JP6907932B2 - Adhesive-imparting resin emulsion for water-based adhesives and adhesives and water-based adhesives / adhesive compositions - Google Patents

Description

The present invention relates to a tackifier resin emulsion for a water-based adhesive / adhesive and a water-based adhesive / adhesive composition.

In recent years, due to consideration for the environment, a viscous / adhesive composition having a low content of volatile organic solvents and the like has been required. For example, in automobile applications and building material applications, due to the problems of sick car syndrome and sick house syndrome, water-based emulsion type Adhesive / adhesive compositions are widely used. Further, in the case of automobile applications, for example, in the case of interior members, the temperature inside the vehicle rises in the summer, while in the case of building materials, the temperature reaches a high temperature when exposed to an environment exposed to direct sunlight in the summer. Therefore, the viscous / adhesive composition used is required to have heat-resistant holding power at such a high temperature, but when trying to change from the conventional organic solvent-based sticky / adhesive to water-based, the heat-resistant holding power is not good. There was a problem that it would be enough.

As a method for improving the heat-resistant holding power, for example, a tackifier resin emulsion in which polymerized rosin is modified with acrylic acid, then esterified with a polyhydric alcohol, and acrylic polymerized rosin ester having a softening point of 135 to 180 ° C. is dispersed in water. Is known (see Patent Document 1). Although the heat-resistant holding power is improved by increasing the softening point of the resin, the molecular weight is rapidly increased and the compatibility with the base polymer is significantly reduced, which is insufficient to obtain a well-balanced adhesive performance. Met.

Further, a tackifier resin emulsion in which a mixture of a rosin-based resin and a cross-linking agent having reactivity with a carboxyl group is dispersed in water is known (see Patent Document 2). This technology proposes a method of increasing the polymer of the tackifier resin component by reacting the rosin-based resin, which is a tackifier resin, with a cross-linking agent at the time of manufacturing or using the pressure-sensitive adhesive to improve the heat-resistant holding power. However, when a rosin-based resin having an acid value of 5 to 130, particularly more than 20, is inevitably reduced in compatibility with the base polymer even if a cross-linking reaction is carried out during the production or use of the pressure-sensitive adhesive, it is required. It was insufficient to satisfy the levels of compatibility and heat retention.

Japanese Unexamined Patent Publication No. 2004-143248 Japanese Unexamined Patent Publication No. 2005-11301

An object of the present invention is to provide a tackifier resin emulsion for water-based adhesives / adhesives, which exhibits excellent heat-resistant holding power without lowering compatibility.

As a result of diligent studies, the present inventor has found that a specific resin emulsion and a tackifier resin emulsion containing a water-soluble polymer solve the above-mentioned problems. That is, the present invention relates to the following tackifier resin emulsions for water-based adhesives and water-based adhesives and adhesive compositions.

1. 1. A resin emulsion (A) containing an emulsified substance of at least one emulsified substance selected from the group consisting of a rosin-based resin (a1), a petroleum resin (a2), and a terpene-based resin (a3), and a heterocyclic nitrogen-containing water-soluble substance. Adhesive-imparting resin emulsion for water-based adhesives and adhesives containing the sex polymer (B).

2. The tackifier resin emulsion for the water-based adhesive / adhesive according to Item 1, wherein the emulsified substance has a softening point of 80 to 160 ° C.

3. 3. The tackifier resin emulsion for the water-based adhesive / adhesive according to item 1 or 2 above, wherein the component (a1) is a rosin ester.

4. (B) A tackifier resin emulsion for an aqueous adhesive / adhesive according to any one of Items 1 to 3 above, wherein the weight average molecular weight of the component is 3,000 to 500,000.

5. (B) A tackifier resin emulsion for an aqueous adhesive / adhesive according to any one of Items 1 to 4, wherein the component is polyvinylpyrrolidone and / or polyvinylimidazole.

6. A tackifier resin emulsion for an aqueous adhesive / adhesive according to any one of Items 1 to 5, which contains 1 to 10 parts by weight of the component (B) with respect to 100 parts by weight of the component (A).

