TWI771600B - Tackifier resin emulsion, water-based adhesive/adhesive composition and adhesive sheet/adhesive sheet - Google Patents

Abstract

[Technical Problem] To provide a novel tackifier resin emulsion that is excellent in emulsifiability and mechanical stability and can impart high water-resistant adhesive force to an aqueous adhesive/adhesive composition. [Technical Means] A tackifier resin emulsion containing: a tackifier resin (A); and a neutralized salt of a polymer (B) containing a polymer (B) derived from an aromatic vinyl compound (b1). Structural unit 1 and structural unit 2 derived from α,β-unsaturated dicarboxylic acids (b2), wherein the structural unit 1 in the neutralized salt of the polymer (B) and the carboxylic acid contained in the structural unit 2 The molar ratio of the salt structure is 1/1 to 3/1.

Description

Tackifier resin emulsion, water-based adhesive/adhesive composition and adhesive sheet/adhesive sheet

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

In the production of tapes, sheets, labels, etc., as adhesive/adhesive compositions to be applied to paper or plastic films as substrates, conventionally, tackifier resins and (methyl) A solution-type composition obtained by dissolving a base polymer such as an acrylic polymer in an organic solvent; however, in recent years, in consideration of the environment, safety and hygiene, and resource saving, emulsion-type water-based adhesive/adhesive compositions are being used. become mainstream.

As water-based adhesive/adhesive compositions, compositions in which the above-mentioned base polymer and tackifier resin are emulsified and mixed in the presence of various anionic emulsifiers and nonionic emulsifiers, respectively, have been proposed (refer to Patent Document 1). , Patent Document 2). However, even in the tackifier resin emulsion obtained by using the above-mentioned emulsifier, a large amount of aggregates may be generated, and the emulsifiability of the emulsion is insufficient. In addition, even if a tackifier resin emulsion with good emulsifying properties is obtained, the water-based adhesive/adhesive containing the emulsion may be easily combined with moisture, and there may be cases where the above-mentioned emulsifying agent is easily combined with moisture, and it may be difficult for various coatings under conditions of high moisture and moisture. When the adhesive force of the sticky body (hereinafter also referred to as water-resistant adhesive force) is low.

Furthermore, among the tackifying resin emulsions obtained by using the above-mentioned emulsifiers, there are also emulsions with poor mechanical stability. A high shear force is applied to the emulsion particles, and the emulsion particles are easily broken, and there is a possibility that agglomerates or the like are generated, and the coatability may be lowered. [Prior Art Literature] (patent literature)

Patent Document 1: Japanese Patent Laid-Open No. 2010-106259 Patent Document 2: Japanese Patent Application Laid-Open No. 11-61087

[Technical problem to be solved by invention] The technical problem of the present invention is to provide a novel tackifier resin emulsion which is excellent in emulsifiability and mechanical stability and can impart high water-resistant adhesive force to an aqueous adhesive/adhesive composition. [Technical means to solve technical problems]

The inventors of the present invention have conducted intensive research and found that the tackifier resin emulsion containing a specific resin and a neutralized salt of a polymer having a specific structure solves the above-mentioned technical problems. That is, the present invention relates to the following tackifier resin emulsion and water-based adhesive/adhesive composition.

1. A tackifying resin emulsion comprising: tackifying resin (A); and, a neutralized salt of a polymer (B) containing a structural unit derived from an aromatic vinyl compound (b1) 1 and structural unit 2 from α,β-unsaturated dicarboxylic acids (b2), The molar ratio of the structural unit 1 in the neutralized salt of the polymer (B) to the carboxylate structure contained in the structural unit 2 is 1/1 to 3/1.

2. The tackifier resin emulsion according to the above item 1, wherein the neutralized salt of the polymer (B) is the polymer (B) and a nitrogen-containing compound (α) having a boiling point of -35°C to 120°C. ) of neutralizing salt.

3. The tackifier resin emulsion according to the above item 1 or 2, wherein the softening point of the component (A) is 70°C to 180°C.

4. The tackifier resin emulsion according to any one of the above items 1 to 3, wherein the component (A) is selected from the group consisting of rosin-based resins (a1), petroleum resins (a2) and terpene-based resins ( a3) at least one of the group consisting of.

5. The tackifier resin emulsion according to any one of the above items 1 to 4, wherein the component (A) is a rosin ester and/or a rosin phenol resin.

6. The tackifier resin emulsion according to any one of the above items 1 to 5, wherein the component (b1) is styrene.

7. The tackifying resin emulsion according to any one of the above items 1 to 6, wherein the component (b2) is selected from the group consisting of maleic acid, maleic anhydride, and maleic acid half esters at least one.

8. The tackifier resin emulsion according to any one of the above items 1 to 7, wherein the weight average molecular weight of the component (B) is 5,000 to 30,000.

9. The tackifier resin emulsion according to any one of the above items 1 to 8, wherein the component (α) is selected from the group consisting of ammonia, monoamines, diamines, and triamines at least one.

10. An aqueous adhesive/adhesive composition comprising the tackifier resin emulsion according to any one of the above items 1 to 9 and a base polymer.

11. The water-based adhesive/adhesive composition according to the above item 10, wherein the base polymer is an acrylic polymer emulsion.

12. An adhesive sheet/adhesive sheet comprising an adhesive layer/adhesive layer and a base material formed from the water-based adhesive/adhesive composition of the above item 10 or 11. [Beneficial effect]

Compared with the case of using a conventional emulsifier, the tackifier resin emulsion of the present invention suppresses the generation of aggregates and the like, and is excellent in emulsifiability. In addition, the water-based adhesive/adhesive composition of the present invention containing the tackifier resin emulsion has high water-resistant adhesive force, and is suitable as an adhesive/adhesive in applications requiring water resistance, such as building materials, automobile interior parts, and film labels. Then agent.

Since the tackifier resin emulsion of the present invention is excellent in mechanical stability, the water-based adhesive/adhesive composition of the present invention containing the tackifier resin emulsion suppresses the generation of aggregates and the like during coating to a substrate. , the coating is good. In addition, the water-based adhesive/adhesive composition of the present invention is excellent in adhesion properties such as retention force compared to the water-based adhesive/adhesive containing the conventional tackifier resin emulsion.

The tackifier resin emulsion of the present invention (hereinafter also referred to as "tackifier resin emulsion") contains tackifier resin (A) (hereinafter also referred to as (A) component) and polymer (B) (hereinafter also referred to as ( B) Ingredient) neutralizing salt.

The component (A) is not particularly limited as long as it is a tackifier resin. The component (A) is preferably selected from the group consisting of rosin-based resin (a1) (hereinafter also referred to as (a1) component), petroleum resin (a2) (hereinafter also referred to as (a2) component), and terpene-based resin (a3). ) (hereinafter also referred to as (a3) component) at least one of the group consisting of.

The component (a1) is not particularly limited, and various known components can be used. (a1) Examples of components include natural rosins (gum rosin, tall oil rosin, wood rosin) derived from masson pine, slash pine, Nanyang pine, simao pine, loblolly pine, and king pine. ; Refined rosin obtained by refining natural rosin by vacuum distillation, steam distillation, extraction, recrystallization, etc. (hereinafter, natural rosin and refined rosin are collectively referred to as raw material rosin); The raw material rosin is hydrogenated to obtain The obtained hydrogenated rosin; the disproportionated rosin obtained by disproportionating the raw material rosin; the polymerized rosin; Ester products (hereinafter referred to as rosin esters); rosin phenol resins, etc. These may be used alone or in combination of two or more. The component (a1) is preferably a rosin ester and/or a rosin phenol resin from the viewpoint of being excellent in water-resistant adhesive strength and adhesive performance.

