JPH05247150A - Aqueous dispersion composition of tackifier resin - Google Patents

Abstract

PURPOSE:To provide a concentrated aqueous dispersion of a tackifier resin which has heretofore been difficult to form a dispersion having high solid content. CONSTITUTION:The objective aqueous dispersion of a tackifier resin is produced by emulsifying 100 pts.wt. of a tackifier resin and 1-100 pts.wt. of a dispersing agent containing a copolymer produced by reacting a monomer having an alpha,beta-unsaturated double bond with a dibasic acid having unsaturated group or its anhydride in the presence of 0.1-50 pts.wt. of an anionic polymeric emulsifier and 0.1-50 pts.wt. of a low-molecular surfactant. It does not cause the lowering of adhesive properties and cohesivity even by using in an aqueous adhesive. It has excellent compatibility and is applicable without problem. It is resistant to degradation and has extremely excellent storage stability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous dispersion composition of a resin usually called a tackifier in the field of adhesives and tackifiers.

[0002]

2. Description of the Related Art Conventionally, as water-based adhesives, natural rubber latex, styrene-butadiene rubber latex (hereinafter referred to as SBR latex), carboxylated styrene-butadiene rubber latex, (hereinafter referred to as carboxylated SBR latex), acrylic emulsion ( These are known as latexes) mixed with an aqueous dispersion of tackifying resin, and are applied to various base materials such as sheets and tapes, and are used for manufacturing labels, PVC tapes, etc. As an adhesive or synthetic resin,
It is widely used as an adhesive for joining wood materials to each other and laminating films and papers.
A tackifying resin aqueous dispersion is generally produced for emulsification and dispersion in water by a method in which a solution of the tackifying resin dissolved in an organic solvent is mixed with water in the presence of a low molecular surfactant while stirring. Has been done.

Tackifying resins generally have a high softening temperature of 100 ° C. or higher, as well as a softening temperature of 100 ° C.
The temperature at the time of emulsion dispersion (usually 50 to 10
Since the melt viscosity at 0 ° C) is very high, stirring may be difficult, or the tackifying resin in the molten state may not be sufficiently micronized. Therefore, the tackifying resin may be emulsified and dispersed in water in the molten state. Is difficult. For this reason, as described above, the tackifying resin is once dissolved in an organic solvent and then emulsified and dispersed in water as a solution. However, when the aqueous dispersion produced using the above organic solvent is used for applications such as adhesives and adhesives, there is a risk of ignition and explosion during storage, and the release of organic solvent during coating processing. The problem of the deterioration of the work environment due to is being highlighted. In addition, it is difficult to completely remove the organic solvent from the aqueous dispersion containing the organic solvent, and if the removal is forcibly performed, the emulsified dispersion system is destroyed.

More recently, water-based adhesives are energy-saving,
Due to the demand for labor saving, the concentration tends to be high, and therefore, it is necessary to increase the concentration of the tackifying resin aqueous dispersion which is a constituent component of the aqueous adhesive. However, when the solid content concentration of the tackifying resin aqueous dispersion is increased (35% by weight or more), the viscosity of the tackifying resin aqueous dispersion is increased, or the particle size of the tackifying resin in the aqueous dispersion is increased, and storage There is a drawback in that stability and mechanical stability are deteriorated, and spots and streaks are formed during coating, which makes uniform coating difficult. Therefore, a method of mixing a natural resin such as casein as a stabilizer or a method of dissolving a tackifying resin in a liquid resin such as a plasticizer and dispersing the same together with a low molecular weight surfactant in an aqueous solution have been used. However, the mixing of these stabilizers and liquid resins is not sufficient for improving the coating processability, and also causes deterioration of the adhesive properties of the water-based adhesive, reduction of cohesive force and rot. It will reduce the product value and quality of the product.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above problems, the present inventors have found that a tackifying resin and a dispersant are used in combination with an anionic polymer emulsifier and a low molecular surfactant. By emulsifying by, it became possible to highly concentrated aqueous dispersion of the tackifying resin, which was conventionally difficult to achieve high solidification, and it was found that the mixture of the organic solvent in the tackifying resin aqueous dispersion was prevented, and the present invention was reached. It was

[0006]

That is, the present invention provides 100 parts by weight of a tackifying resin (A) and a monomer (a) having an α, β unsaturated double bond and a dibasic acid having an unsaturated group, or 1 to 100 parts by weight of a dispersant (B) containing a copolymer or a derivative thereof obtained by reacting with an anhydride (b), 0.1 to 50 parts by weight of an anionic polymer emulsifier (C) and a low molecular interface Provided is a tackifier resin aqueous dispersion composition obtained by emulsifying with 0.1 to 50 parts by weight of an activator (D). Furthermore, the dispersant (B)
Is a copolymer or derivative thereof obtained by reacting a monomer (a) having an α, β unsaturated double bond with a dibasic acid having an unsaturated group or an anhydride thereof (b), or 1 to 50 parts by weight thereof. And a tackifying resin aqueous dispersion composition containing 50 parts by weight or less of the modified tackifying resin (c). The fine particles in the aqueous dispersion composition of the present invention have a core / shell structure in which the tackifying resin and the dispersant serve as cores, and the anionic polymer emulsifier and the low molecular surfactant serve as shells.

The tackifying resin (A) is a resin such as a rosin acid ester, a terpene resin, a petroleum resin, or a dammer. The rosin acid ester is an esterified product of a rosin component and an alcohol component, and specific examples of the rosin component include resin acids such as abietic acid, parastophosphoric acid, neoabietic acid, pimaric acid, isopimaric acid, and dehydroabietic acid. Examples thereof include gum rosin, tall oil rosin, wood rosin, or asymmetrical rosins, hydrogenated rosins, polymerized rosins, maleic acid- or acrylic acid-modified rosins, which are the components. Specific examples of the alcohol component, n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol,
Monohydric alcohols such as stearyl alcohol,
Dihydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, dipropylene glycol, neopentyl glycol and the like, trivalent alcohols such as glycerin and trimethylolpropane,
Examples thereof include tetrahydric alcohols such as pentaerythritol diglycerin and hexahydric alcohols such as dipentaerythritol.

