polymer was 60 degreeC.

Polymerization Example 5.

An emulsion polymer having a nonvolatile content of 30% was obtained in the same manner as in Polymerization Example 1, except that 25 parts by mass of methacrylic acid and 75 parts by mass of ethyl acrylate were used. Tg of this polymer was 32 degreeC.

Example 1:

In a flask equipped with a reflux condenser and agitator, water: 16.5 parts, stearic acid (manufactured by Asahi Denka Co., Ltd., "SA-200"): 6 parts, emulsion polymer obtained in the polymerization example 1: 50.0 parts, glycerin: 6 parts , 6 parts of ethylene glycol were added, and it heated up at 80 degreeC, stirring, and set it as the uniform turbid liquid. Next, 25% sodium hydroxide: 15.5 parts was added little by little, and after stirring for 10 hours, the viscous pale yellow transparent liquid substance was obtained. After heating up this liquid substance at 90 degreeC, it filled in the lipstick container (23 mm of internal diameters and 80 mm of length), cooled, solidified, and obtained the solid adhesive. Table 1 shows the evaluation results of this solid adhesive.

Example 2:

In a flask equipped with a reflux condenser and a stirrer, water: 17.2 parts, stearic acid (manufactured by Asahi Denka Co., Ltd., "SA-200"): 6 parts, emulsion polymer obtained in the polymerization example 2: 50.0 parts, glycerin: 6 parts , 6 parts of ethylene glycol were added, and it heated up at 80 degreeC, stirring, and set it as the uniform turbid liquid. Subsequently, 14.8 parts of 25% sodium hydroxide were added to this white liquid little by little, and after stirring for 10 hours, the viscous pale yellow transparent liquid substance was obtained. After heating up this liquid substance at 90 degreeC, it filled in the lipstick container (23 mm of internal diameters and 80 mm of length), cooled, solidified, and obtained the solid adhesive. Table 1 shows the evaluation results of this solid adhesive.

Example 3:

In a flask equipped with a reflux condenser and agitator, water: 15.5 parts, stearic acid (manufactured by Asahi Denka Co., Ltd., "SA-200"): 6 parts, emulsion polymer obtained in the polymerization example 3: 50.0 parts, glycerin: 6 parts , 6 parts of ethylene glycol were added, and it heated up at 80 degreeC, stirring, and set it as the uniform turbid liquid. Subsequently, 16.5 parts of 25% sodium hydroxide were added to this white liquid small quantity, and after stirring for 10 hours, the viscous pale yellow transparent liquid substance was obtained. After heating up this liquid substance at 90 degreeC, it filled in the lipstick container (23 mm of internal diameters and 80 mm of length), cooled, solidified, and obtained the solid adhesive. Table 1 shows the evaluation results of this solid adhesive.

Comparative Example 1:

In a flask equipped with a reflux condenser and agitator, water: 15.1 parts, stearic acid (manufactured by Asahi Denka Co., Ltd., "SA-200"): 6 parts, emulsion polymer obtained in the polymerization example 4: 50.0 parts, glycerin: 6 parts , 6 parts of ethylene glycol were added, and it heated up at 80 degreeC, stirring, and set it as the uniform turbid liquid. Next, 16.9 parts of 25% sodium hydroxide was added in small portions, and after stirring for 10 hours, a viscous pale yellow transparent liquid was obtained. After heating up this liquid substance at 90 degreeC, it filled in the lipstick container (23 mm of internal diameters and 80 mm of length), cooled, solidified, and obtained the solid adhesive. Table 1 shows the evaluation results of this solid adhesive.

Comparative Example 2:

In a flask equipped with a reflux condenser and a stirrer, water: 19.8 parts, stearic acid (manufactured by Asahi Denka Co., Ltd., "SA-200"): 6 parts, emulsion polymer obtained in the polymerization example 5: 50.0 parts, glycerin: 6 parts , 6 parts of ethylene glycol were added, and it heated up at 80 degreeC, stirring, and set it as the uniform turbid liquid. Next, 25% sodium hydroxide: 12.2 parts were added little by little, and after stirring for 10 hours, the viscous pale yellow transparent liquid substance was obtained. After heating up this liquid substance at 90 degreeC, it filled in the lipstick container (23 mm of internal diameters and 80 mm of length), cooled, solidified, and obtained the solid adhesive. Table 1 shows the evaluation results of this solid adhesive.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tg (℃) of adhesive polymer 46 42 54 60 32 Adhesion time (minutes) 6 6.5 6.75 8.5 8.5

As can be seen from Table 1, the bonding time of the solid adhesives of Examples 1 to 3 is shorter than that of the solid adhesives of Comparative Examples 1 and 2. In actual use forms, such as bonding paper using a solid adhesive, it is obvious that the working efficiency of adhesion is remarkably improved by shortening the time until the effective adhesion is exerted. Therefore, it can be judged that the solid adhesive of Examples 1-3 has the initial stage adhesiveness superior to the solid adhesive of Comparative Examples 1 and 2.

According to this invention, the solid adhesive excellent in initial stage adhesiveness can be manufactured by mix | blending the adhesive polymer whose glass transition temperature (Tg) is 40-55 degreeC.

Claims (3)

A solid adhesive obtained by blending an adhesive polymer having a glass transition temperature (Tg) of 40 to 55 ° C with a gelling agent. The solid adhesive according to claim 1, wherein the adhesive polymer is an adhesive polymer obtained by copolymerizing an ethylenically unsaturated monomer having no acidic group and an acidic monomer. A raw material liquid composition for adjusting the solid adhesive according to claim 1 or 2, wherein the raw material liquid composition for a solid adhesive comprises a adhesive polymer having a glass transition temperature (Tg) of 40 to 55 ° C.