KR102440479B1 - Tackifying resin emulsion, water-based adhesive composition, and adhesive sheet - Google Patents

Abstract

An object of the present invention is to provide a novel tackifying resin emulsion that is excellent in emulsification and mechanical stability and can impart high water-resistance adhesion to a water-based point/adhesive composition. The present invention relates to a tackifying resin (A) and a polymer (B) comprising a structural unit 1 derived from an aromatic vinyl compound (b1) and a structural unit 2 derived from an α,β-unsaturated dicarboxylic acid (b2). It is a tackifying resin emulsion whose molar ratio of the carboxylate structure contained in the structural unit 1 and structural unit 2 in the neutralization salt of the said polymer (B) including a salt is 1/1 - 3/1.

Description

Tackifying resin emulsion, water-based point/adhesive composition, and point/adhesive sheet {TACKIFYING RESIN EMULSION, WATER-BASED ADHESIVE COMPOSITION, AND ADHESIVE SHEET}

The present invention relates to a tackifying resin emulsion, a water-based pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet.

Conventionally, as a point/adhesive composition applied to paper or plastic film, etc. as a base material when manufacturing tapes, sheets, labels, etc., a tackifying resin for imparting adhesive force and a base polymer such as a (meth)acrylic polymer are dissolved in an organic solvent. In recent years, in consideration of the environment, safety and hygiene, resource conservation, etc., the emulsion-type aqueous adhesive composition has become mainstream.

As a water-based adhesive composition, conventionally, the base polymer and the tackifying resin are separately emulsified and mixed in the presence of various anionic emulsifiers or nonionic emulsifiers (see Patent Documents 1 and 2). However, the tackifying resin emulsion obtained using the said emulsifier also generate|occur|produces many aggregates, and the emulsification property of the said emulsion was not yet sufficient. In addition, even if a tackifying resin emulsion with good emulsification property is obtained, the aqueous pressure-sensitive adhesive containing the emulsion may easily bind the above emulsifier to water, so that the emulsifier can be applied to various adherends under conditions of high moisture or moisture. Adhesive force (henceforth water-resistant adhesive force) may become low.

In addition, some tackifying resin emulsions obtained using the emulsifier have poor mechanical stability, and when high-speed application of an aqueous adhesive composition containing the emulsion to various substrates at high speed, high shear force is applied to the emulsion particles, so the emulsion is Particles were easily destroyed, aggregates etc. were generated, and the applicability|paintability may fall.

Japanese Patent Laid-Open No. 2010-106259 Japanese Patent Laid-Open No. 1999-61087

An object of the present invention is to provide a novel tackifying resin emulsion that is excellent in emulsification and mechanical stability and can impart high water-resistant adhesion to a water-based adhesive composition.

As a result of repeating earnest examination, this inventor discovered that the tackifying resin emulsion containing specific resin and the neutralization salt of the polymer which has a specific structure solved the said subject. That is, the present invention relates to the following tackifying resin emulsion and water-based adhesive composition.

1. Neutralization salt of tackifying resin (A) and polymer (B) containing structural unit 1 derived from aromatic vinyl compound (b1) and structural unit 2 derived from α,β-unsaturated dicarboxylic acids (b2) including,

The tackifying resin emulsion whose molar ratio of the carboxylate structure contained in the structural unit 1 and structural unit 2 in the neutralization salt of the said polymer (B) is 1/1 - 3/1.

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

3. (A) The tackifying resin emulsion as described in said item|item 1 or 2 whose softening point is 70-180 degreeC.

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

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

6. (b1) The tackifying resin emulsion in any one of said 1-5 whose component is styrene.

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

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

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

10. Aqueous point/adhesive composition comprising the tackifying resin emulsion according to any one of items 1 to 9 and a base polymer.

11. The aqueous adhesive composition according to item 10, wherein the base polymer is an acrylic polymer emulsion.

12. A point/adhesive sheet comprising a point/adhesive layer comprising the water-based point/adhesive composition according to item 10 or 11, and a base material.