7. The water-based sticky / adhesive composition containing the tackifier resin emulsion for the water-based sticky / adhesive according to any one of Items 1 to 6.

8. An aqueous viscous / adhesive composition containing the tackifier resin emulsion for the water-based viscous / adhesive according to any one of Items 1 to 6 and an acrylic polymer emulsion.

The tackifying resin emulsion for water-based adhesives and adhesives of the present invention exhibits excellent heat-resistant holding power, and can maintain various adhesive performances such as adhesive strength and tack.

The tackifier resin emulsion for water-based adhesives and adhesives of the present invention (hereinafter, also referred to as “tackiness-imparting resin emulsion”) is a rosin-based resin (a1), a petroleum resin (a2), and a terpen-based resin (a3). A resin emulsion (A) containing an emulsion of at least one emulsifying substance selected from the group consisting of (hereinafter referred to as (A) component), and a heterocyclic nitrogen-containing water-soluble polymer (B) (hereinafter, (hereinafter referred to as (A) component). B) It contains a component).

The component (A) is a rosin-based resin (a1) (hereinafter referred to as (a1) component), a petroleum resin (a2) (hereinafter referred to as (a2) component), and a terpene-based resin (a3) (hereinafter referred to as (a3) component). It is an emulsion of at least one emulsifying substance selected from the group consisting of (referred to as).

The component (a1) is not particularly limited, and various known components can be used. For example, unmodified rosins such as gum rosin, wood rosin, and tall oil rosin, polymerized rosin, α, β-unsaturated dicarboxylic acid-modified rosins such as maleated rosin and fumarized rosin, acrylicized rosin, hydrobrosin, and disproportionated rosin. , Or these esterified products, rosin phenol resin and the like. These may be used alone or in combination of two or more. Among these, a rosin ester is preferable from the viewpoint of adhesive properties such as heat retention, and at least one selected from an unmodified rosin ester, a polymerized rosin ester and an unsaturated dicarboxylic acid-modified rosin ester is more preferable.

The component (a2) is not particularly limited, and various known components can be used. For example, C5-based petroleum resin obtained from the C5 distillate of naphtha such as penten, pentadiene and isoprene; C9 obtained from the C9 distillate of naphtha such as inden, methylinden, vinyltoluene, styrene, α-methylstyrene and β-methylstyrene. Petroleum resin; C5-C9 copolymer petroleum resin obtained from the C5 and C9 distillates; pure monomer resin obtained by polymerizing styrene or the like as a main component; DCPD petroleum obtained from cyclopentadiene and dicyclopentadiene. Resin; Examples thereof include hydrides of these petroleum resins. These may be used alone or in combination of two or more. Among these, C9-based petroleum resin is preferable from the viewpoint of adhesive properties such as heat resistance holding power.

The component (a3) is not particularly limited, and examples thereof include a resin obtained by copolymerizing known terpenes and phenols, a polyterpene resin, and the like. The component (a3) may be hydrogenated. Among these, terpene phenol resin is preferable from the viewpoint of adhesive properties such as heat resistance holding power.

Hereinafter, the unmodified rosin ester, the polymerized rosin ester, and the unsaturated dicarboxylic acid-modified rosin ester will be described with respect to the component (a1).

The unmodified rosin ester is obtained by reacting an alcohol with an unmodified rosin such as gum rosin, wood rosin, and tall oil rosin.

As the unmodified rosin, those purified by a vacuum distillation method, a steam distillation method, an extraction method, a recrystallization method or the like may be used.

As the reaction conditions between the unmodified rosin and the alcohols, an esterification catalyst was added to the unmodified rosin and the alcohols in the presence or absence of a solvent, if necessary, at about 250 to 280 ° C. for 1 to 8 hours. You can do it with a degree.

The alcohols are not particularly limited, and are, for example, monohydric alcohols such as methanol, ethanol, propanol and stearyl alcohol, and divalent alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol and dimerdiol. Examples thereof include trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, and hexahydric alcohols such as dipentaerythritol. Among these, polyhydric alcohols having two or more hydroxyl groups are preferable, and pentaerythritol is particularly preferable.

