JPH0925472A - Tackifier emulsion and water-based adhesive composition containing the emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tackifier emulsion excellent in mechanical stability, stability against hard water and miscibility with a base polymer emulsion and useful for electrical insulation, business uses, etc., such as adhesive tapes, adhesive sheets, adhesive labels, etc. SOLUTION: This tackifier emulsion comprises (A) a rosin material containing >=20wt.% reaction product comprising rosins (A1 ) such as hydrated rosin, etc., α,β-unsaturated carboxylic acids (A2 ) such as fumaric acid, etc., sulfocarboxylic acids (A3 ) such as sulfosuccinic acid, its lower dialkyl ester, etc., and ter or more valent polyhydric alcohols (A4 ) such as glycerol, etc., (B) a low molecular weight surfactant and a dispersant of a water soluble high molecular compound, etc., and (C) water. The reaction product of the component A can be obtained e.g. by heating and reacting 1 mole A with 0-0.5 mole A2 , 0.02-0.4 mole A3 and A4 in an mount of an OH equivalent ratio to carboxyls in A1 of 0.8-2.0.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to tackifier emulsions and aqueous pressure sensitive adhesive compositions containing the emulsions. More specifically, the present invention relates to a tackifier emulsion containing a specific amount of a sulfonic group-containing reinforced rosin ester as a substance to be dispersed, and an aqueous pressure-sensitive adhesive composition comprising the emulsion and a base polymer emulsion and / or a base polymer latex. .

[0002]

2. Description of the Related Art Aqueous emulsion type adhesives have various advantages over organic solvent type adhesives, such as no air pollution, excellent safety and health, and resource saving. It has been converted from organic solvent type to aqueous emulsion type. Aqueous emulsion type adhesives mainly include acrylic emulsion type adhesives and rubber latex type adhesives, and any type of adhesive is applied to a support such as polyvinyl chloride or polyolefin, various adhesive tapes, adhesive sheets, Although it is widely used as an adhesive label, acrylic emulsion adhesives are excellent in transparency and weather resistance, and rubber latex adhesives are relatively inexpensive.

As the tackifier, rosin ester, terpene resin, petroleum resin, etc. are generally used. When the tackifier is applied to an aqueous emulsion type tackifier, the tackifier itself is an aqueous emulsion. It needs to be in the form.

For example, in a rosin ester emulsion, which is the most typical of tackifier emulsions, a relatively large amount of a surfactant and a water-soluble polymer are used as an emulsifying dispersant during emulsification, and therefore the rosin ester emulsion is used. Aqueous emulsion-type pressure-sensitive adhesives containing emulsions are not satisfactory in terms of tack, adhesiveness, cohesive strength, water resistance and the like. Furthermore, when the amount of the emulsifying dispersant used is reduced by emphasizing the pressure-sensitive adhesive performance, the mechanical stability of the rosin ester emulsion itself, the hard water stability, the base polymer emulsion and the base polymer latex (hereinafter, both The miscibility with the base polymer emulsion) is greatly reduced.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a tackifier emulsion which is excellent in properties as a tackifier and is excellent in mechanical stability, hard water stability and miscibility with a base polymer emulsion. And an aqueous pressure-sensitive adhesive excellent in tack, adhesiveness, cohesive strength, and water resistance.

[0006]

In order to solve the above-mentioned problems in existing tackifier resin emulsions and water-based pressure-sensitive adhesives using the emulsions, the inventor of the present invention disperses the tackifier resin emulsion as a component to be dispersed. I focused my attention on the rosin substance as a body and conducted extensive research. As a result, the above-mentioned problem is solved by using, as the rosin substance, a tackifier emulsion containing a specific amount of a reinforced rosin ester containing a sulfone group, and an aqueous tackifier containing the tackifier emulsion. The present inventors have completed the present invention by finding that they can be solved.

That is, the present invention is a tackifier emulsion comprising a rosin substance, a dispersant and water, wherein the rosin substance is (A) rosin, (B) α, β-unsaturated carboxylic acid, ( The tackifier emulsion is characterized by containing 20% by weight or more of a reaction product composed of C) a sulfocarboxylic acid and (D) a polyhydric alcohol having a valence of 3 or more. The present invention also relates to an aqueous pressure-sensitive adhesive composition comprising the tackifier emulsion and a base polymer emulsion and / or a base polymer latex.