Compared with the case where the conventional emulsifier is used, the tackifying resin emulsion of this invention suppresses generation|occurrence|production of aggregates, etc., and is excellent in emulsification property. In addition, the water-based adhesive composition of the present invention comprising the tackifying resin emulsion has a high water-resistant adhesive strength, for example, a point/adhesive in applications requiring water resistance such as building materials, automobile interior members, and film labels. very suitable as

Since the tackifying resin emulsion of the present invention has excellent mechanical stability, the aqueous point/adhesive composition of the present invention containing the tackifying resin emulsion has good applicability because generation of aggregates and the like is suppressed in application to a substrate. do. Moreover, the water-based adhesive composition of this invention is excellent in adhesive performance, such as holding force, compared with the water-based adhesive agent containing the conventional tackifying resin emulsion.

The tackifying resin emulsion (hereinafter also referred to as tackifying resin emulsion) of the present invention is composed of a tackifying resin (A) (hereinafter also referred to as (A) component) and a polymer (B) (hereinafter also referred to as (B) component). It contains neutral salts.

(A) A component will not be specifically limited if it is tackifying resin. (A) component is 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, (a3)). At least one selected from the group consisting of components) is preferable.

(a1) It does not specifically limit as a component, Various well-known things can be used. The component (a1) is, for example, natural rosin (gum rosin, tall oil rosin, wood rosin) derived from pine pine, slash pine, mercus pine, samosa pine, taeda pine, and giant pine, and natural rosin by vacuum distillation. , purified rosin obtained by purification by steam distillation method, extraction method, recrystallization method, etc. (hereinafter referred to as raw material rosin by combining natural rosin and purified rosin), hydrogenated rosin obtained by hydrogenating the raw material rosin, and disproportionately reacting the raw material rosin α, β-unsaturated carboxylic acid-modified rosin, such as obtained disproportionated rosin, polymerized rosin, acrylated rosin, maleized rosin, and fumarated rosin, or esters thereof (hereinafter referred to as rosin esters), rosin phenolic resins, and the like; can These may be individual or may combine 2 or more types. As for the component (a1), rosin esters and/or rosin phenolic resins are preferable from the viewpoint of excellent water-resistance adhesive strength and adhesion performance.

(a2) It does not specifically limit as a component, Various well-known things can be used. The component (a2) is, for example, a C5 petroleum resin obtained from a C5 fraction of naphtha such as pentene, pentadiene and isoprene; indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, etc. C9 petroleum resin obtained from C9 fraction of naphtha; C5-C9 copolymer petroleum resin obtained from the above C5 fraction and C9 fraction; Pure monomer resin obtained by polymerization of styrene or the like as a main component; Cyclopentadiene, dicyclopentadiene DCPD-type petroleum resin obtained from; Hydrogenide of these petroleum resin, etc. are mentioned. These may be individual or may combine 2 or more types. (a2) A C9-type petroleum resin is preferable at the point which is excellent in water-resistant adhesive force and adhesive performance.

(a3) It does not specifically limit as a component, Resin which copolymerized well-known terpenes and phenols, polyterpene resin, etc. are mentioned. In addition, a hydrogenated thing may be sufficient as (a3) component. The component (a3) is preferably a terpene phenol resin from the viewpoint of excellent water-resistant adhesive strength and adhesion performance.

Hereinafter, rosin esters and a rosin phenol resin are demonstrated about (a1) component. In the present specification, rosin esters refer to rosin esters, polymerized rosin esters, and unsaturated carboxylic acid-modified rosin esters. As for rosin esters, a polymerized rosin ester is more preferable at the point which is excellent in water-resistant adhesive force and adhesive performance.

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

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

It does not specifically limit as said alcohol, For example, monohydric alcohols, such as methanol, ethanol, propanol, stearyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimerdiol, etc. of dihydric alcohols, trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, and hexavalent alcohols such as dipentaerythritol. . As for the said alcohol, polyhydric alcohols which have two or more hydroxyl groups are preferable, and pentaerythritol is preferable.

Polymerized rosin ester is obtained by reacting polymerized rosin with alcohol. Polymerized rosin is a rosin derivative comprising a dimerized resin acid.

As a method for producing the polymerized rosin, a known method can be employed. In this production method, for example, the raw material rosin is prepared in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride or titanium tetrachloride at a temperature of about 40 to 160° C. for 1 to 5 hours. The method of making it react to a degree, etc. are mentioned.