The component (a2) is not particularly limited, and various known components can be used. (a2) Components include, for example: C5-based petroleum resins obtained from C5 fractions of naphthas such as pentene, pentadiene, and isoprene; C9 class petroleum resins obtained from the C9 fractions of naphtha such as styrene, β-methylstyrene, etc.; C5-C9 copolymerized petroleum resins obtained from the above-mentioned C5 fractions and C9 fractions; The pure monomer resins obtained; DCPD-based petroleum resins obtained from cyclopentadiene and dicyclopentadiene (DCPD); hydrides of these petroleum resins, etc. These may be used alone or in combination of two or more. The component (a2) is preferably a C9-based petroleum resin from the viewpoint of being excellent in water-resistant adhesive strength and adhesive performance.

The component (a3) is not particularly limited, and examples thereof include resins obtained by copolymerizing known terpenes and phenols, polyterpene resins, and the like. In addition, the component (a3) may be a hydrogenated component. The component (a3) is preferably a terpene phenol resin from the viewpoint of being excellent in water-resistant adhesive strength and adhesive performance.

Hereinafter, regarding the component (a1), rosin esters and rosin phenol resins will be described. In this specification, rosin esters refer to rosin esters, polymerized rosin esters, and unsaturated carboxylic acid-modified rosin esters. The rosin esters are more preferably polymerized rosin esters from the viewpoint of being excellent in water-resistant adhesive strength and adhesive properties.

The rosin ester is obtained by reacting the above-mentioned raw material rosin, hydrogenated rosin, and disproportionated rosin with alcohols.

As the reaction conditions for the above-mentioned rosin and alcohols, in the presence or absence of a solvent, an esterification catalyst may be added as necessary, and the rosin and alcohols may be reacted at about 250°C to 280°C for about 1 to 8 hours.

The above-mentioned alcohols are not particularly limited, and examples thereof include monohydric alcohols such as methanol, ethanol, propanol, and stearyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimer Diols such as diols; triols such as glycerol, trimethylolethane, trimethylolpropane; tetraols such as pentaerythritol and diglycerol; hexaols such as dipentaerythritol, etc. The above-mentioned alcohols are preferably polyhydric alcohols having two or more hydroxyl groups, and preferably pentaerythritol.

Polymerized rosin esters are obtained by reacting polymerized rosin with alcohols. Polymeric rosin is a rosin derivative containing dimerized resin acids.

As a method for producing the polymerized rosin, a known method can be adopted. This production method includes, for example, reacting the above-mentioned raw material rosin in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, and titanium tetrachloride at a temperature of about 40°C to 160°C for 1 hour to 5 hours. method, etc.

Examples of polymerized rosin include rosin-based polymerized rosin using gum rosin as the above-mentioned raw material rosin (for example, trade name "polymerized rosin B-140", manufactured by Xinzhou (Wuping) Forest Chemical Co., Ltd.), tall oil rosin using tall oil rosin Oil-based polymerized rosin (eg, trade name "Sylvatac 140", manufactured by Arizona Chemical Company), wood-based polymerized rosin using wood rosin (eg, trade name "Dimerex", manufactured by ASHLAND Corporation), and the like.

In addition, as the polymerized rosin, a polymerized rosin that has been subjected to various treatments such as hydrogenation, disproportionation, acrylic acidization, maleation, and fumaric acidification can also be used. In addition, various processes may be performed independently, and may be performed in combination of 2 or more types. The polymerized rosin is preferably acrylated, maleated or fumarated.

As the reaction conditions of the above-mentioned polymerized rosin and alcohols, in the presence or absence of a solvent, an esterification catalyst may be added as necessary to make the polymerized rosin and alcohols react at about 250°C to 280°C for about 1 to 8 hours.

The alcohols used in the esterification of the polymerized rosin are the same as those described above.

In addition, the order of the above-mentioned polymerization reaction and the above-mentioned esterification reaction is not particularly limited to the above-mentioned case, and the polymerization reaction may be carried out after the esterification reaction.

The physical properties as the polymerized rosin ester are not particularly limited. From the viewpoint of being excellent in water-resistant adhesive force and adhesive performance, the physical properties of the polymerized rosin ester preferably have a softening point of about 150°C to 180°C. In addition, in this invention, a softening point is the value measured by the ring and ball method (JISK5902).

Unsaturated carboxylic acid-modified rosin ester is a modified rosin (α, β-unsaturated carboxylic acid-modified rosin) obtained by addition reaction of α, β-unsaturated carboxylic acids and the above-mentioned raw material rosin, and further mixed with alcohols. The rosin ester obtained by reaction and esterification.

It does not specifically limit as said (alpha), (beta)- unsaturated carboxylic acid, Various well-known thing can be used. Examples of α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride , muconic anhydride, etc. Among them, acrylic acid, maleic acid, maleic anhydride, and fumaric acid are preferred. From the viewpoint of emulsifiability, the amount of α,β-unsaturated carboxylic acids used is usually about 1 to 20 parts by weight, preferably about 1 to 3 parts by weight, relative to 100 parts by weight of the raw material rosin. .

The method for producing α,β-unsaturated carboxylic acid-modified rosin is not particularly limited. For example, the above-mentioned α,β-unsaturated carboxylic acid is added to the above-mentioned raw material rosin melted under heating, and the temperature is 180°C to 240°C. It is made to react for about 1 to 9 hours. Moreover, the said reaction can also be performed, blowing inert gas, such as nitrogen gas, into a closed reaction system. Further, in the reaction, known catalysts such as Lewis acids such as zinc chloride, ferric chloride, and tin chloride; and Bronsted acids such as p-toluenesulfonic acid and methanesulfonic acid can also be used, for example. The usage-amount of these catalysts is about 0.01 weight part - 10 weight part normally with respect to 100 weight part of said raw material rosin.

The obtained α,β-unsaturated carboxylic acid-modified rosin may contain resin acid derived from the above-mentioned raw material rosin.

The reaction conditions for the above-mentioned α,β-unsaturated carboxylic acid-modified rosin and alcohols are not particularly limited. It is made to react for about 15 to 20 hours at about 280 degreeC. In addition, the above-mentioned reaction may be performed while blowing an inert gas such as nitrogen into a closed reaction system, or the above-mentioned catalyst may be used.

The alcohols used in esterifying the α,β-unsaturated carboxylic acid-modified rosin are the same as those described above.

In addition, the order of the addition reaction and esterification reaction performed with respect to the said raw material rosin is not specifically limited to the above-mentioned case, The addition reaction may be performed after the esterification reaction.

The rosin phenol resin is obtained by reacting the above-mentioned raw material rosin with phenols.

It does not specifically limit as a phenol, Various well-known thing can be used. Specifically, alkylphenols, such as cresol, butylphenol, octylphenol, and nonylphenol; phenols; bisphenols; naphthols, etc. are mentioned. These may be used individually by 1 type, and may be used in mixture of 2 or more types. From the viewpoint of emulsifiability, the amount of the phenols to be used may be generally about 0.8 mol to 1.5 mol to react with respect to 1 mol of the above-mentioned raw material rosin.