(About polymerized rosin ester)
The polymerized rosin ester is obtained by reacting the polymerized rosin with alcohols. The polymerized rosin is a rosin derivative containing a dimerized resin acid.

As a method for producing the polymerized rosin, a known method can be adopted. Specifically, for example, as a raw material, unmodified rosin such as gum rosin, tall oil rosin, and wood rosin is used in a solvent such as toluene and xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, and titanium tetrachloride at a temperature of 40. Examples thereof include a method of reacting at about 160 ° C. for about 1 to 5 hours.

Specific examples of the polymerized rosin include gum-based polymerized rosin (for example, trade name "polymerized rosin B-140", manufactured by Shinshu (Takehira) Rinka Co., Ltd.) Tall oil-based polymerized rosin (for example, trade name "Silva Tack 140"). , Manufactured by Arizona Chemical Co., Ltd.), wood-based polymerized rosin (for example, trade name "Dymalex", manufactured by Hercules Co., Ltd.) and the like.

As the polymerized rosin, the polymerized rosin is subjected to various treatments such as modification such as hydrogenation, disproportionation and acrylicization, and α, β-unsaturated dicarboxylic acid modification such as maleation and fumarization. You may use it. Further, various treatments may be performed alone or in combination of two or more.

As the reaction conditions between the polymerized rosin and the alcohols, an esterification catalyst was added to the polymerized rosin and the alcohols in the presence or absence of a solvent as necessary, and the temperature was about 250 to 280 ° C. for about 1 to 8 hours. You can do it with.

The alcohols used for esterifying the polymerized rosin are the same as described above.

The order of the polymerization reaction and the esterification reaction is not limited to the above, and the polymerization reaction may be carried out after the esterification reaction.

(About unsaturated dicarboxylic acid-modified rosin ester)
The unsaturated dicarboxylic acid-modified rosin ester is an esterified product of a modified rosin obtained by addition-reacting an unmodified rosin with an α, β-unsaturated dicarboxylic acid and further reacting with alcohols.

Examples of the unmodified rosin include gum rosin, tall oil rosin, wood rosin and the like. As the unmodified rosin, those purified by a vacuum distillation method, a steam distillation method, an extraction method, a recrystallization method or the like may be used.

The α, β-unsaturated dicarboxylic acid is not particularly limited, and various known ones can be used. Specific examples thereof include maleic anhydride, maleic acid, fumaric acid and the like. From the viewpoint of emulsifying property, the amount of α, β-unsaturated dicarboxylic acid used is usually about 1 to 20 parts by weight, preferably about 1 to 3 parts by weight, based on 100 parts by weight of the unmodified rosin.

The method for producing the α, β-unsaturated dicarboxylic acid-modified rosin is not particularly limited, but for example, α, β-unsaturated dicarboxylic acid is added to the unmodified rosin melted under heating, and the temperature is 180 to 240. The reaction may be carried out at about ° C. for about 1 to 9 hours. Further, the above reaction may be carried out while blowing an inert gas such as nitrogen into the closed reaction system. Further, in the reaction, known catalysts such as Lewis acid such as zinc chloride, iron chloride and tin chloride, and Bronsted acid such as paratoluenesulfonic acid and methanesulfonic acid may be used. The amount of these catalysts used is usually about 0.01 to 10% by weight based on the unmodified rosin.

The obtained α, β-unsaturated dicarboxylic acid-modified rosin may contain a resin acid derived from unmodified rosin.

The reaction conditions between the α, β-unsaturated dicarboxylic acid-modified rosin and alcohols are not particularly limited, but for example, alcohol is added to the α, β-unsaturated dicarboxylic acid-modified rosin melted under heating. Therefore, the reaction may be carried out at a temperature of about 250 to 280 ° C. for about 15 to 20 hours. Further, the above reaction may be carried out while blowing an inert gas such as nitrogen into the closed reaction system, or the above-mentioned catalyst may be used.

The alcohols used for esterifying the α, β-unsaturated dicarboxylic acid-modified rosin are the same as described above.