In the tackifier emulsion of the present invention, the rosin substance to be dispersed is 20% by weight or more, preferably 30% by weight or more of the reaction product in the rosin substance.
It is indispensable that the content is at least wt%. When the content of the reaction product is less than 20% by weight,
Mechanical stability, hard water stability, and miscibility with the base polymer emulsion of the resulting tackifier emulsion are not sufficiently improved, and the tackiness, adhesiveness, cohesive strength, and water resistance of the resulting aqueous pressure-sensitive adhesive composition are sufficient. Does not improve to

In the present invention, the reaction product contained in the rosin substance to be dispersed is, as described above, rosin (hereinafter referred to as component (A)), α, β-unsaturated carboxylic acid (hereinafter referred to as “component (A)”). , A component (B), a sulfocarboxylic acid (hereinafter, component (C)), and a polyhydric alcohol having 3 or more valences (hereinafter, component (D)).

Specific examples of the component (A) include gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and aldehyde-modified rosin, which can be used alone or in combination.

Specific examples of the component (B) include fumaric acid,
Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, acrylic acid,
Methacrylic acid and the like can be mentioned, and these can be used alone or in combination.

As the component (C), a sulfone group (--SO
₃ M, M is a compound having a hydrogen atom, ammonium or an alkali metal) and a carboxyl group in the same molecule, and is capable of reacting with at least one of the components (A), (B) and (D). It is not particularly limited as long as it is one. Specific examples of the component (C) include sulfosuccinic acid, lower dialkyl ester of sulfosuccinic acid, 2,4-disulfobenzoic acid, 3,5-disulfobenzoic acid, 3-sulfophthalic acid, 4-sulfophthalic acid and 3,5- Disulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid; their corresponding acid anhydrides, their corresponding lower alkyl mono- or diesters, their corresponding alkyl-substituted sulfocarboxylic acids, Examples thereof include salts corresponding to these, and these can be used alone or in combination.

Examples of the component (D) include glycerin, trimethylolethane, trimethylolpropane, 3-methylpentane-1,3,5-triol, pentaerythritol, diglycerin and sorbitol.
Incidentally, as long as the performance of the aqueous pressure-sensitive adhesive composition obtained by using the obtained tackifier emulsion is not reduced, ethylene glycol, diethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene poly Various known dihydric alcohols such as oxypropylene glycol, ethylene oxide adducts of bisphenols, and propylene oxide adducts of bisphenols can be used in combination with the component (D).
It can be replaced up to the equivalent%.

The proportion of each component in the reaction product is not particularly limited, but is usually in the following respective charging ranges. That is, the charging ratio of the components (A) and (B) is in the range of 0 to 0.5 mol, preferably 0 to 0.4 mol of the component (B) per 1 mol of the component (A). Further, the charging ratio of the components (A) and (C) is 0.02 to 0.4 mol of the component (C), preferably 0.
It is in the range of 04 to 0.3 mol. Further, the charging ratio of the components (A) and (D) is the equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the component (A) [-OH (eq) /-
COOH (eq)] is 0.5 to 2.5, preferably 0.
The range is 8 to 2.0.

When the amount of the component (B) exceeds 0.5 mol with respect to 1 mol of the component (A), the water resistance of the obtained tackifier emulsion, the tackiness of the water-based adhesive, and the water resistance are sufficiently improved. do not do. Ingredient (C) to 1 mole of ingredient (A)
When it is less than 0.02 mol, the mechanical and hard water stability of the obtained tackifier emulsion is not sufficiently improved, and when it is more than 0.4 mol, the hydrophilicity of the obtained tackifier emulsion. The water resistance of the water-based pressure-sensitive adhesive is not sufficiently improved due to excessive properties. When the equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the component (A) is less than 0.5 or exceeds 2.5, both of the resulting tackifier emulsions and water-based adhesives are sufficiently improved in water resistance. Not.