Although it does not specifically limit as a manufacturing method of a rosin phenol resin, For example, the method of heating the said raw material rosin and phenols in presence of an acid catalyst as needed, and making it react is mentioned. As reaction conditions, the reaction may be generally conducted at 180°C to 350°C for about 6 hours to 18 hours. In addition, the acid catalyst that can be used in this reaction is not particularly limited, and examples thereof include inorganic acid catalysts such as sulfuric acid, hydrogen chloride, and boron trifluoride; and organic acid catalysts such as p-toluenesulfonic acid and methanesulfonic acid. When using an acid catalyst, about 0.01 weight part - 1.0 weight part should just be used with respect to 100 weight part of said raw material rosin. Moreover, the resin obtained by making the resin obtained by the said reaction react with alcohols, and esterification may be sufficient as a rosin resin. The alcohols used at this time are the same as those described above.

The physical properties of the component (A) are not particularly limited. From the viewpoint of being excellent in water-resistant adhesive strength and adhesive performance, the softening point is preferably about 70°C to 180°C in terms of the physical properties of the component (A). In addition, in this invention, a softening point is the value measured by the ring and ball method (JISK5902).

The component (B) contains the structural unit 1 (hereinafter also referred to as the structural unit 1) derived from the aromatic vinyl compound (b1) (hereinafter also referred to as the component (b1)) and derived from α,β-unsaturated dicarboxylic acids ( b2) The polymer of the structural unit 2 (henceforth also called the structural unit 2) (henceforth (b2) component).

As long as the component (b1) is an aromatic vinyl compound, various known ones can be used without limitation. Herein, the aromatic vinyl compound refers to a compound having an aromatic ring and a vinyl moiety. The aromatic ring may or may not have a substituent. (b1) Component, for example, styrene, α-methylstyrene, tertiary butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene and other styrenes; vinyltoluene, chlorine Vinyltoluenes such as vinyltoluene; allylbenzene; allyltoluenes such as p-allyltoluene and o-allyltoluene; vinylnaphthalene; vinylanthracene, etc. From the viewpoint of being excellent in emulsifiability, water-resistant adhesive force, and mechanical stability, the component (b1) is preferably styrene, and more preferably styrene.

As long as the component (b2) is α,β-unsaturated dicarboxylic acids, various known ones can be used without limitation. In this context, α,β-unsaturated dicarboxylic acids are selected from the group consisting of α,β-unsaturated dicarboxylic acids, α,β-unsaturated dicarboxylic acid anhydrides and α,β-unsaturated dicarboxylic acid half esters at least one of the group consisting of.

As said (alpha), (beta)- unsaturated dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, muconic acid, etc. are mentioned, for example. As said (alpha), (beta)- unsaturated dicarboxylic acid anhydride, maleic anhydride, itaconic anhydride, a citraconic anhydride etc. are mentioned, for example. Examples of the α,β-unsaturated dicarboxylic acid half ester include the α,β-unsaturated dicarboxylic acid (or the α,β-unsaturated dicarboxylic acid anhydride) and the monoalcohol in a molar ratio of 1/1. The monoester obtained by the reaction. Examples of the above-mentioned monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, 3-methoxybutanol, 4-methoxybutanol, 1-ethoxybutanol, and 2-ethoxybutanol Monohydric alcohols having an alkyl group having 1 to 18 carbon atoms, such as alcohol, 4-ethoxybutanol, pentanol, hexanol, heptanol, octanol, and stearyl alcohol. The (b2) component is more preferably at least one selected from the group consisting of maleic acid, maleic anhydride, and maleic acid half esters, mainly from the viewpoint of being excellent in emulsifiability, water resistance, and mechanical stability.

In the above-mentioned structural unit 2, the structural unit derived from the α,β-unsaturated dicarboxylic acid contains a dicarboxylic acid structure (two COOH). The structural unit derived from the α,β-unsaturated dicarboxylic acid anhydride contains two COOH dehydration ring-closed acid anhydride rings of the above-mentioned dicarboxylic acid structure. The structural unit derived from the α,β-unsaturated dicarboxylic acid half ester contains a half ester structure in which any one of the above-mentioned dicarboxylic acid structures COOH is an ester group (COOR, R is an alkyl group).

Regarding the molar ratio of the structural unit 1 and the structural unit 2 in the component (B), the carboxylate structure (COOM) of the structural unit 1 in the neutralized salt of the component (B) and the carboxylate structure (COOM) contained in the structural unit 2 The molar ratio (the number of moles of the structural unit 1/the number of moles of the carboxylate structure contained in the structural unit 2) may be set so as to be 1/1 to 3/1. This carboxylate structure is formed by neutralizing the above-mentioned dicarboxylic acid structure, acid anhydride ring, and half ester structure contained in the structural unit 2 of the component (B). Specifically, when the structural unit 2 contains a dicarboxylic acid structure or an acid anhydride ring, each structural unit 2 forms two carboxylate structures; similarly, when the structural unit 2 contains a half-ester structure, every one Structural unit 2 forms a carboxylate structure.

The molar ratio of the structural unit 1 and the structural unit 2 in the (B) component is set in consideration of the above-mentioned molar ratio in the neutralized salt of the (B) component and the number of the above-mentioned carboxylate structures formed in the structural unit 2 That's it. For the molar ratio of structural unit 1 and structural unit 2 in (B) component (molar number of structural unit 1/molar number of structural unit 2), in structural unit 2, it is derived from α,β-unsaturated dicarboxylic acid and α,β-unsaturated dicarboxylic acid anhydride, it is about 2/1 to 6/1, preferably about 2/1 to 4/1; when structural unit 2 is derived from α,β-unsaturated dicarboxylic acid half ester It is about 1/1 to 3/1, preferably about 1/1 to 2/1.

In addition, in the production method of the following (B) component, when α,β-unsaturated dicarboxylic acid and/or α,β-unsaturated dicarboxylic acid anhydride are used as the component (b2), there is a possibility that a polymerization reaction is performed. When the obtained polymer is esterified with a monoalcohol to half-esterify the structural unit 2 derived from the component (b2). In such a case, the molar ratio of the structural unit 1 and the structural unit 2 in the component (B) is usually about 1/1 to 3/1, preferably about 1/1 to 2/1.

In addition to the (b1) component and the (b2) component, other components (hereinafter also referred to as "other components") that can be the structural unit of the (B) component are not particularly limited, but the inventors of the present invention have intensively studied As a result, when the following components are used as the other components, the emulsifiability and the water-resistant adhesive force tend to be insufficient mainly due to the fact that α,β-unsaturated such as (meth)acrylic acid, crotonic acid, and isocrotonic acid are used. Monocarboxylic acids; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate base) lauryl acrylate, stearyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate (meth)acrylates such as cyclohexyl acrylate, cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, polyethylene glycol (meth)acrylate, and polypropylene glycol (meth)acrylate (meth)acrylamide, N,N'-dimethylacrylamide and N,N'-dimethylmethacrylamide and other (meth)acrylamide.

(B) The content rate of the structural unit derived from the said other component in a component is not specifically limited. The content ratio of the structural unit in the component (B) was determined by the molar ratio of the structural unit derived from the other components described above to the structural unit 1 and the structural unit 2 (the number of moles of the structural unit derived from the other component/the structural unit 1 and the structural unit 2). The total number of moles of the structural unit 2) is usually about 0 to 1/1, preferably about 0 to 1/2.