The physical properties of the emulsified substance are not particularly limited, but are preferably about 80 to 160 ° C. from the viewpoint of adhesive properties. In the present invention, the softening point is a value measured by the ring-and-ball method (JIS K 5902).

The component (A) of the present invention is obtained by emulsifying a specific emulsifying substance in the presence of an emulsifier, and can be used as a tackifier resin for water-based adhesives and adhesives.

The emulsifier used for producing the component (A) is not particularly limited, and a known emulsifier can be used. Specific examples thereof include a high molecular weight emulsifier obtained by polymerizing a monomer, a low molecular weight anionic emulsifier, and a low molecular weight nonionic emulsifier. These may be used alone or in combination of two or more. Among these, a low molecular weight anionic emulsifier is preferable from the viewpoint of emulsifying property.

Examples of the monomer used for producing the high molecular weight emulsifier include (meth) acrylic acid ester-based monomers such as methyl (meth) acrylate and ethyl (meth) acrylate; Monocarboxylic acid-based vinyl monomers ;; Dicarboxylic acid-based vinyl monomers such as maleic acid and maleic anhydride; and sulfonic acid-based vinyl monomers such as vinyl sulfonic acid and styrene sulfonic acid; and alkali metals of these various organic acids. Salts, alkaline earth metal salts, ammonium salts, organic base salts; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol (meth) acrylamide; nitrile-based monomers such as (meth) acrylonitrile Vinyl ester-based monomers such as vinyl acetate; Hydroxy group-containing (meth) acrylic acid ester-based monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Methylvinyl ether, glycidyl ( Examples thereof include meta) acrylates, urethane acrylates, α-olefins having 6 to 22 carbon atoms, and other monomers such as vinylpyrrolidone. These may be used alone or in combination of two or more.

Examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization using a reactive emulsifier other than the high molecular weight emulsifier described later, and a non-reactive emulsifier other than the high molecular weight emulsifier.

The weight average molecular weight of the high molecular weight emulsifier thus obtained is not particularly limited, but is preferably about 1,000 to 500,000 in terms of the adhesive properties of the tackifier resin.

Reactive emulsifiers other than the above high molecular weight emulsifier include, for example, those having a hydrophilic group such as a sulfonic acid group and a carboxyl group and a hydrophobic group such as an alkyl group and a phenyl group, and have a carbon-carbon double bond in the molecule. Those having a bond.

The low molecular weight anionic emulsifier is not particularly limited, and for example, dialkyl sulfosuccinate salt, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate salt, polyoxyethylene styrylphenyl ether. Sulfosuccinic acid ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene dialkyl ether sulfate ester salt, polyoxyethylene trialkyl ether sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt, etc. Can be mentioned.

The low molecular weight nonionic emulsifier is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitan fatty acid ester.

The emulsifier other than the high molecular weight emulsifier may be used alone or two or more kinds may be appropriately selected and used.

The amount of the emulsifier used is about 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the component (A) in terms of solid content. By using 1 part by weight or more of the emulsifier, reliable emulsification can be performed, and by using 10 parts by weight or less, high water resistance and adhesive performance of the tackifying resin emulsion can be ensured. can.

The emulsification method is not particularly limited, and known emulsification methods such as a high-pressure emulsification method and a phase inversion emulsification method can be adopted.

The high-pressure emulsification method is a method in which an emulsifier and water are premixed after the emulsified substance is in a liquid state, finely emulsified using a high-pressure emulsifier, and then the solvent is removed if necessary. The method of making the emulsified substance into a liquid state may be heated only by heating, dissolved in a solvent and then heated, or mixed with a non-volatile substance such as a plasticizer and heated, but it should be performed only by heating. Is preferable. Examples of the solvent include organic solvents capable of dissolving an emulsion such as toluene, xylene, methylcyclohexane, and ethyl acetate.

In the above phase inversion emulsification method, after the emulsion is heated and melted, an emulsifier and water are added while stirring to form a W / O emulsion first, and then the emulsion is converted into an O / W emulsion by adding water or changing the temperature. It is a method of matching.