Examples of the terpene-based resin include gum turpentine oil containing α-pinene and β-pinene as main components, and terpene-based resin obtained by polymerization from wood turpentine oil or the like, or a phenol addition product thereof. As petroleum-based resins, among cracked oils obtained by removing olefins having 2 to 4 carbon atoms such as ethylene, propylene and butadiene in naphtha cracking, aliphatic, alicyclic, aromatic groups having 5 or more carbon atoms are used. The resin obtained by polymerizing the residual olefins of is mentioned. In addition, coumarone-based resins, which are polymers of coumarone and indene, which are fractions of coal tar, and resins such as dammers and copals can be mentioned.

Monomers having α, β unsaturated double bonds
There is no particular limitation on (a), for example, α-olefin,
Examples include diolefins, allyl monomers, N-vinyl monomers, vinyl ethers, vinyl sulfides, (meth) acrylic acid ester monomers and other copolymerizable vinyl monomers and vinylidene monomers, and one or more of them may be used. More specifically, as the α-olefin, ethylene, propylene, butylene, isobutylene, pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,
1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-
Examples thereof include tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene, and mixtures thereof. As a commercially available product, dialen 208 (C
20-28), Dialen 30 (C30 or more) (Mitsubishi Kasei Co., Ltd.) and the like.

Examples of diolefins include butadiene, isoprene, neoprene, chloroprene and the like, and mixtures thereof. Examples of the allyl monomer include allyl acetate, isopropenyl acetate, allyl chloride, isopropenyl chloride, trans-propenyl chloride, cis-propenyl chloride and the like, and mixtures thereof. Examples of the N-vinyl monomer include N-vinylcarbazole, N-vinyl-2-pyrrolidone, N-vinylphthalimide and the like, and mixtures thereof. Examples of vinyl ethers include linear or branched aliphatic alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, and hexyl vinyl ether; p-dioxene; and mixtures thereof.

Examples of vinyl sulfides include ethyl vinyl sulfide, phenyl vinyl sulfide and the like, and mixtures thereof. (Meth) acrylic acid ester monomers include linear or branched fats such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, etc. Examples thereof include acrylic acid esters of group alcohols and corresponding methacrylic acid esters and the like, and mixtures thereof. Other copolymerizable vinyl monomers include vinyl esters,
Examples thereof include vinyl pyridine, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, β-methylstyrene, acrylonitrile, methacrylonitrile, and the like and mixtures thereof.

Examples of the dibasic acid having an unsaturated group or its anhydride (b) include maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride and citraconic anhydride. One or two or more are used, but maleic anhydride is industrially advantageous. The copolymer obtained by reacting a monomer having an α, β unsaturated double bond (a) with a dibasic acid having an unsaturated group or an anhydride thereof (b) is a solution polymerization, a bulk polymerization or an emulsion polymerization. It can be produced by suspension polymerization or the like, but is not particularly limited in these polymerization methods and reaction operations. As the polymerization initiator, benzoyl peroxide, lauryl peroxide, cumene peroxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, peroxides such as t-butyl peroxybenzoate, azobisisobutyronitrile,
Examples thereof include azo compounds such as azobis-2,4-dimethylvaleronitrile and inorganic compounds such as ammonium persulfate and potassium persulfate.

Further, the carboxyl group based on the carboxylic acid anhydride in the copolymer is esterified with a compound having at least one hydroxyl group in the molecule, amidated with a compound having at least one amino group, or Modification such as imidization or chelation with a metal compound may be performed. By modifying, various physical properties such as acid value, molecular weight, viscosity, softening point, strength, various resistances, flexibility, compatibility and dispersibility can be freely controlled.

The hydroxide used for esterification is not particularly limited as long as it has one or more hydroxyl groups in the molecule, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol,
sec-butanol, tert-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, α-oxybutyric acid, 12 -Hydroxystearic acid and the like and mixtures thereof are used.

The amino compound used for amidation and imidation is not particularly limited as long as it has one or more amino groups in the molecule, and examples thereof include methylamine, ethylamine and propylamine. , Isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o-toluidine, 2-ethylaniline, 2-
Fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindane, aspartic acid, glutamic acid, γ-aminobutyric acid and the like and mixtures thereof. Be done.

Further, as the metal compound used for chelation, for example, sodium, potassium, calcium,
Acetate salts of magnesium, aluminum, zinc, nickel, iron, cobalt, manganese, copper and the like, acetylacetone salts, inorganic metal compounds represented by organic metal compounds and oxides represented by metal alkoxides, and the like are particularly preferable. It is not limited.

These reactions may be carried out in an aqueous system, without solvent or in combination with a solvent, but the acid value of the reaction product is 0 to 400, preferably 10 to 200.
Those in the range of are preferable. When the acid value is 400 or more, the viscosity of the tackifying resin aqueous dispersion becomes high, and the particle size thereof increases, resulting in poor storage stability and mechanical stability of the aqueous dispersion.
This is because the coating processability is deteriorated. A copolymer or a derivative thereof obtained by reacting a monomer (a) having an α, β unsaturated double bond with a dibasic acid having an unsaturated group or an anhydride thereof (b) is a tackifier resin (A ) For 1 ~
Used in the range of 50% by weight, preferably 5 to 20% by weight
Used in. If it is less than 1% by weight, the dispersibility of the tackifier resin is poor and the particle size is large, so that spots or streaks are likely to occur during coating. If it exceeds 50% by weight, the performance as a tackifying resin is inferior, and therefore the improvement of the adhesive property and cohesive force of the compounded water-based adhesive is not recognized.