The (B) component can be obtained by subjecting the (b1) component, the (b2) component, and other components described above to a polymerization reaction if necessary. As the method of the polymerization reaction, various well-known polymerization methods such as solution polymerization and emulsion polymerization are exemplified. Examples of the solvent used for solution polymerization include benzene, toluene, xylene, hexane, cyclohexane, methanol, ethanol, isopropanol, ethyl acetate, acetone, methyl isobutyl ketone, and dioxane. Alkane, dimethylformamide and dimethyl sulfoxide, etc. In addition, when using emulsion polymerization, as various well-known non-reactive low molecular weight emulsifiers, for example, dialkyl sulfosuccinates, alkyl sulfosuccinates, α-olefin sulfonates, polymer Oxyethylene alkyl ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate and polyoxyethylene alkane Anionic emulsifiers such as phenyl ether sulfate salts; nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene styryl phenyl ethers and polyoxyethylene sorbitan fatty acid esters. In addition, the usage-amount of this low-molecular-weight emulsifier is not particularly limited, but from the viewpoint of water resistance, it is usually 5 wt % or less with respect to the total weight of the components (b1) and (b2) and other components as needed. , preferably about 0.1% by weight to 2% by weight.

In addition, with respect to the total weight of (b1) component and (b2) component and other components as needed, in the polymerization reaction, usually in the range of about 0.1% by weight to 10% by weight: benzyl peroxide, Tertiary Butyl Peroxide, Lauryl Peroxide, Cumyl Peroxide, Tertiary Butyl Hydroperoxide, Cumene Hydroperoxide, Azobisisobutyronitrile, 2,2 -Azobis-(2,4-dimethylvaleronitrile), hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, 2,2'-azobis-(2-amidinopropane)- Persulfates such as hydrochlorides, redox initiators (hydrogen peroxide-ferrous chloride, ammonium persulfate-acidic sodium sulfite, etc.), peroxides, azo compounds, and redox initiators, etc.

In addition, it can be used in a range of about 0.1 wt % to 5 wt % in the polymerization reaction with respect to the total weight of the components (b1) and (b2) and other components as needed: methyl mercaptan, ethane mercaptan , Propanethiol, Butanethiol, Octanethiol, Dodecylthiol, Thiol, Thiol, α-thionaphthalene, β-thionaphthalene, mercaptomethanol, mercaptoethanol, mercaptopropanol, Chain transfer agents such as mercaptobutanol.

In the production method of the component (B), when an α,β-unsaturated dicarboxylic acid and/or an α,β-unsaturated dicarboxylic acid anhydride is used as the component (b2), the polymer obtained by the above-mentioned polymerization reaction may be polymerized. The compound further undergoes an esterification reaction with a monoalcohol to half-esterify the structural unit 2 derived from the component (b2). As for the usage-amount of a monoalcohol, what is necessary is just to make the molar ratio of (b2) component and monoalcohol about 1/1 normally. The monoalcohol is not particularly limited. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, 3-methoxybutanol, 4-methoxybutanol, 1-ethoxybutanol, and 2-ethoxybutanol Monohydric alcohols having an alkyl group having 1 to 18 carbon atoms, such as alcohol, 4-ethoxybutanol, pentanol, hexanol, heptanol, octanol, and stearyl alcohol. The method of the esterification reaction is not particularly limited, and various known methods are exemplified.

The physical properties of the component (B) are not particularly limited. When the component (b2) above is an α,β-unsaturated dicarboxylic acid and/or an α,β-unsaturated dicarboxylic acid anhydride, the acid value of the component (B) from the viewpoint of being excellent in emulsifiability and water resistance It is preferably about 140 mgKOH/g to 450 mgKOH/g, more preferably about 190 mgKOH/g to 450 mgKOH/g. When the component (b2) above is an α,β-unsaturated dicarboxylic acid half ester, the acid value of the component (B) is preferably 90 mgKOH/g to 300 mgKOH/g from the viewpoint of being excellent in emulsifying properties and water-resistant adhesive strength about, more preferably about 160 mgKOH/g to 300 mgKOH/g. In addition, the acid value is a value measured by the following method. >Determination of acid value> To the acetone solution obtained by dissolving 0.3 g of the component (B) in 50 mL of acetone, 25 mL of a 0.1 mol/L potassium hydroxide aqueous solution was added to prepare a solution. The solution was left to stand for 10 minutes, 2 or 3 drops of phenolphthalein was added as an indicator, and then titrated with 0.1 mol/L hydrochloric acid. The acid value of the (B) component was calculated from the hydrochloric acid titration amount and the above-mentioned weight of the (B) component by the following formula. Acid value (mgKOH/g) = {25-hydrochloric acid titration (mL)} × 5.611/(B) weight of component (g)

The weight average molecular weight of the component (B) is preferably about 5,000 to 30,000, and more preferably 8,000 to 28,000, from the viewpoint of being excellent in emulsifiability, water resistance, mechanical stability, and retention. In addition, the weight average molecular weight is a polystyrene conversion value based on a gel permeation chromatography (GPC) method.

Examples of commercially available products of the component (B) include: SMA (registered trademark) 2000, SMA (registered trademark) 3000, SMA (registered trademark) EF-30, SMA (registered trademark) EF-40, SMA (registered trademark) EF-60, SMA (registered trademark) 1440, SMA (registered trademark) 2625, SMA (registered trademark) 3840 (the above are manufactured by Cray Valley Corporation), etc., but not limited to these.

The neutralized salt of the component (B) is used in the tackifier resin emulsion of the present invention to emulsify the component (A) above in water. Although conventional tackifier resin emulsions are obtained by emulsification using known anionic emulsifiers and nonionic emulsifiers, it is difficult to achieve all of excellent emulsifiability, water-resistant adhesive force, and mechanical stability. In addition, when a known polymer emulsifier is used, although excellent mechanical stability can be obtained, the emulsification property is often poor, and the water-resistant adhesive force is also insufficient. It turned out that the tackifier resin emulsion of this invention is excellent in the balance of emulsifying property, water-resistant adhesive force, and mechanical stability by using the neutralization salt of (B) component which has a specific structure. Moreover, it turned out that the tackifying resin emulsion containing this neutralization salt is excellent in the retention force in the aqueous adhesive agent/adhesive containing this tackifying resin emulsion.

The neutralized salt of the (B) component can be obtained by neutralizing the above-mentioned (B) component with various basic substances by various known methods. The alkaline substance is not particularly limited. Examples of the basic substance include hydroxides of alkali metals, hydroxides of alkaline earth metals, oxides of alkaline earth metals, ammonia, alkylamines, alkanolamines, and the like.

The above-mentioned basic substance is preferably a nitrogen-containing compound (α) (hereinafter referred to as (α) component) having a boiling point of -35°C to 120°C. By neutralizing the component (B) with the component (α), the water-based adhesive/adhesive composition containing the tackifier resin emulsion of the present invention is more excellent in water-resistant adhesive force. Although the details are not clear, the (α) component having the above-mentioned boiling point is likely to be released from the coating film to the atmosphere in the step of drying the water-based adhesive/adhesive composition applied on the substrate. As a result, it is presumed that this The hydrophobicity of the coating film is increased, and the water-resistant adhesive force is further improved.

（1） （式（1）中，X¹ 、X² 和X³ 各自獨立地表示氫或碳原子數1～5的烷基。）The (α) component is more preferably a compound represented by the following general formula (1) from the viewpoint of being excellent in emulsifying properties and water-resistant adhesive strength:

(1) (In formula (1), X ¹ , X ² and X ³ each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms.)

(α) Component, for example, ammonia; monoamine such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, secondary butylamine, tertiary butylamine, isobutylamine, pentylamine, tertiary amylamine, and isoamylamine. Amines; diamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine; triamines such as trimethylamine, triethylamine, etc. The (α) component is preferably at least one selected from the group consisting of ammonia, monoamines, diamines, and triamines, and more preferably ammonia, from the viewpoint of being excellent in emulsifiability and water-resistant adhesive strength.