The concentration of the component (A) thus obtained is not particularly limited, but is usually adjusted appropriately so as to be about 20 to 70% by weight before use. The volume average particle diameter of the obtained component (A) is usually about 0.1 to 2 μm, and most of the particles are uniformly dispersed as particles of 1 μm or less, but it may be 0.7 μm or less. , Preferred from the viewpoint of storage stability. The component (A) has a white to milky white appearance, and the viscosity is usually about 10 to 1,000 mPa · s (temperature 25 ° C., concentration 50% by weight). The pH is usually about 2 to 10, but if necessary, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; alkanolamines such as monomethylamine, monoethanolamine, diethanolamine and diisopropanolamine; ethylamine, n- An aliphatic amine such as butylamine or triethylamine; an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide; an alkaline earth metal hydroxide such as calcium hydroxide may be appropriately added to adjust the pH. ..

The component (B) of the present invention is a component added to improve the adhesive properties of the tackifier resin, particularly the heat-resistant holding power.

The component (B) is not particularly limited, and various known components can be used. For example, polyvinylpyrrolidone, polyvinylimidazole, polyvinylcarbazole, polyvinylpiperidin, polyvinylcaprolactam and the like can be mentioned. These may be used alone or in combination of two or more. Among these, polyvinylpyrrolidone and polyvinylimidazole are preferable, and polyvinylpyrrolidone is more preferable, from the viewpoint of heat retention.

The weight average molecular weight of the component (B) is not particularly limited, but is usually about 3,000 to 1,000,000, preferably about 3,000 to 500,000 from the viewpoint of heat retention. More preferably, it is about 5,000 to 500,000. The weight average molecular weight is a polyethylene oxide equivalent value obtained by gel permeation chromatography.

The amount of the component (B) used is not particularly limited, but is usually 1 to 10 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content. If it is less than 1 part by weight, the heat-resistant holding power tends to decrease.

The method for mixing the component (A) and the component (B) is not particularly limited, and the component (A) and the component (B) may be mixed at the same time, or the component (B) may be mixed with the agitated component (A).

The present invention is also a water-based adhesive / adhesive composition containing the pressure-imparting resin emulsion. The water-based adhesive / adhesive composition of the present invention can be obtained by mixing the tackifier resin emulsion and the base polymer. Further, the water-based adhesive / adhesive composition of the present invention can be used as a water-based adhesive / adhesive.

Examples of the base polymer include acrylic polymer emulsions, rubber latex and synthetic resin emulsions, each of which can be used in combination, and if necessary, a cross-linking agent, a defoaming agent, a thickener, and a filling agent. Agents, antioxidants, water resistant agents, film-forming aids and the like can also be used. Further, a known tackifier resin emulsion may be used. The concentration of these water-based adhesive / adhesive compositions is usually about 40 to 70% by weight, preferably 55 to 70% by weight. At least one base polymer may be used.

The mixing method is not particularly limited, and the tackifier resin emulsion may be emulsified and mixed, or the tackifier resin emulsion may be added to the base polymer and mixed using a high shear rotary mixer.

As the above-mentioned acrylic polymer emulsion, those generally used for various acrylic adhesives / adhesives can be used, and a monomer batch-preparation polymerization method such as (meth) acrylic acid ester, a monomer sequential addition polymerization method, and emulsification can be used. It can be easily produced by a known emulsion polymerization method such as a monomer sequential addition polymerization method and a seed polymerization method.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. Meta) 2-hydroxyethyl acrylate and the like can be mentioned, and these are used alone or in combination of two or more. Further, in order to impart storage stability to the obtained emulsion, a small amount of (meth) acrylic acid may be used instead of the above (meth) acrylic acid ester. Further, if desired, a copolymerizable monomer such as vinyl acetate or styrene can be used in combination to the extent that the adhesive properties of the (meth) acrylic acid ester polymer are not impaired. An anionic emulsifier, partially saponified polyvinyl alcohol, or the like can be used as the emulsifier used in the acrylic polymer emulsion, and the amount used is about 0.1 to 5 parts by weight, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the polymer. It is about 0.5 to 3 parts by weight.