The method for producing the reaction product is not particularly limited with respect to the order of preparation and the reaction conditions, as long as the usage ratio of each component satisfies the above range. For example,
A method of simultaneously charging each component and reacting by heating, by heating the components (A) and (B) to cause Diels-Alder reaction to obtain a so-called reinforced rosin, and then adding the components (C) and (D) to form an ester. Method, ingredient (A)
And (D) are esterified, then components (B) and (C)
Can be appropriately selected and employed, such as a method of further adding and continuing the reaction. In any of the above-mentioned production methods, after charging each predetermined component into a reaction vessel, the reaction vessel is subjected to normal pressure, reduced pressure or increased pressure under the presence or absence of a catalyst.
While stirring at about 50 to 300 ° C for about 3 to 30 hours,
A dehydration reaction may be performed. At this time, benzene, toluene,
The dehydration reaction may be carried out azeotropically using a solvent such as xylene. The end point of the reaction is not particularly limited, but usually, the acid value of the content of the reaction system at the time of initial charging is traced,
It may be confirmed that the esterification reaction rate is 75% or more, preferably 85% or more.

As described above, the tackifier emulsion of the present invention contains a rosin substance as a substance to be dispersed, and the rosin substance is 20% by weight or more, preferably 3%.
It is composed of 0% by weight or more of the reaction product and the following residual components. The residual component in the rosin substance is not particularly limited, but is usually rosin such as gum rosin, wood rosin, tall oil rosin; hydrogenated rosin,
Modified rosins such as disproportionated rosin, polymerized rosin, aldehyde-modified rosin, and reinforced rosin; rosin esters such as rosin ester and reinforced rosin ester; waxes such as paraffin wax and microcrystalline wax; petroleum resin, terpene resin, etc. Examples thereof include hydrocarbon resins such as hydrides, and these can be used alone or in combination of two or more kinds. Particularly preferred are the rosin esters and the hydrocarbon resin.

The tackifier emulsion of the present invention can be obtained by emulsifying and dispersing in water the rosin substance containing the reaction product and the residual component in specified amounts. In the dispersion operation, various well-known emulsifying dispersants such as low molecular weight surfactants and water-soluble polymer compounds may be appropriately selected and used in a relatively small amount.

The low molecular weight surfactant may be anionic, nonionic or cationic ionic. Examples of the anionic surfactant include dialkyl sulfosuccinic acid ester salts, alkane sulfonic acid salts, α-olefin sulfonic acid salts, polyoxyethylene alkyl ether sulfosuccinic acid ester salts, polyoxyethylene styryl phenyl ether sulfosuccinic acid ester salts, and naphthalene sulfone. Acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, etc .; as nonionic surfactants, for example, polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene Sorbitan fatty acid ester and reactive surfactants in which a vinyl group or an allyl group is introduced into these surfactants; examples of the cationic surfactant include Tiger alkyl ammonium chloride, trialkyl benzyl ammonium chloride, alkylamine acetate, alkyl amine hydrochloride can be exemplified polyoxyethylene alkyl amines, polyoxyethylene alkyl amines, etc., respectively, which are alone or possibly in combination.

Examples of the water-soluble polymer compound include casein, lecithin, polyvinyl alcohol, various modified starches, various ionic acrylic acid ester-based copolymers, carboxylic acid vinyl ester-based copolymers, and acrylamide-based copolymers. Examples thereof include polymers.

The method for dispersing the rosin substance in water using the emulsifying dispersant is, for example, Japanese Patent Publication No. 53-48.
Japanese Patent Publication No. 66-53, Japanese Patent Publication No. 53-
Any known method such as a solvent high pressure emulsification method described in JP-A-22090 or an inversion emulsification method described in JP-A-52-77206 and JP-B-58-4938 can be used. In the tackifier emulsion of the present invention, the reaction product itself has an emulsifying and dispersing ability, so that the amount of the emulsifying dispersant used can be significantly reduced as compared with known tackifier emulsions. That is, in the known tackifier emulsion, it is usually 7 to the solid content of the rosin substance.
In the present invention, 1 to 4% by weight is sufficient, while 1 to 4% by weight is sufficient.

The solid content of the tackifier emulsion of the present invention obtained as described above is usually 20 to 60% by weight, preferably 30 to 50% by weight, and the average particle diameter of the rosin substance is usually 0.4 μm. It is a degree.