The modified tackifying resin (c) used in the dispersant (B) constituting the core part is used for increasing the compatibility with the anionic polymer emulsifier in the shell part. The resin of the same type as the tackifying resin (A) is modified with a monomer having a polymerizable unsaturated double bond. Specifically, the acrylic resin is subjected to acrylic copolymerization in the molten state of the tackifying resin (husk-like polymerization) or in the presence of an organic solvent (solution polymerization) to graft, block or interpenetrate the polymer of the acrylic monomer ( IPN) is prepared by acrylic modification, or a tackifying resin is kneaded with a liquid synthetic rubber such as liquid polybutadiene and graft-modified with peroxide or the like, and rubber-modified such as blocking.

The acrylic monomer used in the modified tackifying resin (c) is composed of a (meth) acrylic acid alkyl ester and a copolymerizable polar functional group-containing monomer. (Meth) acrylic acid alkyl ester has 1 to 20 carbon atoms in the alkyl group, preferably 4 to 1
Eight alkyl esters, more specifically, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, acrylic Examples thereof include acrylic acid esters of linear or branched aliphatic alcohols such as dodecyl acid acid, lauryl acrylate, and stearyl acrylate, and corresponding methacrylic acid esters.

The polar functional group-containing monomer is one having a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a methylol group, a glycidyl group, an amino group, an amide group, an ethyleneimine group, an isocyanate group, and the like. As, acrylic acid, methacrylic acid, maleic anhydride, maleic acid, maleic acid monoester, itaconic acid, crotonic acid, mono- (2-hydroxyethyl-α-chloroacrylate) acid phosphate, (meth) acrylic acid 2- Hydroxypropyl, 2-hydroxyethyl (meth) acrylate, polyethylene glycol acrylate, N-methylol acrylamide, N-methylol methacrylamide, N-methylaminoethyl acrylate, N-tributylaminoethyl acrylate, N, N-dimethylaminoethyl Acrylate, N, N-dime Examples thereof include tylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, acrylamide, methacrylamide, vinylpyrrolidone, glycidyl acrylate, glycidyl methacrylate and vinyl isocyanate. The polar functional group-containing monomer is contained in an amount of 0.01 to 25% by weight of the acrylic monomer, and is contained in one kind or two or more kinds.

Further, in the modified tackifying resin (c),
In addition to the above monomers, a monomer having a polymerizable unsaturated double bond such as vinyl ester, vinyl pyridine, vinyl acetate, vinyl propionate, styrene, acrylonitrile, methacrylonitrile, butadiene, chloroprene can be contained. These monomers are appropriately selected according to the desired physical properties and may be used alone or in combination of two or more. In addition, a part of the tertiary ammonium salt of the tackifying resin (c) obtained by copolymerizing a tertiary amino group-containing monomer is reacted with an epoxy group such as glycidyl (meth) acrylate to form a polymerizable unsaturated diamine. It is also possible to introduce a heavy bond to make the core part reactive.

The ratio of the tackifying resin to the monomer having a polymerizable unsaturated double bond used is usually 100: by weight.
It is 0.1 to 50, preferably 100: 1 to 30. Modified tackifying resin (c) is
.About.50% by weight, preferably 0 to 30% by weight. Examples of the polymerization initiator of the modified tackifying resin (c) include peroxides such as benzoyl peroxide, lauryl peroxide and cumene peroxide, and azo compounds such as azobisisobutyronitrile. Further, as the organic solvent used when produced by solution polymerization, n-pentane, toluene, benzene, n-hexane, dioxane,
Methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate and the like, and alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol may be mixed.

The anionic polymer emulsifier (C) is composed of a reactive monomer containing an acid component as an essential component and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms (meth). Acrylic copolymer, which contains other polar functional group-containing monomers and copolymerization components as needed, and which is usually neutralized with an alkaline compound in order to exhibit the function as an emulsifier. Is. The acid component-containing reactive monomer has a carboxyl group, a phosphoric acid group, a sulfonic acid group, and the like, and specifically, acrylic acid, methacrylic acid, maleic anhydride, maleic acid, maleic acid monoester, itaconic acid, Examples thereof include crotonic acid and mono- (2 hydroxyethyl-α-chloroacrylate) acid phosphate. (Meta)
As the acrylic acid alkyl ester, the same compounds as those used for the modified tackifying resin (c) can be used.

Other copolymerizable polar functional group-containing monomers are those having a hydroxyl group, a methylol group, a glycidyl group, an amino group, an amide group, an ethyleneimine group, an isocyanate group and the like. ) 2-Hydroxypropyl acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol acrylate, N-methylol acrylamide, N-methylol methacrylamide, N-methylaminoethyl acrylate, N-tributylaminoethyl acrylate, N, N -Dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, acrylamide, methacrylamide, vinylpyrrolidone, glycidyl acrylate, glycidyl methacrylate, vinyl isocyanate, etc. It is below. The polar functional group-containing monomer is a (meth) acrylic copolymer of 0.
It is contained in an amount of 01 to 25% by weight, and is contained in one kind or two or more kinds.

The (meth) acrylic copolymer may contain monomers such as vinyl ester, vinyl pyridine, vinyl acetate, vinyl propionate, styrene, acrylonitrile, methacrylonitrile, butadiene and chloroprene, in addition to the above monomers. .. The anionic polymer emulsifier (C) can be produced by solution polymerization, bulk polymerization or the like. Examples of the polymerization initiator include peroxides such as benzoyl peroxide, lauryl peroxide and cumene peroxide, and azo compounds such as azobisisobutyronitrile. The organic solvent used in the case of producing by solution polymerization, n-pentane, toluene, benzene, n-hexane, dioxane, methyl ethyl ketone,
Methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate and the like, and alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol may be mixed.