The content ratio of the above-mentioned acrylic polymer emulsion and the tackifier resin emulsion is not particularly limited, but the effect of modification by the tackifier resin emulsion can be sufficiently exhibited, and the heat retention and tackiness can be reduced due to excessive use. As an appropriate range of use that does not cause the problem, it is preferable that the pressure-imparting resin emulsion is usually about 2 to 40 parts by weight with respect to 100 parts by weight of the acrylic polymer emulsion in terms of solid content.

Further, as the rubber-based latex, various known rubber-based latexes used in the water-based adhesive / adhesive composition can be used. For example, natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex and the like can be mentioned.

The content ratio of the rubber latex and the tackifying resin emulsion is not particularly limited, but it is appropriate that the effect of modification by the tackifying resin emulsion can be sufficiently exhibited and the adhesive strength, tack, etc. are not deteriorated due to excessive use. As a range of use, it is preferable that the pressure-imparting resin emulsion is usually about 10 to 150 parts by weight with respect to 100 parts by weight of the rubber-based latex in terms of solid content.

As the synthetic resin emulsion, various known emulsions used in the water-based adhesive composition can be used, and examples thereof include synthetic resin emulsions such as vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, and urethane emulsion. ..

The content ratio of the synthetic resin emulsion and the tackifier resin emulsion is not particularly limited, but the effect of modifying the tackifier resin emulsion can be sufficiently exhibited, and excessive use does not cause deterioration of adhesive strength, tack, etc. As an appropriate usage ratio, it is preferable that the pressure-imparting resin emulsion is usually about 2 to 40 parts by weight with respect to 100 parts by weight of the synthetic resin emulsion in terms of solid content.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" in the examples are based on weight.

Production Example 1 [Production of base polymer emulsion]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 43.4 parts of water and polyoxyethylene alkyl ether sulfate ammonium salt (anionic emulsifier: trade name) under a nitrogen gas stream. An aqueous solution consisting of 0.92 parts of "Hitenol LA-16" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was charged and the temperature was raised to 70 ° C. Next, a mixture consisting of 90 parts of butyl acrylate, 7 parts of 2-ethylhexyl acrylate and 3 parts of acrylic acid, 0.24 part of potassium persulfate (polymerization initiator), 0.11 part of baking soda (pH adjuster) and water. A 1/10 amount of an initiator aqueous solution consisting of 8.83 parts was added to the reaction vessel, and a prepolymerization reaction was carried out at 70 ° C. for 30 minutes under a nitrogen gas stream. Then, the remaining 9/10 amount of the mixture and the aqueous initiator solution were added to the reaction vessel for 2 hours to carry out emulsion polymerization, and then held at 70 ° C. for 1 hour to complete the polymerization reaction. The acrylic polymer emulsion thus obtained was cooled to room temperature and then filtered using a 100-mesh wire mesh to obtain an acrylic polymer emulsion having a solid content of 47.8%.

Production Example 2-1 [α, β-unsaturated dicarboxylic acid-modified rosin ester]
Add 100 parts of gumrosin (acid value 160 mgKOH / g, softening point 70 ° C.) and 1 part of fumaric acid to a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction tube / steam introduction tube, and add 2 parts at 200 ° C. After the time reaction, 13 parts of pentaerythritol was charged and then reacted at 280 ° C. for 5 hours under a nitrogen gas stream to complete the esterification. Then, water and the like were removed under reduced pressure to obtain an α, β-unsaturated dicarboxylic acid-modified rosin ester having a softening point of 100 ° C. (hereinafter referred to as “fumarated rosin ester”).

Production Example 2-2 [Production of gum rosin ester]
100 parts of gum rosin (same as Production Example 2-1) and 12 parts of glycerin were charged in the same reaction vessel as in Production Example 2-1 and then reacted at 250 ° C. for 1 hour under a nitrogen gas stream. Further, the temperature was raised to 280 ° C. and the reaction was carried out at the same temperature for 6 hours to complete the esterification. Then, water and the like were removed under reduced pressure to obtain a gum rosin ester having a softening point of 80 ° C.