(α) The usage-amount of a component is not specifically limited. The usage-amount of the component (α) is usually in the range of about 50 mol % to 500 mol % with respect to 100 mol % of the molar number of the carboxylate structure (COOM) formed by neutralization in the (B) component inside.

For the neutralized salt of the component (B), the molar ratio of the structural unit 1 in the neutralized salt to the carboxylate structure (COOM) contained in the structural unit 2 (the number of moles of the structural unit 1 / the structural unit 2 The molar number of the carboxylate structure contained in the carboxylate) must be 1/1 to 3/1. In the text, M represents alkali metal, alkaline earth metal, ammonium, primary ammonium, secondary ammonium, tertiary ammonium or quaternary ammonium. With respect to the neutralized salt of the component (B), by setting the molar ratio to be 1/1 to 3/1, the balance of hydrophobicity and hydrophilicity in the neutralized salt becomes favorable, and the emulsifiability of the tackifier resin emulsion is enhanced. And mechanical stability and water-based adhesive/adhesive becomes excellent in water resistance. For the neutralized salt of the component (B), when the molar ratio is less than 1/1, the emulsifiability of the tackifier resin emulsion and the water-resistant adhesive force of the water-based adhesive/adhesive are poor; when the molar ratio exceeds 3/ 1, the emulsification of the tackifier resin emulsion is poor. From the viewpoint of being excellent in emulsifiability and water-resistant adhesive strength, the molar ratio of the neutralized salt of the component (B) is preferably about 1/1 to 3/1, and more preferably about 1/1 to 2/1.

The neutralized salt of the component (B) has the same structure as the component (B) except that the acid component and the acid anhydride component contained in the component (B) are neutralized to form a salt.

The usage-amount of the neutralization salt of (B) component is not specifically limited. From the viewpoint of being excellent in emulsifying properties and water-resistant adhesive strength, the amount of the neutralized salt of the component (B) is preferably about 1 to 10 parts by weight, more preferably, based on 100 parts by weight of the component (A) in terms of solid content. It is about 2 to 5 parts by weight. By making the usage-amount of the neutralizing salt of the component (B) 1 part by weight or more, the emulsifiability of the above-mentioned tackifier resin emulsion becomes excellent, and by making it 10 parts by weight or less, the water-based adhesion of the emulsion containing the emulsion becomes excellent. The water-resistant adhesive strength of the agent/adhesive becomes excellent.

The tackifier resin emulsion of the present invention may contain an emulsifier (C) (hereinafter also referred to as (C) component) as necessary for the purpose of improving the emulsifiability of the emulsion as long as the desired properties of the present invention are not impaired. ). In addition, (C) component is different from (B) component.

As long as the desired properties of the present invention are not impaired, various known emulsifiers can be used as the component (C) without any particular limitation. Specifically, a high molecular weight emulsifier obtained by polymerizing a monomer, a low molecular weight anionic emulsifier, a low molecular weight nonionic emulsifier, etc. are mentioned. 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 being excellent in emulsifiability.

Examples of monomers used in the production of the high molecular weight emulsifier include (meth)acrylate-based monomers such as methyl (meth)acrylate and ethyl (meth)acrylate; (meth)acrylic acid, Monocarboxylic acid-based vinyl monomers such as crotonic acid; dicarboxylic acid-based vinyl monomers such as maleic acid and maleic anhydride; sulfonic acid-based vinyl monomers such as vinyl sulfonic acid and styrene sulfonic acid; and these Alkali metal salts, alkaline earth metal salts, ammonium salts, salts of organic bases of various organic acids; (meth)acrylamides such as (meth)acrylamides, N-methylol (meth)acrylamides, etc. Nitrile monomers such as (meth)acrylonitrile; vinyl ester monomers such as vinyl acetate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Hydroxyl-containing (meth)acrylate-based monomers such as esters; methyl vinyl ether, glycidyl (meth)acrylate, urethane acrylate, α with 6 to 22 carbon atoms -Olefins, vinylpyrrolidone and other monomers, etc. 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 reactive emulsifiers other than the following high molecular weight emulsifiers, non-reactive emulsifiers other than high molecular weight emulsifiers, and the like.

The weight average molecular weight of the above-mentioned high molecular weight emulsifier thus obtained is not particularly limited from the viewpoint of the adhesive properties of the obtained tackifier resin emulsion, but is usually preferably about 1,000 to 500,000. The weight average molecular weight referred to here is a polystyrene conversion value obtained by gel permeation chromatography (GPC).

Reactive emulsifiers other than the above-mentioned high molecular weight emulsifiers include, for example, a reactive emulsifier 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 having a carbon-carbon double bond in the molecule. agent.

Examples of the low molecular weight anionic emulsifier include dialkylsulfosuccinate, alkylsulfonate, α-olefinsulfonate, alkylbenzenesulfonate, and polyoxyethylene alkyl ether sulfonate. Succinate, polyoxyethylene styryl phenyl ether sulfosuccinate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene dialkyl ether sulfate, Polyoxyethylene trialkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, etc.

As said low molecular weight nonionic emulsifier, a polyoxyethylene alkyl ether, a polyoxyethylene styryl phenyl ether, a polyoxyethylene sorbitan fatty acid ester, etc. are mentioned, for example.

Emulsifiers other than the above-mentioned high molecular weight emulsifier may be used alone, or two or more of them may be appropriately selected and used.

From the viewpoint of being excellent in emulsifiability and water-resistant adhesive strength, the amount of the component (C) to be used is preferably about 1 to 10 parts by weight based on 100 parts by weight of the component (A) in terms of solid content, more preferably About 2 to 8 parts by weight.

As long as the desired properties are not impaired, the tackifying resin emulsion of the present invention may contain a defoaming agent; a thickening agent; a filler; an antioxidant; a water-resistance agent; pH adjusters, etc.

The tackifier resin emulsion of the present invention is obtained by emulsifying the (A) component in the presence of the (B) component and, if necessary, the (C) component (hereinafter, these are collectively referred to as "emulsifiers"), and can be used as a tackifier resin use.

The said emulsification method is not specifically limited, Well-known emulsification methods, such as a high pressure emulsification method and a phase inversion emulsification method, can be used.

The said high-pressure emulsification method is a method of making (A) component into a liquid state, premixing an emulsifier and water, performing micro-emulsification using a high-pressure emulsifier, and then removing the solvent if necessary. The method for bringing the component (A) into a liquid state may be only heating, or may be dissolved in a solvent and then heated, or a nonvolatile substance such as a plasticizer may be mixed and heated, but it is preferably performed only by heating. Moreover, as a solvent, the organic solvent which can melt|dissolve (A) component, such as toluene, xylene, methylcyclohexane, and ethyl acetate, is mentioned.

The above-mentioned phase inversion emulsification method is the following method: after the component (A) is heated and melted, an emulsifier and water are added while stirring to form a W/O emulsion, and then the phase is inverted by addition of water and temperature changes. O/W emulsion.

The concentration of the tackifier resin emulsion thus obtained is not particularly limited, and it is usually used so that the solid content is appropriately adjusted to about 20% by weight to 70% by weight. In addition, the volume average particle diameter of the obtained tackifying resin emulsion is usually about 0.1 μm to 2 μm, and most of them are uniformly dispersed as particles of 1 μm or less, but from the viewpoint of storage stability, it is preferably 0.7 μm or less. Moreover, (A) component has a white to milky white appearance, and a viscosity is about 10 mPa*s - 1,000 mPa*s normally (temperature 25 degreeC, density|concentration 50weight%). In addition, the pH is usually about 2 to 10, and the following substances may be appropriately added to adjust the pH as needed: inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; alkanolamines such as monomethylamine, monoethanolamine, diethanolamine, and diisopropanolamine ; Aliphatic amines such as ethylamine, n-butylamine, triethylamine; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, etc.