In preparing the anionic polymer emulsifier (C), examples of the alkaline compound used for neutralization include metal hydroxides, ammonia and tertiary organic amines, but the tertiary organic amines are used. Is desirable.
For example, triethylamine, tributylamine, N, N-dimethylbutylamine, N-ethyl-1,2-dimethylpropylamine, tri-n-octylamine, N-methyl-di-n-octylamine, triallylamine, N-methyl Diallylamine, N, N-diisopropylethylamine, 3-dimethylaminopropanol, dimethylaminoethanol, N-isobutyldiethanolamine, N-methylmorpholine, N-methylpiperidine, N-methyl-2-pipecoline, N-methyl-
3-piperidinemethanol, N-methyl-3-hydroxypiperidine, N-ethyl-3-hydroxypiperidine, dipiperidinomethane, N, N-dimethylbenzylamine, N-methylpyrrolidine, pyrazine, pyridine, α-picoline, Examples thereof include organic amines such as 2-pyridinemethanol and N, N-dimethylaniline, and mixtures thereof, but are not particularly limited thereto.

These anionic polymer emulsifiers are used as they are, or a part of the tertiary ammonium salt of a copolymer obtained by copolymerizing a monomer containing a tertiary amino group is reacted with an epoxy group such as glycidyl (meth) acrylate. As a result, a polymerizable unsaturated double bond is introduced, and it can also be used as a reactive polymer emulsifier. By using the reactive polymer emulsifier, the fine particles in the aqueous dispersion become microgel fine particles. Further, if a double bond is present in the core portion of the microgel fine particles, it becomes possible to fix the polymeric emulsifier to the core portion. The tackifying resin aqueous dispersion prepared by using the reactive polymer emulsifier can improve various resistances such as water resistance and heat resistance. Anionic polymer emulsifier (C) is 0.1 to 50% by weight with respect to the tackifying resin (A),
Desirably 3 to 20% by weight is used. If it is less than 0.1% by weight, a stable emulsion cannot be obtained and the mechanical stability is deteriorated. If it exceeds 50% by weight, the performance as a tackifying resin cannot be sufficiently obtained.

Examples of the low-molecular-weight surfactant (D) include anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants. Anionic surfactants or nonionic surfactants It is desirable to use an activator. Examples of the anionic surfactant include a phosphate emulsifier, a sulfonate emulsifier, a sulfate emulsifier, and a fatty acid emulsifier such as sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate. , Sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulphonate, alkoxyalkyl phosphate, alkyl phosphate, alkyl phosphate diethylamine salt, alkyl phosphate potassium salt, poly Sodium oxyethylene lauryl ether sulfate, polyoxyethylene sodium alkyl ether sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, polyoxyethylene Sodium alkyl phenyl ether sulfate, sodium alkyl sulfonate, mixed fatty acid soda soap, semi-hardened beef tallow fatty acid soda soap, semi-hardened beef tallow fatty acid soap, stearic acid soda soap, potassium oleate soap, castor oil Examples thereof include potassium soap, higher alcohol sodium sulfate, sodium salt of β-naphthalene sulfonic acid formalin condensate, special aromatic sulfonic acid formalin condensate, and special carboxylic acid type surfactant.

As the nonionic surfactant, a general nonionic emulsifier, for example, glycerol monostearate, glycerol monooleate, sorbitan monolaurate, sorbitan monopalmineate, sorbitan monostearate is used. -, Sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmineate, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate
, Polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol tetraoleate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether -, Polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc., but are not particularly limited and are not affected by HLB and the like.

Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt, an alkylpyridinium salt, an alkylimidazolium salt and the like. Examples of the amphoteric surfactant include alkylbetaine, alkylamine oxide, phosphadylcholine (also referred to as lecithin), and the like. Among these emulsifiers, one kind or a mixture of two or more kinds can be used. The low molecular weight surfactant (D) is used in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, of the tackifying resin (A). If it is less than 0.1% by weight, a stable emulsion cannot be obtained and the mechanical stability is deteriorated. If it exceeds 50% by weight, sufficient water resistance cannot be obtained.

When emulsifying the tackifying resin, first, the tackifying resin (A), the dispersant (B), the anionic polymer emulsifier
(C) and the low-molecular-weight surfactant (D) are blended to remove the solvent, and then water substitution is performed to emulsify to prepare an aqueous dispersion. If the solvent is removed after water replacement, a stable emulsion cannot be obtained. The particle size of the fine particles in the aqueous dispersion is 0.1 to 10.0 μm. In addition, a microgel aqueous dispersion can be prepared by emulsion polymerization using a reactive anionic polymer emulsifier (C). Considering the properties as an emulsion and various physical properties when blended in an aqueous adhesive, it is desirable to prepare a microgel aqueous dispersion. The particle size of the microgel obtained by emulsion polymerization is usually 0.01 to 0.5 μm as measured by the light scattering method. The temperature of the emulsion polymerization is 50 to 95 ° C, preferably 65 to 80 ° C, and the solid content ratio in the emulsion polymerization is 10 to 70% by weight, preferably 30 to 60% by weight. Further, the polymerization initiator used for emulsion polymerization includes peroxides, azo compounds and persulfates, but is not particularly limited.

Seed polymerization in which an acrylic monomer is reacted with the tackifying resin aqueous dispersion obtained in the present invention as a seed component is also possible, and an excellent aqueous adhesive can be prepared. Further, the tackifying resin aqueous dispersion composition, if necessary, a pigment, a filler, a pigment dispersant, a plasticizer,
Usual compounding agents such as thickeners, preservatives and defoamers can be added, and they can also be used for applications such as lubricants, hot melt resins, inks and paints in addition to adhesives.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. (1) Preparation of a copolymer or a derivative thereof obtained by reacting a monomer having an α, β unsaturated double bond with a dibasic acid having an unsaturated group or an anhydride thereof [Production Example 1] 1-octadecene Charge 757.4 g, di-t-butyl peroxide 2.7 g, and toluene 10 g to the flask,
After purging with nitrogen, 294.2 g of maleic anhydride was added 9.8 g every 2 minutes, and 2.1 g of di-t-butyl peroxide was added 0.7 g every 20 minutes while heating and stirring at 150 ° C. After the addition was completed, the temperature of the system was kept at 160 ° C., and the reaction was further continued for 6 hours. Then, the contents were taken out while being heated, cooled and solidified to obtain a resin having an acid value of 320.