The aqueous pressure-sensitive adhesive composition of the present invention is produced by blending the tackifier emulsion obtained above and the base polymer emulsion. As the aqueous pressure-sensitive adhesive composition of the present invention, as described above, the base polymer emulsion is an acrylic acid-based polymer emulsion and / or a methacrylic acid-based polymer emulsion (hereinafter referred to as (meth) acrylic-based emulsion). A water-based pressure-sensitive adhesive composition) and a water-based pressure-sensitive adhesive (hereinafter, referred to as a rubber-based water-based pressure-sensitive adhesive composition) in which the base polymer emulsion is a styrene / butadiene copolymer latex and / or a natural rubber latex.

As the (meth) acrylic polymer emulsion, emulsions used for various general (meth) acrylic pressure-sensitive adhesives can be used. The (meth) acrylic polymer emulsion is usually an acrylic ester and / or
Or various known emulsion polymerization methods of methacrylic acid ester,
For example, it can be easily produced by subjecting it to a batch charge polymerization method, a monomer sequential addition polymerization method, an emulsion monomer sequential addition polymerization method, a seed polymerization method and the like.

The acrylic ester used here,
Methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester) monomers include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2
-Ethylhexyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid 2-hydroxyethyl ester, etc. can be mentioned, and these 1 type can be used individually or in mixture of 2 or more types. Further, in order to impart stability to the obtained polymer emulsion, a small amount of (meth) acrylic acid can be used in place of part of the (meth) acrylic acid ester. Further, if desired, a copolymerizable monomer such as vinyl acetate or styrene may be used in combination as long as the adhesive property of the (meth) acrylic acid ester polymer is not impaired. The glass transition temperature (henceforth Tg) of the polymer which has these (meth) acrylic acid ester as a main component is usually -70-0 degreeC.
The degree is preferably -60 to -10 ° C. If the temperature exceeds 0 ° C., the tack is remarkably reduced, which is not preferable. Also,
As the emulsifier used in the emulsion of the acrylic polymer, an anionic emulsifier, partially saponified polyvinyl alcohol or the like can be used, and the amount thereof is usually about 0.1 to 5 parts by weight, preferably about 100 parts by weight of the polymer. 0.5 to 3 parts by weight.

Styrene-butadiene latex (hereinafter,
The term "SBR latex" refers to carboxy-modified SBR latex in addition to unmodified SBR latex, and those commercially available for pressure-sensitive adhesives can be preferably used. The SBR latex preferably has a styrene / butadiene bond ratio of 25/75 to 45/55 in weight ratio in consideration of imparting rubber elasticity and low temperature physical properties. If the amount of styrene is less than 25 parts by weight, the Tg will be lowered, so that sufficient cohesive force cannot be obtained.
Since g becomes high, the tackiness tends to decrease. Also,
The gel fraction (toluene-insoluble matter weight%) is preferably 35 to 65%. If the gel fraction is less than 35%, sufficient tack cannot be obtained. The modification rate of the carboxy-modified SBR latex is generally 0.5 to 7% by weight. As a commercially available product, for example, "PL-20" manufactured by POLYSAR CORPORATION
8 ”,“ PL-222 ”and the like. Also, as the natural rubber latex (hereinafter referred to as NR latex), generally, it can be used without particular limitation as long as it is for an adhesive, and it may be depolymerized or not. Furthermore, the above SB
The R latex and the NR latex can be appropriately used together.

In the preparation of the aqueous pressure-sensitive adhesive composition of the present invention, the mixing ratio of the tackifier emulsion and the (meth) acrylic polymer emulsion is not particularly limited, but it is usually a (meth) acrylic polymer. Emulsion 1
5 to 30 parts by weight (solid content) of the tackifier resin emulsion, preferably 7 to 2 parts, relative to 00 parts by weight (solid content).
0 parts by weight. When the amount of the tackifier resin emulsion used is less than 5 parts by weight, the adhesiveness of the resulting aqueous pressure-sensitive adhesive composition is not sufficiently improved, and when it exceeds 30 parts by weight, the tack tends to decrease. There is. The mixing ratio of the tackifier emulsion and the rubber-based latex is not particularly limited, but usually 25 to 100 parts by weight of the tackifier resin emulsion with respect to 100 parts by weight (solid content) of the rubber-based latex. (Solid content), preferably 40 to 80 parts by weight. When the amount of the tackifier resin emulsion used is less than 25 parts by weight, the adhesiveness of the resulting aqueous pressure-sensitive adhesive composition is not sufficiently improved.
If it exceeds 100 parts by weight, the cohesive force tends to decrease.