Production Example 2-3 [Production of Polymerized Rosin Ester]
100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140 ° C.) and 14 parts of pentaerythritol were charged in the same reaction vessel as in Production Example 2-1 and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. After that, the temperature was further raised to 280 ° C. and the reaction was carried out at the same temperature for 12 hours to complete the esterification. Then, water and the like were removed under reduced pressure to obtain a polymerized rosin ester having a softening point of 160 ° C.

Production Example 3-1 [Preparation of resin emulsion]
100 parts of the fumarated rosin ester of Production Example 2-1 was melted at 180 ° C. for about 1 hour and then cooled to 150 ° C. Next, 3 parts of an anionic emulsifier (sodium dodecylbenzenesulfonate) was added in terms of solid content, and kneading was carried out at 120 ° C. for 60 minutes under pressurized conditions. Further, 105 parts of water was added and stirred for 10 minutes to obtain a resin emulsion (A-1) having a solid content of 50%.

Production Example 3-2 [Preparation of resin emulsion]
A resin emulsion (A-2) was obtained in the same manner as in Production Example 3-1 except that the fumarized rosin ester was changed to the gum rosin ester of Production Example 2-2.

Production Example 3-3 [Preparation of resin emulsion]
After dissolving 100 parts of the polymerized rosin ester of Production Example 2-3 in 70 parts of toluene at 80 ° C. for 3 hours, 3 parts of an anionic emulsifier (sodium dodecylbenzenesulfonate) and 140 parts of water in terms of solid content were added. Was added, and the mixture was stirred for 1 hour. Then, a high-pressure emulsifier (manufactured by Menton Gaulin Co., Ltd.) was used to high-pressure emulsify at a pressure of 30 MPa to obtain an emulsion. Then, it was distilled under reduced pressure for 6 hours under the condition of 70 ° C. and 2.93 × 10-2 MPa to obtain a resin emulsion (A-3) having a solid content of 50%.

Production Example 3-4 [Preparation of resin emulsion]
In Production Example 3-3, the same procedure was carried out except that the polymerized rosin ester was changed to C9 petroleum resin (trade name "Nisseki Neopolymer 120", manufactured by JX Energy Co., Ltd., softening point 120 ° C.), and the resin emulsion (A). -4) was obtained.

Production Example 3-5 [Preparation of resin emulsion]
In Production Example 3-3, the same procedure was carried out except that the polymerized rosin ester was changed to a terpene phenol resin (trade name "Dertopene T-115", manufactured by DRT, softening point 125 ° C.) to obtain a resin emulsion (A-5). rice field.

Example 1
100 parts of resin emulsion (A-1) (in terms of solid content), 3 components of (B) are polyvinylpyrrolidone (trade name "Polyvinylpyrrolidone K-30, manufactured by Kishida Chemical Co., Ltd., weight average molecular weight: 22,000)". Parts (in terms of solid content) were blended to obtain a tackifier resin emulsion (C-1).

Examples 2-11, Comparative Examples 1-6
Adhesive resin emulsions (C-2) to (C-17) were obtained with the compositions shown in Table 1.

※各成分の使用量については固形分換算で示す。

* The amount of each component used is shown in terms of solid content.

<About water-soluble polymers>
-Polyvinylpyrrolidone Weight average molecular weight: 6,000 (trade name "Polyvinylpyrrolidone K-15", manufactured by Kishida Chemical Co., Ltd.)
-Polyvinylpyrrolidone Weight average molecular weight: 22,000 (trade name "Polyvinylpyrrolidone K-30", manufactured by Kishida Chemical Co., Ltd.)
-Polyvinylpyrrolidone Weight average molecular weight: 370,000 (trade name "Polyvinylpyrrolidone K-90", manufactured by Kishida Chemical Co., Ltd.)
-Polyvinyl imidazole Weight average molecular weight: 15,000: (Product name "Marcalinker NPVI", manufactured by Maruzen Petrochemical Co., Ltd.)
-Polyvinyl alcohol Weight average molecular weight: 30,000 (trade name "Kuraray Poval PVA110", manufactured by Kuraray Co., Ltd.)