[Production Example 2] 1276 g of diallen 208 (manufactured by Mitsubishi Kasei), 3.6 g of di-t-butyl peroxide, and 14 g of toluene were charged into a flask, which was purged with nitrogen and then heated at 150 ° C. with stirring to give maleic anhydride. 412 g of acid every 2 minutes
13.7 g each and 20 g of di-t-butyl peroxide 1.8 g
0.9 g was added every minute. After the addition was completed, 1 g of di-t-butyl peroxide was further added, the temperature of the system was kept at 160 ° C, and the reaction was continued for 6 hours. Then, the contents were taken out at the time of heating to cool and solidify to obtain a resin having an acid value of 234. Obtained. Then,
200 g of the obtained resin and 74.7 g of stearylamine were placed in a flask and melted in a nitrogen stream with stirring to 180 ° C.
The reaction was carried out for 5 hours. After completion of the reaction, the content was taken out while being hot, cooled and solidified to obtain a resin having an acid value of 71.9. [Production Example 3] 200 g of the resin obtained in Production Example 1 and 34.0 g of cyclohexylamine were placed in a flask, melted in a nitrogen stream while stirring, and reacted at 180 ° C for 5 hours. After the reaction was completed, the content was taken out while being hot, cooled and solidified to obtain a resin having an acid value of 108.

(2) Preparation of anionic polymer emulsifier [Production Example 4] The following monomers were charged in a 2 L 4-neck flask equipped with a stirrer, thermometer, condenser, and dropping funnel, and 2-ethylhexyl acrylate 90 parts methacrylic acid 50 parts 2-Dimethylaminoethyl methacrylate 10 parts Azobisisobutyronitrile 1.6 parts 2-Propanol 200 parts Polymerization reaction is carried out at 80 ° C in a nitrogen atmosphere while heating with stirring, and after 2 hours, azobisbutyronitrile 0.4 Part added,
Then, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and a reaction product was obtained. After cooling to room temperature, triethylamine
A mixture of 58 parts and 90 parts of deionized water was added to obtain a polymer emulsifier having a solid content of 30%. [Production Example 5] To the reaction product obtained in the same manner as in Production Example 4, 10 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C in an air atmosphere and held for 3 hours to cause a reaction in which a methacryl group was pendant. I got a thing. After cooling to room temperature, a mixture of 58 parts of triethylamine and 110 parts of deionized water was added to obtain a reactive polymer emulsifier with a solid content of 30%.

[Production Example 6] The following monomers were charged in a flask, and in the same manner as in Production Example 4, a polymer emulsifier with a solid content of 30% was obtained. Octyl acrylate 70 parts Butyl acrylate 35 parts Acrylic acid 45 parts Azobisisobutyronitrile 1.6 parts 2-Propanol 200 parts [Production Example 7] The following monomers were charged in a flask and Production Example 4
A polymerization reaction was carried out in the same manner as above to obtain a reaction product. Octyl acrylate 70 parts Butyl acrylate 25 parts Acrylic acid 45 parts 2-Dimethylaminoethyl methacrylate 10 parts Azobisisobutyronitrile 1.6 parts 2-Propanol 200 parts Then, 10 parts of glycidyl methacrylate is added to the obtained reaction product. Then, by heating to 70 ° C. in an air atmosphere and holding for 3 hours, a reaction product having a pendant methacrylic group was obtained. After cooling to room temperature, 50 parts of pyridine and deionized water
118 parts of the mixture was added to obtain a reactive polymer emulsifier having a solid content of 30%.

(3) Preparation of modified tackifying resin [Production Example 8] Pentaline H (manufactured by Rika Hercules Co., Ltd.) was charged with the following monomers in a 2 L 4-neck flask equipped with a stirrer, thermometer, condenser and dropping funnel. 200 parts 2-Ethylhexyl acrylate 50 parts Butyl acrylate 35 parts Acrylic acid 5 parts 2-Dimethylaminoethyl methacrylate 10 parts Benzyl peroxide 1.0 part Toluene 50 parts Polymerization reaction at 80 ° C in a nitrogen atmosphere while heating while stirring After 1 and 2 hours, 1.0 part of benzyl peroxide was added, and then the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization to obtain a reaction product. This was cooled to room temperature to obtain an acrylic-modified tackifying resin having a solid content of 85%. [Production Example 9] To the reaction product obtained in the same manner as in Production Example 8, 5 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C. in an air atmosphere and held for 3 hours so that methacryl groups were pendant. A reaction product was obtained. After cooling to room temperature, a reactive acrylic modified tackifying resin having a solid content of 87% was obtained.

[Production Example 10] The following monomers were charged in a flask and a polymerization reaction was carried out in the same manner as in Production Example 8 to obtain a reaction product. FTR 6100 (Mitsui Petrochemical Co., Ltd.) 200 parts Butyl acrylate 80 parts Methacrylic acid 2 parts 2-Hydroxyethyl methacrylate 8 parts 2-Dimethylaminoethyl methacrylate 10 parts Benzyl peroxide 1.0 part Toluene 50 parts Then, the obtained reaction To the product, 5 parts of glycidyl methacrylate was added, and the solid content ratio was 87% in the same manner as in Production Example 9.
A reactive acrylic modified tackifying resin of was obtained.