The tackifier emulsion and the aqueous pressure-sensitive adhesive composition of the present invention may contain a small amount of a defoaming agent, a thickener, a filler, an antioxidant, a water-proofing agent, a film-forming aid, etc., if necessary. May be. The tackifier emulsion of the present invention may be used in combination with an emulsion of a known tackifier (rosin ester, reinforced rosin ester, terpene resin, petroleum resin, etc.) without departing from the object of the present invention.

[0029]

EFFECT OF THE INVENTION The tackifier emulsion of the present invention has excellent properties as a tackifier, mechanical stability,
Excellent in hard water stability and miscibility with base polymer emulsion. Further, the aqueous pressure-sensitive adhesive composition of the present invention using the tackifier emulsion has tackiness, adhesiveness, cohesive strength,
It has excellent water resistance and can be suitably used for pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels, etc. in various applications such as electrical insulation, electric wire bundling, miscellaneous goods, cosmetics, office work and the like.

[0030]

EXAMPLES The present invention will be described in more detail below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. In each example, part and%
Are by weight unless otherwise noted.

Production Example 1 (Production of Reaction Product) Purified disproportionated rosin 100 having an acid value of 170 was placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a water divider and a condenser.
Parts, 5 parts of fumaric acid, 5 parts of sodium 5-sulfoisophthalate and 13 parts of glycerin, were charged under a nitrogen stream to 2
The mixture was heated to 50 ° C. and esterified at the same temperature for 12 hours to obtain a reaction product having an acid value of 15 with a reaction rate of about 90% or more.

Production Examples 2 to 9 (Production of Reaction Product) Reactions were the same as in Production Example 2, except that at least one item of the type of each component and the amount used was changed as shown in Table 1. Esterification up to 90% or more,
Various reaction products were obtained.

Production Example a (Rosin Ester Remaining Component of Rosin Substance) A rosin ester (acid value 15 obtained by reacting 100 parts of purified disproportionated rosin having an acid value of 170 and 12 parts of pentaerythritol for 12 hours at 250 ° C. ).

Production Example b (Reinforced Rosin Ester Remaining Component of Rosin Substance) 100 parts of purified disproportionated rosin having an acid value of 170, glycerin 1
A toughened rosin ester (acid value 18) obtained by reacting 2 parts and 4 parts of fumaric acid at 250 ° C. for 12 hours.

Examples 1 to 9 (high pressure emulsification method) 100 parts of each rosin substance (reaction product) shown in Table 1 was dissolved in 100 parts of toluene, and then an emulsifying dispersant (polyoxyethylene (n = 13) di 3 parts of styryl phenyl ether sulfate ester sodium salt) and 103 parts of warm water at 60 ° C. are mixed, and then the shearing force is 300 kg / cm.
Emulsify by passing it twice through a piston type high pressure emulsifier adjusted to ² , and further reduce the pressure to distill off toluene to obtain a nonvolatile content of 50%.
A tackifier emulsion of was obtained.

Example 10 (inversion method) 100 parts of the reaction product obtained in Production Example 1 was charged into 150 parts.
After heating and melting at 0 ° C., 3 parts of the emulsifying dispersant and 30 parts of hot water at 95 ° C. were gradually added with stirring to obtain a water-in-oil emulsion. Hot water of 90 ℃ 73 with vigorous stirring
Parts were added over 1 minute and the phases were inverted to obtain an oil-in-water type tackifier emulsion having a nonvolatile content of 50%.

Comparative Example 1 In Example 1, instead of using the reaction product obtained in Production Example 1 alone, 10% of the reaction product and the remaining components (45% each in Production Example a and Production Example b) High pressure emulsification was carried out in the same manner as in Example 1 except that the mixture consisting of
% Tackifier emulsion was obtained.

Comparative Example 2 In Example 1, the rosin substance was replaced by the reaction product obtained in Production Example 1 by using the strengthened rosin ester of Production Example b, and the amount of the emulsifying dispersant used was 8 parts. High pressure emulsification was carried out in the same manner as in Example 1 except that the non-volatile content was 50%.
A tackifier emulsion of was obtained.