The water-based adhesive/adhesive composition of the present invention contains the tackifier resin emulsion of the present invention and a base polymer. In addition, the water-based adhesive/adhesive composition of the present invention can be used as a water-based adhesive/adhesive. In addition, in this specification, "adhesive/adhesive" means to clarify the fact that either or both of an adhesive and an adhesive are contained.

Examples of the above-mentioned base polymers include acrylic polymer emulsions, rubber-based emulsions, synthetic resin-based emulsions, and the like, and they may be used in combination respectively, and further, crosslinking agents; defoaming agents; Thickener; Filler; Antioxidant; Water-resistant agent; Film-forming aid; pH adjuster such as ammonia and sodium bicarbonate, etc. In addition, a known tackifier resin emulsion can be further used. The concentration of these water-based adhesive/adhesive compositions is usually about 40 to 70% by weight of solid content, preferably 55 to 70% by weight. At least one or more of the base polymers may be used.

As the above-mentioned acrylic polymer emulsion, emulsions commonly used in various acrylic adhesives/adhesives can be used, and can be polymerized by one-time addition polymerization of monomers such as (meth)acrylates or by sequential addition of monomers. It can be easily produced by known emulsion polymerization methods such as the emulsion monomer sequential addition polymerization method and the seed polymerization method.

Examples of the above (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Glycidyl meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. may be used alone or in combination of two or more. In addition, in order to impart storage stability to the obtained emulsion, (meth)acrylic acid may be used instead of a part of the above-mentioned (meth)acrylate. Further, as desired, copolymerizable monomers such as vinyl acetate and styrene may be used in combination to such an extent that the adhesive properties of the (meth)acrylate polymer are not impaired. In addition, as the emulsifier used in the acrylic polymer emulsion, an anionic emulsifier, partially saponified polyvinyl alcohol, etc. can be used, and the usage amount is based on 100 parts by weight of the (meth)acrylate polymer in terms of solid content. It is about 0.1 to 5 parts by weight, preferably about 0.5 to 3 parts by weight.

The content ratio of the above-mentioned acrylic polymer emulsion and tackifier resin emulsion is not particularly limited, as it can fully express the modification effect produced by the tackifier resin emulsion and will not cause retention, viscosity, etc. due to excessive use. The suitable use range for reduction is generally about 2 to 40 parts by weight of the tackifier resin emulsion based on 100 parts by weight of the acrylic polymer emulsion in terms of solid content.

As the rubber-based latex, various well-known latexes used in water-based adhesive/adhesive compositions can be used. For example, natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex, etc. are mentioned.

The content ratio of the above-mentioned rubber latex to the tackifying resin emulsion is not particularly limited, and it is suitable as a suitable material that can fully express the modification effect produced by the tackifying resin emulsion and will not cause a decrease in adhesion, viscosity, etc. due to excessive use. The range of use is generally about 10 to 150 parts by weight of the tackifier resin emulsion based on 100 parts by weight of the rubber-based latex in terms of solid content.

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

The content ratio of the above-mentioned synthetic resin emulsion and tackifier resin emulsion is not particularly limited, but it can fully express the modification effect of the tackifier resin emulsion and does not cause a decrease in adhesion, viscosity, etc. due to excessive use. The suitable range of use is generally about 2 to 40 parts by weight of the tackifier resin emulsion with respect to 100 parts by weight of the synthetic resin emulsion in terms of solid content.

The water-based adhesive/adhesive composition of the present invention is obtained by mixing the above-mentioned tackifier resin emulsion and the above-mentioned base polymer. The mixing method is not particularly limited, and various known methods can be used.

The pressure-sensitive adhesive sheet/adhesive sheet of the present invention includes an adhesive layer/adhesive layer and a base material formed from the above-mentioned water-based pressure-sensitive adhesive/adhesive composition. The adhesive sheet/adhesive sheet of the present invention may be a substrate-attached adhesive sheet/adhesive sheet having the form of the adhesive layer/adhesive layer on one side or both sides of the substrate; or the adhesive layer/adhesive layer may be maintained until peeling A base-free pressure-sensitive adhesive sheet/adhesive sheet in the form of a liner (understood as a base material having a release surface). The concept of the adhesive sheet/adhesive sheet mentioned herein may include so-called adhesive tape/adhesive tape, adhesive label/adhesive label, adhesive film/adhesive film, and the like.

As the base material, for example, polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.) films, polyester (polyethylene terephthalate, etc.) films, vinyl chloride-based resin films can be used , vinyl acetate resin film, polyimide resin film, polyamide resin film, fluorine resin film, other cellophane and other plastic films; Japanese paper, kraft paper, translucent ( Glassine) paper, high-quality paper, synthetic paper, top coat paper and other paper; woven and non-woven fabrics formed by various fibrous substances alone or blended, etc.; made of natural rubber, butyl rubber, etc. Rubber sheets; foam sheets formed from foams such as foamed polyurethane and foamed polychloroprene rubber; metal foils such as aluminum foil and copper foil; composites thereof, etc.

The pressure-sensitive adhesive sheet/adhesive sheet of the present invention can be produced by a known method. First, the above-mentioned water-based adhesive/adhesive composition is coated on one or both surfaces of a substrate to form a coating layer formed of the water-based adhesive/adhesive composition. A known method can be used for the coating method, and examples thereof include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a screen method, and a gravure coater method. Then, by heating or drying the coating layer, an adhesive layer/adhesive layer formed of the above-mentioned water-based adhesive/adhesive composition is formed. Conditions during heating or drying can be appropriately set according to the thickness of the adhesive layer/adhesive layer, etc. The temperature is, for example, 10° C. to 120° C., and the time is, for example, 0.1 hour to 10 hours. The thickness (thickness after drying) of the adhesive layer/adhesive layer varies depending on the application, but is preferably 5 μm to 200 μm.

Since the adhesive sheet/adhesive sheet of the present invention contains an adhesive layer/adhesive layer formed of the above-mentioned water-based adhesive/adhesive composition, it has high water-resistant adhesive force, and is suitable for use as building materials, automotive interior parts, film labels, etc. requiring water resistance, for example Adhesive/adhesive for sexual applications. In addition, the adhesive sheet/adhesive sheet of the present invention is also excellent in adhesive properties such as holding force. [Example]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" in the examples are by weight.

[Manufacture of base polymer] Manufacturing Example 1 In a reaction vessel equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 43.4 parts of water and polyoxyethylene alkyl ether sulfate ammonium salt (anionic emulsifier: commercial product) were added under nitrogen gas flow. Named "HITENOL LA-16", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) 0.92 parts of an aqueous solution, and the temperature was raised to 70°C. Then, a mixture of 90 parts of butyl acrylate, 7 parts of 2-ethylhexyl acrylate, and 3 parts of acrylic acid, 0.24 parts of potassium persulfate (polymerization initiator), and sodium bicarbonate (pH adjuster) were added to the reaction vessel. 1/10 of the amount of the initiator aqueous solution formed by 0.11 parts and 8.83 parts of water was prepolymerized at 70° C. for 30 minutes under nitrogen flow. Then, the above mixture and the remaining 9/10 amount of the above initiator aqueous solution were added to the reaction vessel within 2 hours to carry out emulsion polymerization, and then kept 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 metal mesh to obtain an acrylic polymer emulsion having a solid content concentration of 47.8%.