[Production Example 11] The following monomers were charged in a flask and a polymerization reaction was carried out in the same manner as in Production Example 8 to obtain a reaction product. YS Resin Px1250 (Yasuhara Chemical Co., Ltd.) 200 parts 2-Ethylhexyl acrylate 70 parts Ethyl acrylate 10 parts Acrylic acid 10 parts 2-Hydroxyethyl methacrylate 2 parts 2-Dimethylaminoethyl methacrylate 8 parts Benzyl peroxide 1.0 parts Toluene 50 parts Then, 5 parts of glycidyl methacrylate was added to the obtained reaction product, and the solid content was 87% in the same manner as in Production Example 9.
A reactive acrylic modified tackifying resin of was obtained.

[Production Example 12] The following monomers were charged in a flask and a polymerization reaction was carried out in the same manner as in Production Example 8 to obtain a reaction product. Super ester S-115 (Arakawa Chemical Co., Ltd.) 200 parts Butyl acrylate 35 parts Ethyl acrylate 30 parts Acrylic acid 10 parts Vinyl acetate 20 parts 2-Dimethylaminoethyl methacrylate 5 parts Benzyl peroxide 1.0 part Toluene 50 parts To the obtained reaction product, 5 parts of glycidyl methacrylate was added, and the solid content ratio was 87% in the same manner as in Production Example 9.
A reactive acrylic modified tackifying resin of was obtained.

[Production Example 13] The following monomers were charged in a flask and a polymerization reaction was carried out in the same manner as in Production Example 8 to obtain a reaction product. Super Ester S-115 (Arakawa Chemical Co., Ltd.) 200 parts Acrylated polybutadiene MAC-1000-80 50 parts (Nippon Petrochemical Co., Ltd.) Butyl acrylate 35 parts Acrylic acid 10 parts 2-Dimethylaminoethyl methacrylate 5 parts Benzyl peroxide 1.0 part Toluene 50 parts Then, 5 parts of glycidyl methacrylate was added to the obtained reaction product, and the solid content was 87% in the same manner as in Production Example 9.
A reactive rubber-modified tackifying resin of was obtained.

Example 1 A 2 L 4-necked flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with the following compounds, and 100 parts of pentaline H (manufactured by Rika Hercules Co., Ltd.) Dispersion obtained in Production Example 1 Agent resin 100 parts Modified tackifying resin obtained in Production Example 10 10 parts Polymeric emulsifier obtained in Production Example 30 30 parts Dodecylbenzene sulfonate sodium 2 parts Polyoxyethylene nonylphenyl ether 2 parts After warming and mixing at 120 ° C. for 1 hour, the temperature in the flask was lowered to 80 ° C. to remove the solvent under vacuum, and 100 parts of deionized water was added dropwise over 1 hour to obtain an aqueous dispersion. Further, in a nitrogen atmosphere, 8 parts of 10% 4,4'-azobis (4-cyanovaleric acid) aqueous solution was added and the mixture was kept for 2 hours. Then, 2 parts of a 10% 4,4′-azobis (4-cyanovaleric acid) aqueous solution was added. After the addition was completed, the reaction mixture was heated at 80 ° C for 4
Polymerization was completed by holding for a period of time to obtain an aqueous microgel dispersion.

Example 2 The following compounds were charged in a flask and the same procedure as in Example 1 was carried out to obtain an aqueous microgel dispersion. Pentaline H (manufactured by Rika Hercules) 100 parts Dispersant resin obtained in Production Example 1 10 parts Modified tackifying resin obtained in Production Example 18 10 parts Polymeric emulsifier obtained in Production Example 15 30 parts Dodecyl Sodium benzene sulfonate 2 parts Polyoxyethylene nonyl phenyl ether 2 parts

Example 3 The following compounds were charged in a flask, and 100 parts of deionized water was replaced with 90 parts, and the other example 1 was used.
An aqueous microgel dispersion was obtained in the same manner as in. Pentaline H (Rika Hercules) 100 parts Dispersant resin obtained in Preparation Example 10 parts Polymeric emulsifier obtained in Preparation Example 15 30 parts Sodium dodecylbenzene sulfonate 2 parts Polyoxyethylene nonylphenyl ether 2 parts

Example 4 A 2 L 4-necked flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with the following compounds, and 100 parts of Pentaline H (manufactured by Rika Hercules Co., Ltd.) were dispersed. Agent resin 10 parts Polymeric emulsifier obtained in Production Example 14 30 parts Sodium dodecylbenzene sulfonate 2 parts Polyoxyethylene nonylphenyl ether 2 parts While heating with stirring and mixing at 120 ° C for 1 hour, The temperature was lowered to 80 ° C., the solvent was removed under vacuum, and 90 parts of deionized water was added dropwise over 1 hour to obtain an aqueous dispersion.

Example 5 The following compounds were charged in a flask, and 90 parts of deionized water was replaced with 100 parts, and other example 4 was used.
An aqueous dispersion was obtained in the same manner as in. Pentaline H (Rika Hercules) 100 parts Dispersant resin obtained in Preparation Example 10 10 parts Modified tackifying resin obtained in Preparation Example 10 10 parts Polymeric emulsifier obtained in Preparation Example 30 30 parts Dodecyl Sodium benzene sulfonate 2 parts Polyoxyethylene nonyl phenyl ether 2 parts

Comparative Example 1 The microgel aqueous dispersion was obtained by emulsifying and polymerizing in the same manner as in Example 1 except that the dispersant resin obtained in Production Example 1 was not used. [Comparative Example 2] Emulsification was attempted in the same manner as in Example 2 except that the polymer emulsifier obtained in Production Example 15 was not used, but it was not an aqueous dispersion. [Comparative Example 3] Instead of sodium dodecylbenzene sulfonate and polyoxyethylene nonylphenyl ether (low-molecular-weight surfactant), the polymer emulsifier of Production Example 15 was used.
Emulsification was attempted to be carried out in the same manner as in Example 1 using 60 parts, but a high-viscosity yogurt-like product could not be obtained, and an aqueous microgel dispersion could not be prepared.