Comparative Example 3 High pressure emulsification was carried out in the same manner as in Example 1 except that the rosin substance used in Example 1 was replaced with the reaction product obtained in Production Example 1 by using the reinforced rosin ester of Production Example b. However, a considerable amount of aggregate was generated. Therefore, after filtering the aggregate through a 100-mesh wire net, a tackifier emulsion having a nonvolatile content of 46% was obtained.

Production Example c (Production of Acrylic Polymer Emulsion) In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, under a nitrogen stream at 70 ° C., 44.46 parts of water and an anionic system were prepared. After 0.90 parts of an emulsifier (trade name Hitenol S, solid content 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was mixed and dissolved, a monomer mixture (n-butyl acrylate 43.90, 43.90) was stirred and stirred under a nitrogen stream. Parts and acrylic acid 1.36 parts) and an aqueous initiator solution (potassium persulfate 0.
23 parts, pH adjuster (heavy soda) 0.11 part and water 9.
04 parts) and 1/10 amount of each, and the prepolymerization reaction was carried out at 70 ° C. for 30 minutes, after which the remaining monomer mixture and the remaining aqueous initiator solution were added dropwise over 2 hours, and further 1
The time was maintained to complete the polymerization. 100 after cooling to room temperature
It was filtered through a mesh wire net to obtain an acrylic polymer emulsion having a solid content of 45.7%.

(Evaluation of Performance of Tackifier Emulsion) The tackifier emulsions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated for mechanical stability, hard water dilution stability and miscibility with a base polymer. It was measured and evaluated by the following method. Table 2 shows the results.

(Mechanical stability): 50 g of a tackifier emulsion was added to a Marlon type stability tester (Shinsei Sangyo Co., Ltd.).
(Manufactured by Mitsui Chemical Co., Ltd.), and a mechanical shear was added for 10 minutes at a temperature of 25 ° C., a load of 20 kg, and a rotation speed of 1000 rpm.
Then, the produced aggregate was filtered through a 200-mesh wire net, and the amount of precipitation with respect to the total solid content was measured and expressed as a percentage. (Stability in hard water): diluted with hard water having a hardness of 100 so that the solid content concentration of the tackifier emulsion becomes 5%, and then 2 at room temperature.
After leaving for 4 hours, the presence or absence of change in properties such as aggregation, precipitation, and separation of the diluted solution was visually judged. (Mixability): 10 parts of tackifier emulsion (solid content)
And 90 parts (solid content) of the acrylic polymer emulsion of Production Example C were mixed and allowed to stand at 40 ° C. for 1 month, and then the presence / absence of change in properties such as aggregation, precipitation and separation of the mixture was visually judged.

(Preparation of Acrylic Emulsion Adhesive Composition) The tackifier emulsion obtained in the above Examples or Comparative Examples and the acrylic polymer emulsion obtained in Production Example C were mixed at the ratios shown in Table 3. Blended to obtain various aqueous pressure-sensitive adhesive compositions.

(Evaluation of Performance of Acrylic Emulsion Adhesive Composition) The adhesive thickness after drying the aqueous adhesive composition is 30.
It is applied to a polyester film having a thickness of 40 μm so as to have a thickness of
An adhesive sheet was created. The performance of the obtained pressure-sensitive adhesive sheet was evaluated by the following test methods. The results are shown in Table 3.

(Adhesive strength): measurement temperature 20 ° C., pulling speed 3
Adhesive force (g when peeled 180 degrees at 00 mm / min)
/ Cm) was measured. The adherend is a stainless steel plate (SS)
It is. (Tack): J. J. described in JIS Z 0237. D
The ow method was used to measure the inclination at 30 degrees and the measurement temperature at 20 ° C. The numerical values in Table 3 are Ball No. Is shown. (Cohesive force): According to JIS C 2107, the sticking area is 2
The shift (mm) after 1 hour at 40 ° C. with respect to the stainless steel plate was measured with 5 × 25 mm ² and a load of 1 kg. (Muddyness of sheet): The adhesive sheet after drying was visually evaluated. X indicates turbidity, and Δ indicates slightly turbidity. (Water resistance): After the pressure-sensitive adhesive sheet was immersed in water for 24 hours, the degree of whitening of the pressure-sensitive adhesive layer was visually determined. X indicates remarkable whitening, Δ indicates considerable whitening, and ○ indicates almost no whitening.