(Weight average molecular weight)
The weight average molecular weight of the water-soluble polymer used was gel permeation chromatography (manufactured by Toso Co., Ltd., trade name "HLC-8320", column: manufactured by Toso Co., Ltd., trade name "TSK-GEL GMPWXL" and " TSK-GEL G2500PWXL ”was concatenated) and determined by polyethylene oxide conversion.

Evaluation Examples 1 to 11, Comparative Evaluation Examples 1 to 6
90 parts (solid content equivalent) of the acrylic resin emulsion synthesized in Production Example 1 and 10 parts (solid content equivalent) of the tackifier resin emulsion (C-1) were mixed to obtain an aqueous viscous / adhesive composition. The same was performed for the tackifying resin emulsions (C-2) to (C-17) to obtain a water-based adhesive / adhesive composition.

The water-based adhesive / adhesive composition of Evaluation Example 1 was applied to a polyester film (trade name "S-100", manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), thickness: 38 μm), and to a dice type applicator (manufactured by Daisuke Equipment Co., Ltd.). The film was applied so that the dry film thickness was about 35 μm, and then dried in a circulating air dryer at 105 ° C. for 5 minutes to prepare a sample tape. The water-based adhesive / adhesive compositions of Evaluation Examples 2 to 11 and Comparative Evaluation Examples 1 to 6 were also applied in the same manner to prepare sample tapes, respectively.

(Heat-resistant holding power)
A sample tape (25 mm × 25 mm) was placed on a stainless steel plate, a load of 0.7 kg was applied to the sample film at 60 ° C., and the time (h) until the sample film fell was measured.

(Adhesive strength)
A sample tape (length 150 mm × width 25 mm) was placed on a polyethylene plate, a roll weighing 2 kg was reciprocated once, and the adhesive force (g / 25 mm) at the time of 180 ° peeling was measured. The test conditions are a temperature of 23 ° C. and a peeling speed of 300 mm / min.

(Probe tack)
Using an NS probe tack tester (manufactured by Nichiban Co., Ltd.), the probe AA # 40 was polished, the load was 100 g / cm ² , and the dwell time was 1 second, and the probe tack (g / 25 mmφ) of the sample tape was measured.

(Compatibility)
Using a spectrophotometer (manufactured by Hitachi, Ltd., trade name "U-3210 type self-recording spectrophotometer"), the sample tape was irradiated with light of 500 nm and the transmittance was measured. The compatibility was evaluated from the obtained transmittance as follows.
◯: Transmittance 70% or more Δ: Transmittance 50% or more and less than 70% ×: Transmittance less than 50%

Claims (7)

A resin emulsion (A) containing an emulsion of at least one emulsifying substance selected from the group consisting of a rosin-based resin (a1), a petroleum resin (a2), and a terpene-based resin (a3), and a heterocyclic nitrogen-containing water-soluble substance. Contains a plastic polymer (B) ,
A tackifier resin emulsion for water-based adhesives containing 2 to 10 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). The tackifier resin emulsion for a water-based adhesive / adhesive according to claim 1, wherein the softening point of the emulsified substance is 80 to 160 ° C. The tackifier resin emulsion for the water-based adhesive / adhesive according to claim 1 or 2, wherein the component (a1) is a rosin ester. (B) A tackifier resin emulsion for an aqueous adhesive / adhesive according to any one of claims 1 to 3, wherein the component has a weight average molecular weight of 3,000 to 500,000. (B) A tackifier resin emulsion for an aqueous adhesive / adhesive according to any one of claims 1 to 4, wherein the component is polyvinylpyrrolidone and / or polyvinylimidazole. A water-based sticky / adhesive composition containing a tackifying resin emulsion for the water-based sticky / adhesive according to any one of claims 1 to 5. A water-based sticky / adhesive composition containing the tackifier resin emulsion for the water-based sticky / adhesive according to any one of claims 1 to 5 and an acrylic polymer emulsion.