Comparative Example 4 Casein-ammonium salt was used as a stabilizer in place of the polymeric emulsifier obtained in Production Example 14.
An aqueous dispersion was obtained in the same manner as in Example 4 except that 35 parts was used. [Comparative Example 5] 100 parts of pentaline H (tackifying resin) was added to 150 parts.
Melt to 5 ℃, and add 5 parts of sodium dodecylbenzene sulfonate and polyoxyethylene nonyl phenyl ether.
To 150 parts of 80 ° C deionized water containing 5 parts dissolved, homogenize with vigorous stirring for 2 hours to emulsify and cool to room temperature (25 ° C) with vigorous stirring. Then, an aqueous dispersion of tackifying resin was obtained.

Comparative Example 6 100 parts of pentaline H was mixed with 30 parts of dioctyl phthalate (plasticizer) by heating at 120 ° C., and 5 parts of sodium dodecylbenzenesulfonate and 5 parts of polyoxyethylene nonylphenyl ether were dissolved. Emulsify by dropping into 210 parts of 80 ° C deionized water with a homomixer with vigorous stirring for 2 hours, cool to room temperature (25 ° C) with vigorous stirring, and then neutralize with ammonia water to give a tackifier resin. An aqueous dispersion was obtained. Comparative Example 7 100 parts of pentaline H was dissolved in 30 parts of toluene, and 120 parts of deionized water containing 5 parts of sodium dodecylbenzene sulfonate and 5 parts of polyoxyethylene nonylphenyl ether was vigorously stirred with a homomixer. The mixture was added dropwise over 2 hours for emulsification and neutralized with aqueous ammonia to obtain a tackifying resin aqueous dispersion.

Example 6 The following compounds were charged in a flask and an aqueous dispersion was obtained in the same manner as in Example 1. FTR 6100 (manufactured by Mitsui Petrochemical Co., Ltd.) 100 parts 15 parts dispersant resin obtained in Production Example 3 12 parts modified tackifying resin obtained in Production Example 20 28 parts polymeric emulsifier obtained in Production Example 17 Sodium dodecylbenzene sulfonate 2 parts Polyoxyethylene nonyl phenyl ether 2 parts Further, 8 parts of 10% azobisamidinopropane dihydrochloric acid aqueous solution was added in a nitrogen atmosphere and the mixture was maintained for 2 hours. Then 10
% Aqueous solution of azobisamidinopropane dihydrochloride was added. After the addition was completed, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and an aqueous microgel dispersion was obtained.

Example 7 The following compounds were charged in a flask and an aqueous dispersion was obtained in the same manner as in Example 1. YS Resin Px1250 (Yasuhara Chemical Co., Ltd.) 100 parts Dispersant resin obtained in Preparation Example 10 10 parts Modified tackifying resin obtained in Preparation Example 21 30 parts Polymeric emulsifier obtained in Preparation Example 16 28 parts Poly Oxyethylene olein ether 5 parts

Example 8 An aqueous dispersion was obtained in the same manner as in Example 7, except that the polymer emulsifier obtained in Production Example 16 was replaced with the polymer emulsifier obtained in Production Example 17. Further, in a nitrogen atmosphere, 8 parts of 10% 2,2'-azobisisobutyramide dihydrate aqueous solution was added and the mixture was kept for 2 hours. Then 10%
2 parts of 2,2'-azobisisobutyramide dihydrate aqueous solution was added. After the addition was completed, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and an aqueous microgel dispersion was obtained.

Example 9 The following compounds were charged in a flask and an aqueous dispersion was obtained in the same manner as in Example 1. YS resin Px1250 (manufactured by Yasuhara Chemical Co., Ltd.) 100 parts Dispersant resin obtained in Production Example 3 10 parts Polymeric emulsifier obtained in Production Example 17 28 parts Polyoxyethylene olein ether 5 parts Further, in a nitrogen atmosphere, 10% 8 parts of 2,2'-azobisisobutyramide dihydrate aqueous solution was added and the mixture was kept for 2 hours. Then, 2 parts of 10% 2,2'-azobisisobutyramide dihydrate aqueous solution was added. After the addition was completed, the reaction mixture was heated at 80 ° C for 4
Polymerization was completed by holding for a period of time to obtain an aqueous microgel dispersion.

Example 10 An aqueous dispersion was obtained in the same manner as in Example 1 except that the following compounds were charged in a flask and 100 parts of deionized water was replaced with 70 parts. Super Ester S-115 (Arakawa Chemical Co., Ltd.) 100 parts Dispersant resin obtained in Preparation Example 10 10 parts Modified tackifying resin obtained in Preparation Example 22 15 parts Polymeric emulsifier obtained in Preparation Example 17 25 parts Polyoxyethylene lauryl ether sodium sulfate 6 parts Further, 16 parts of 10% ammonium persulfate aqueous solution was added in a nitrogen atmosphere and the mixture was kept for 2 hours. Then 4 parts of 10% aqueous ammonium persulfate solution was added. After the addition was completed, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and an aqueous microgel dispersion was obtained.

Example 11 A microgel aqueous dispersion was prepared in the same manner as in Example 10 except that the modified tackifying resin obtained in Production Example 22 was not used, and 70 parts of deionized water was replaced with 100 parts. Got the body [Example 12] A microgel aqueous dispersion was obtained in the same manner as in Example 10 except that the following compound was charged in a flask and 70 parts of deionized water was replaced with 100 parts. Super Ester S-115 (manufactured by Arakawa Chemical Co., Ltd.) 100 parts PAR-124 (manufactured by Mitsubishi Kasei) 10 parts Modified tackifying resin obtained in Production Example 22 15 parts Polymeric emulsifier obtained in Production Example 15 25 Part Polyoxyethylene lauryl ether sodium sulfate 6 parts