[Production of polymerized rosin ester] Manufacturing Example 2 100 parts of polymerized rosin (acid value 145 mgKOH/g, softening point 140° C.) and 14 parts of pentaerythritol were placed in a reaction vessel equipped with a stirring device, a condenser, a thermometer, a nitrogen introduction pipe, and a water vapor introduction pipe, and the mixture was placed under a nitrogen stream. After making it react at 250 degreeC for 2 hours, it heated up again to 280 degreeC, and it was made to react at the same temperature for 12 hours, and esterification was completed. Then, water and the like were removed under reduced pressure to obtain a polymerized rosin ester having a softening point of 160° C. (hereinafter referred to as (A-1) component).

[Production of Rosinol Resin] Manufacturing Example 3 In the same reaction vessel as in Production Example 2, 50 parts of gum rosin (acid value 160 mgKOH/g, softening point 70° C.) and 100 parts of phenol were added, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was added, and the mixture was heated under nitrogen flow. It was allowed to react for 3 hours. Then, after adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 4 hours. Then, moisture etc. were removed, and the rosin resin (hereinafter referred to as (A-2) component) with a softening point of 150 degreeC was obtained.

[Manufacture of gum rosin ester] Manufacturing Example 4 In the same reaction vessel as in Production Example 2, 100 parts of gum rosin (acid value of 160 mgKOH/g, softening point of 70° C.) and 1 part of fumaric acid were added, and then heated under nitrogen flow until the temperature in the system reached 220° C. to make It was reacted for 1 hour. Then, after adding 13 parts of pentaerythritol, it was made to react at 250 degreeC for 2 hours, and it heated up to 280 degreeC, made it react at the same temperature for 12 hours, and completed esterification. Then, water and the like were removed under reduced pressure to obtain gum rosin ester (hereinafter referred to as (A-3) component) having a softening point of 100°C.

[Manufacture of neutralized salt of polymer (B)] Manufacturing Example 5 Styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) 2000"), manufactured by Cray Valley Co., Ltd., mol ratio of styrene/maleic anhydride: 2/1) was put into 65 g of a 25% ammonia solution. (hereinafter referred to as (B-1) component) 50 g and 150 g of water were stirred at 80° C. for 1 hour to obtain a neutralized salt of a styrene/maleic anhydride copolymer (mol ratio of styrene/carboxylate structure: 1/1; weight average molecular weight: 10,000; solid content concentration 20%) 265g.

Manufacturing Example 6 To 15 g of a 25% ammonia solution, a styrene/maleic acid half-ester copolymer (trade name "SMA (registered trademark) 2625", manufactured by Cray Valley Co., Ltd., molar ratio of styrene/maleic acid half-ester: 2) was put /1) (hereinafter referred to as component (B-2)) 50 g and 200 g of water were stirred at 80° C. for 1 hour to obtain a neutralized salt of a styrene/maleic acid half-ester copolymer (styrene/carboxylate structure) molar ratio: 2/1; weight average molecular weight: 11,000; solid content concentration 20%) 265g.

Manufacturing Example 7 Into 80 g of a 25% aqueous ammonia solution, a styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) EF60", manufactured by CRAY VALLEY, molar ratio of styrene/maleic anhydride: 6/1) ( Hereinafter, 50 g of (B-3) component) and 200 g of water were stirred at 80° C. for 1 hour to obtain a neutralized salt of a styrene/maleic anhydride copolymer (mol ratio of styrene/carboxylate structure: 3) /1; weight average molecular weight: 16,000; solid content concentration 15%) 330g.

Manufacturing Example 8 Into 85 g of a 25% aqueous ammonia solution, a styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) 1000", manufactured by Cray Valley Co., Ltd., molar ratio of styrene/maleic anhydride: 1/1) ( The following as (B'-1) component) 50 g and water 200 g were stirred at 80° C. for 1 hour to obtain a neutralized salt of a styrene/maleic anhydride copolymer (mol ratio of styrene/carboxylate structure: 1/2; weight average molecular weight: 7,000; solid content concentration 15%) 335g.

Production Example 9 Into 80 g of a 25% aqueous ammonia solution, a styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) EF80", manufactured by CRAY VALLEY Co., Ltd., molar ratio of styrene/maleic anhydride: 8/1) ( The following as (B'-2) component) 50 g and water 200 g were stirred at 80° C. for 1 hour to obtain a neutralized salt of a styrene/maleic anhydride copolymer (mol ratio of styrene/carboxylate structure: 4/1; weight average molecular weight: 15,000; solid content concentration 15%) 330g.

Manufacturing Example 10 50 g of isobutylene/maleic anhydride copolymer (trade name "ISOBAM600", manufactured by KURARAY Co., Ltd.) (hereinafter referred to as (B'-3) component) and 200 g of water were put into 15 g of a 25% aqueous ammonia solution, and the mixture was heated at 80°C. After stirring for 1 hour, 265 g of a neutralized salt (weight average molecular weight: 6,000; solid content concentration: 20%) of an isobutylene/maleic anhydride copolymer was obtained.

[Measurement of weight average molecular weight] The weight average molecular weights of the neutralized salts of components (B-1) to (B-3) and the neutralized salts of components (B'-1) to (B'-3) were determined by gel permeation chromatography (Tosoh Corporation) Co., Ltd., trade name "HLC-8320"; Column: Tosoh Co., Ltd. product, connecting trade names "TSK-GEL GMPWXL" and "TSK-GEL G2500PWXL") to measure, and obtained by conversion of polyethylene oxide .

[Manufacture of tackifier resin emulsion] Example 1 After dissolving 100 parts of (A-1) component obtained in Production Example 2 in 80 parts of methylcyclohexane at 80° C. for 3 hours, the neutralization of the (B-1) component obtained in Production Example 5 was added. 5.0 parts of salts (in terms of solid content) and 140 parts of water were stirred for 1 hour. Then, high-pressure emulsification was performed under a pressure of 30 MPa using a high-pressure emulsifier (manufactured by Manton Gaulin) to obtain an emulsion. Then, vacuum distillation was performed under the conditions of 70° C. and 2.93×10 −2 MPa for 6 hours to obtain a tackifier resin emulsion having a solid content concentration of 50%.

Example 2 to Example 3 Except changing the neutralized salt of the component (B-1) into the neutralized salt of the component (B-2) and the neutralized salt of the component (B-3) obtained in Production Example 6 and Production Example 7, it is the same as the Example 1 In the same manner, a tackifier resin emulsion (both solid content concentration of 50%) was obtained.

Example 4 to Example 5 Except having changed the component (A-1) into the component (A-2) and the component (A-3) obtained in Production Example 3 and Production Example 4, it was carried out in the same manner as in Example 1 to obtain a tackifier resin emulsion ( All are solid content concentration 50%).

Example 6 Except that 100 parts of component (A-1) was changed to 70 parts of component (A-1) and C9-type petroleum resin (trade name "Neopolymer 140", manufactured by JXTG Energy Co., Ltd.) was used in combination (hereinafter referred to as (A-4) components) except for 30 parts, it carried out similarly to Example 1, and obtained the tackifier resin emulsion (both solid content concentration 50%). In addition, the softening point when 70 parts of (A-1) components and 30 parts of (A-4) components were used in combination was 155°C.