(Preparation of rubber latex adhesive composition)
The tackifier emulsions obtained in the above Examples or Comparative Examples, and carboxy-modified SBR latex (manufactured by Polycer Co.,
"PL-222", bound styrene content 42%, nonvolatile content 5
2%) in the proportions shown in Table 4 to obtain various aqueous pressure-sensitive adhesive compositions.

(Performance Evaluation of Rubber Latex Adhesive Composition) "Hiker 1571C" (BF Goodrich) as a primer on a soft vinyl chloride tape having a thickness of 150 μm.
Co., Ltd.) / “PL-222” = 1/1 (weight ratio) was applied to a dry weight of ² to 3 g / m ² and then 3 at 70 ° C.
The film was dried in a circulating air drier for 2 minutes and left in a room at a temperature of 20 ° C. and a relative humidity of 65% for 2 hours. Further, the weight of the aqueous pressure-sensitive adhesive composition after drying on the primer-coated surface is 28 to
It was coated at 30 g / m ² and dried at 105 ° C. for 3 minutes in a circulating air drier, and immediately wound up to prepare a vinyl chloride tape. Then, it was left to stand in a room at a temperature of 20 ° C. and a relative humidity of 65% for 24 hours. The performance of the vinyl chloride tape thus obtained was evaluated by the following test method. Table 4 shows the results
Shown in

(Adhesive strength): Same as above (Tack): Same as above (Cohesive strength): Laminating area 19 × 20 mm ² , load 1 k
Glue the adhesive surfaces of vinyl chloride tape together at 20 ° C
Retention time (minutes) in.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

Claims (10)

[Claims] 1. A tackifier emulsion comprising a rosin substance, a dispersant and water, the rosin substance comprising:
(A) rosins, (B) α, β-unsaturated carboxylic acids,
A tackifier emulsion comprising 20% by weight or more of a reaction product comprising (C) a sulfocarboxylic acid and (D) a polyhydric alcohol having a valence of 3 or more. 2. The reaction product, wherein the component (B) is 0 to 0.5 mol per 1 mol of the component (A), and the component (C) is 0.02 to 0. The tackifier according to claim 1, wherein each component is heated and reacted in an amount of 4 mol and a use ratio such that the equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the component (A) is 0.5 to 2.5. Agent emulsion. 3. The reaction product contains 0 to 0.4 mol of the component (B) with respect to 1 mol of the component (A) and 0.04 to 0.3 mol of the component (C) with respect to 1 mol of the component (A). Molar and component (A)
The tackifier emulsion according to claim 1 or 2, wherein each component is heated and reacted at a use ratio such that the equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the above is 0.8 to 2.0. 4. The tackifier emulsion according to claim 1, 2 or 3, wherein the content of the reaction product in the rosin substance is 30% by weight or more. 5. The residual component other than the reaction product in the rosin substance is at least one of rosins, modified rosins, rosin esters, waxes, and hydrocarbon resins. The tackifier emulsion according to any one of claims. 6. An aqueous pressure-sensitive adhesive composition comprising the tackifier emulsion according to any one of claims 1 to 5 and a base polymer emulsion and / or a base polymer latex. 7. The aqueous pressure-sensitive adhesive composition according to claim 6, wherein the base polymer emulsion is an acrylic acid polymer emulsion and / or a methacrylic acid polymer emulsion. 8. The aqueous pressure-sensitive adhesive composition according to claim 6, wherein the base polymer latex is a styrene / butadiene copolymer latex and / or a natural rubber latex. 9. An acrylic polymer emulsion and / or
Alternatively, 5 to 30 parts by weight (as solid content) of the tackifier resin emulsion is added to 100 parts by weight (as solid content) of the methacrylic acid polymer emulsion.
The aqueous pressure-sensitive adhesive composition described. 10. A tackifier resin emulsion is added in an amount of 25 to 100 parts by weight (as solid content) to 100 parts by weight (as solid content) of styrene-butadiene copolymer latex and / or natural rubber latex. The aqueous pressure-sensitive adhesive composition according to claim 8.