Example 13 A microgel aqueous dispersion was obtained in the same manner as in Example 10 except that the following compounds were charged in a flask and 70 parts of deionized water was replaced with 100 parts. S-Crystal A-120 (manufactured by Nippon Steel Chemical Co., Ltd.) 100 parts Admast 1000 (manufactured by Idemitsu Petrochemical Co., Ltd.) 8 parts Polymeric emulsifier obtained in Production Example 15 25 parts Polyoxyethylene lauryl ether sodium sulfate 6 parts

Example 14 A microgel aqueous dispersion was obtained in the same manner as in Example 10, except that the following compound was charged in a flask and 70 parts of deionized water was replaced with 100 parts. S-Crystal A-120 (manufactured by Nippon Steel Chemical Co., Ltd.) 100 parts Modified tackifying resin obtained in Production Example 23 8 parts Polymeric emulsifier obtained in Production Example 15 25 parts Polyoxyethylene lauryl ether sodium sulfate 6 parts

Table 1 shows the measurement results of viscosity, solid content, PH and particle size of the aqueous dispersions obtained in Examples and Comparative Examples. However, the viscosity is BM type rotational viscometer No.2,3 / 12rpm 25 ℃
The particle size is measured by dynamic light scattering particle size distribution meter (DL manufactured by Otsuka Electronics Co., Ltd.
S700). The solid content is non-volatile content after oven drying at 150 ℃ for 20 minutes. In addition, nylon cloth (200
(Mesh) was used to evaluate the filterability, and the results are shown in Table 1. ○ If the cloth is smooth and does not leave any lumps on the nylon cloth, the cloth is good, but if the cloth has some lumps on the nylon cloth, △, if the cloth is poor, and there are many lumps on the nylon cloth Was judged as x. Moreover, about Example 1 and Comparative Examples 4-7, it was left to stand for 6 months under the condition of 25 ° C., and a decay test was conducted. The results of sensory evaluation of appearance and odor are shown in Table 2.

Next, a general-purpose water-based adhesive [BPW4655]
(Manufactured by Toyo Ink Mfg. Co., Ltd.)], the aqueous dispersions obtained in Examples and Comparative Examples were blended in a solid content ratio of 20%, and each was applied to a commercially available high-quality paper separator at a dry weight of 20 to 30 g / m ^2. ,
It was dried at 100 ° C. for 2 minutes and inverted on a commercial high-quality paper to prepare a coated product. Based on JIS-Z-0237, Table 3 shows the results of measuring the adhesive strength and the holding power with respect to the polyethylene plate.
The coating left at 23 ℃ -65% RH is the normal coating, 50 ℃ -95
After leaving in the atmosphere of high temperature and high humidity of% RH for 3 days, 23 ℃ -65
The coating that was left for 1 day at% RH was used as the humidified heat aged coating, and the value of the adhesive strength of the humidified heat aged coating relative to the adhesive strength of the normal coating was taken as the humidified heat aged retention rate, and the wet heat deterioration resistance Was evaluated. That is, the closer the value is to 100%, the less the resistance to heat and humidity deterioration, and the closer it is to 0%, the greater the resistance to heat and humidity deterioration. Furthermore, the coated surface was observed with the naked eye and a microscope of 50 times to evaluate the coating property. Even if 50-fold microscopic observation does not show any spots or streaks on the coated surface, ○, no visible spots or streaks are visible on the coated surface, but can be confirmed by 50-fold microscopic observation. When the coated surface had spots or streaks, it was marked with x.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

EFFECTS OF THE INVENTION According to the present invention, a high-concentration aqueous dispersion of a tackifying resin, which has hitherto been difficult to achieve high solidification, can be carried out without mixing an organic solvent in the obtained aqueous dispersion.
Further, since the tackifying resin aqueous dispersion composition of the present invention is an emulsion of fine particles having a core / shell structure, there is no reduction in adhesive properties or cohesive force even when used in an aqueous adhesive,
It has good compatibility, and since it can be a fine particle emulsion having a particle size such as colloid, for example, 0.01 to 10 μm, generally 1 μm or less, it does not affect the coating processability. Further, since the amine neutralization is performed, the aqueous dispersion composition of the present invention does not cause putrefaction and has extremely excellent storage stability.

Claims (7)

[Claims] 1. A reaction of 100 parts by weight of a tackifying resin (A) with a monomer (a) having an α, β unsaturated double bond and a dibasic acid having an unsaturated group or an anhydride thereof (b). Dispersant (B) containing the resulting copolymer or its derivative 1 ~
An aqueous tackifier resin dispersion composition obtained by emulsifying 100 parts by weight of an anionic polymer emulsifier (C) in an amount of 0.1 to 50 parts by weight and a low molecular weight surfactant (D) in an amount of 0.1 to 50 parts by weight. 2. A dispersant (B) obtained by reacting a monomer (a) having an α, β unsaturated double bond with a dibasic acid having an unsaturated group or an anhydride thereof (b). The tackifier resin aqueous dispersion composition according to claim 1, which contains 1 to 50 parts by weight of the polymer or a derivative thereof and 50 parts by weight or less of the modified tackifier resin (c). 3. The aqueous tackifier resin dispersion composition according to claim 1, wherein the anionic polymer emulsifier (C) contains a carboxyl group as a polar functional group, and optionally contains a polymerizable double bond. 4. The tackifying resin aqueous dispersion composition according to claim 1, wherein the low-molecular-weight surfactant (D) is a nonionic surfactant and / or an anionic surfactant. 5. The tackifying resin aqueous solution according to claim 2, wherein the modified tackifying resin (c) is obtained by carrying out a polymerization reaction of an acrylic monomer or a modification reaction of a rubber during melting of the tackifying resin or in an organic solvent. Dispersion composition. 6. A monomer having an α, β unsaturated double bond
The tackifier resin aqueous dispersion composition according to claim 1, wherein (a) is an α-olefin. 7. The tackifying resin aqueous dispersion composition according to claim 1, wherein the dibasic acid having an unsaturated group or its anhydride (b) is maleic anhydride.