Example 7 The same procedure as in Example 1 was carried out, except that the component (A-1) was changed to terpene phenol (trade name "Dertophene T115", manufactured by DRT Corporation, softening point: 125°C) (hereinafter referred to as the component (A-5)). A tackifier resin emulsion (both solid content concentration of 50%) was obtained.

Comparative Example 1 to Comparative Example 3 The same procedure as in Example 1 was carried out, except that the neutralized salt of the component (B-1) was changed to the neutralized salt of the component (B'-1) to (B'-3) obtained in Production Examples 8 to 10. proceeded to obtain a tackifier resin emulsion (both with a solid content concentration of 50%).

Comparative Example 4 Except having changed the neutralized salt of the component (B-1) into sodium dodecylbenzenesulfonate (hereinafter referred to as the component (C-1)), it was carried out in the same manner as in Example 1 to obtain a tackifier resin emulsion (both 50% solid content).

[Evaluation of Emulsifying Properties] The volume average particle size of the tackifying resin emulsions of the respective Examples and Comparative Examples was measured using a laser diffraction particle size analyzer (manufactured by Shimadzu Corporation, trade name "SALD-7500nano"), with a refractive index of 1.70-0.20i. , Measured under the condition of absorbance 0.06. The obtained volume average particle diameter was evaluated according to the following criteria. The results are shown in Table 1. The smaller the volume average particle size, the better the emulsification and storage stability of the tackifying resin emulsion. ○: The volume average particle size is less than 0.7 μm △: The volume average particle diameter is 0.7 μm or more and less than 1.5 μm ×: The volume average particle size is 1.5 μm or more

In addition, the tackifying resin emulsions of the Examples and Comparative Examples were filtered with a 400-mesh metal mesh (manufactured by Nippon Gold Net Shoko Co., Ltd., with a pore size of 34 μm), and the weight % of the obtained residues relative to the tackifying resin (A) was measured. The weight % of the residue was evaluated according to the following criteria. The results are shown in Table 1. The smaller the weight % of the residue, the more suppressed the generation of aggregates in the tackifier resin emulsion, and the better the emulsifiability. ○: less than 0.1% by weight △: 0.1% by weight or more and less than 1.0% by weight ×: 1.0% by weight or more

[Evaluation of Mechanical Stability] The Maron test (according to JIS K 6828) was performed on the tackifier resin emulsions of the respective examples and comparative examples, and the occurrence rate of aggregates ((amount of aggregates/initial solid content) × 100) was calculated. The mechanical stability was evaluated according to the following criteria. The results are shown in Table 1. The higher the occurrence rate (ppm) of agglomerates, the worse the mechanical stability. ○: The occurrence rate of aggregates is less than 250 ppm △: The occurrence rate of aggregates is 250 ppm or more and less than 500 ppm ×: The occurrence rate of aggregates is 500 ppm or more >Test conditions> Sample: 30g tackifier resin emulsion (solid content 15g) Metal mesh: 200 mesh metal mesh (manufactured by Nippon Goldnet Shoko Co., Ltd., aperture 76μm) Weight: 10kg Speed: 1000rpm Spin time: 10 minutes

[Manufacture of water-based adhesive/adhesive composition] 70 parts (in terms of solid content) of the acrylic polymer emulsion synthesized in Production Example 1 and 30 parts (in terms of solid content) of the tackifier resin emulsion of Example 1 were mixed to obtain an aqueous adhesive/adhesive composition. About each tackifier resin emulsion of Examples 2 to 7 and Comparative Examples 1 to 4, water-based adhesive/adhesive compositions were produced in the same manner.

[Production of sample tape] Using a dice-type applicator (manufactured by Taiyou Machinery Co., Ltd.), the above-mentioned water-based adhesive/adhesive composition was applied on a polyester film (trade name "S-100", manufactured by Mitsubishi Chemical Co., Ltd., thickness: 38 μm) or more. It coats so that it may become about 50 micrometers in thickness, and it dries for 5 minutes in a 105 degreeC loop air dryer to prepare a sample tape.

[Evaluation of water-resistant adhesive strength] The above-mentioned sample tape was cut into a width of 25 mm, and a 2 kg roll was reciprocated on the adherend (stainless steel plate (SS)) for 2 reciprocating lamination, and it was left to stand for 1 day. Then, use a constant temperature and humidity machine (60°C, 90%RH) to leave the adherend with the sample tape attached for 7 days, take out the adherend from the constant temperature and humidity machine, and immediately stretch at a speed of 300mm/ A 180-degree peel test was performed under the conditions of a measurement temperature of 23° C., and the adhesion force (N/25 mm) was measured. The results are shown in Table 1.

[Evaluation of retention] The above-mentioned sample tapes (25 mm×25 mm) were superimposed on a stainless steel plate, and the rollers with a weight of 2 kg were reciprocated once for bonding. A load of 1.2 kg was applied to the sample tape at 60°C, and the time (h) until the sample tape dropped was measured. The results are shown in Table 1. It can be said that the longer the time until it falls, the stronger the holding power.

[Table 1]

※Notes are as follows: 1) The number of moles of structural unit 1 in the neutralized salt of component (B)/the number of moles of the carboxylate structure of structural unit 2 in the neutralized salt of component (B); 2) In the vacuum distillation of the resin emulsion, a large amount of insoluble matter was generated, and the tackifying resin emulsion could not be obtained, so the water-resistant adhesive force, mechanical stability, and retention force could not be evaluated.

Domestic storage information (please note in the order of storage institution, date and number) none

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Claims (12)

A tackifying resin emulsion comprising: tackifying resin (A); and, a neutralized salt of a polymer (B) containing structural units 1 and 1 derived from an aromatic vinyl compound (b1) Structural unit 2 derived from α,β unsaturated dicarboxylic acids (b2), wherein the molar structure of structural unit 1 in the neutralized salt of the polymer (B) and the carboxylate structure contained in structural unit 2 The ratio is 1/1~3/1. The tackifying resin emulsion according to claim 1, wherein the neutralized salt of the polymer (B) is a mixture of the polymer (B) and a nitrogen-containing compound (α) having a boiling point of -35°C to 120°C Neutralize the salt. The tackifier resin emulsion according to claim 1 or 2, wherein the softening point of the component (A) is 70°C to 180°C. The tackifier resin emulsion according to claim 1 or 2, wherein the component (A) is selected from the group consisting of a rosin-based resin (a1), a petroleum resin (a2), and a terpene-based resin (a3). at least one of. The tackifier resin emulsion according to claim 1 or 2, wherein the component (A) is a rosin ester and/or a rosin phenol resin. The tackifier resin emulsion according to claim 1 or 2, wherein the component (b1) is styrene. The tackifying resin emulsion according to claim 1 or 2, wherein Among them, the component (b2) is at least one selected from the group consisting of maleic acid, maleic anhydride, and maleic acid half ester. The tackifier resin emulsion according to claim 1 or 2, wherein the weight average molecular weight of the component (B) is 5,000 to 30,000. The tackifier resin emulsion according to claim 2, wherein the component (α) is at least one selected from the group consisting of ammonia, monoamines, diamines, and triamines. An aqueous adhesive/adhesive composition comprising the tackifier resin emulsion according to any one of claims 1 to 9 and a base polymer. The water-based adhesive/adhesive composition according to claim 10, wherein the base polymer is an acrylic polymer emulsion. An adhesive sheet/adhesive sheet comprising an adhesive layer/adhesive layer and a base material formed from the water-based adhesive/adhesive composition according to claim 10 or 11.