The polymerized rosin is, for example, a gum-based polymerized rosin using gum rosin as the raw material rosin (for example, trade name “polymerized rosin B-140”, manufactured by Xinzhou (Wufing) Lingfuwa Co., Ltd.), tall oil-based rosin using tall oil. polymerized rosin (for example, trade name "Silvatac 140", manufactured by Arizona Chemicals), wood-based polymerized rosin using wood rosin (for example, trade name "Dymarex", manufactured by ASHLAND), etc. are mentioned.

Moreover, as polymerized rosin, you may use what carried out various processes, such as hydrogenation, disproportionation, acrylation, maleization, and fumarating, to polymerized rosin. Moreover, various processes may be individual, or may combine 2 or more types. The polymerized rosin is preferably acrylated, maleized, or fumarated.

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

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

In addition, the order of the said polymerization reaction and the said esterification reaction is not specifically limited above, You may perform a polymerization reaction after the esterification reaction.

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

The unsaturated carboxylic acid-modified rosin ester is obtained by further reacting a modified rosin (α, β-unsaturated carboxylic acid-modified rosin) obtained by addition reaction of α,β-unsaturated carboxylic acids to the raw material rosin, followed by further reaction with alcohol.

It does not specifically limit as said (alpha), (beta)- unsaturated carboxylic acid, Various well-known thing can be used. As α, β-unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic acid anhydride, etc. can be heard Among these, acrylic acid, maleic acid, maleic anhydride, and fumaric acid are preferable. The amount of the α,β-unsaturated carboxylic acid to be 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 raw material rosin from the viewpoint of emulsification properties.

Although it does not specifically limit as a manufacturing method of α, β-unsaturated carboxylic acid-modified rosin, for example, the α, β-unsaturated carboxylic acids are added to the raw material rosin dissolved under heating, and 1 to at a temperature of about 180 to 240°C. Reaction for about 9 hours is mentioned. Moreover, you may carry out the said reaction, blowing inert gas, such as nitrogen, into the sealed reaction system. Moreover, you may use well-known catalysts, such as Lewis acids, such as zinc chloride, iron chloride, and a tin chloride, and Bronsted acid, such as para-toluenesulfonic acid and methanesulfonic acid, for reaction, for example. The amount of these catalysts used is usually about 0.01 to 10 parts by weight based on 100 parts by weight of the raw material rosin.

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

The reaction conditions of the α,β-unsaturated carboxylic acid-modified rosin and alcohol are not particularly limited, but for example, alcohol is added to the α,β-unsaturated carboxylic acid-modified rosin dissolved under heating, and the temperature is about 250 to 280°C for 15 minutes. Reaction for about 20 hours is mentioned. Moreover, the said reaction may be performed, blowing inert gas, such as nitrogen, into the sealed reaction system, and the above-mentioned catalyst may be used.

Alcohols used for esterification of α,β-unsaturated carboxylic acid-modified rosin are the same as above.

In addition, the order of addition reaction and esterification reaction with respect to the said raw material rosin is not specifically limited above, You may perform addition reaction after esterification reaction.

The rosin phenolic resin is obtained by reacting the raw material rosin with phenols.

It does not specifically limit as phenols, Various well-known things can be used. Specific examples thereof include alkylphenols such as cresol, butylphenol, octylphenol and nonylphenol, phenol, bisphenol, and naphthol. These may be used individually by 1 type, or may mix and use 2 or more types. From the viewpoint of emulsification properties, the amount of the phenols to be used is usually about 0.8 to 1.5 moles per mole of the raw material rosin.

Although it does not specifically limit as a manufacturing method of a rosin phenol resin, For example, heating and making the said raw material rosin and phenols react in presence of an acid catalyst as needed is mentioned. As reaction conditions, what is necessary is just to make it react at 180-350 degreeC normally for about 6-18 hours. The acid catalyst usable for the 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 paratoluenesulfonic acid and methanesulfonic acid. In the case of using an acid catalyst, about 0.01 to 1.0 parts by weight may be used based on 100 parts by weight of the raw material rosin. Further, the rosin phenol resin may be esterified by further reacting the resin obtained by the above reaction with alcohols. The alcohols used in that case are the same as the above.

(A) It does not specifically limit as a physical property of a component. It is preferable that the softening point of the physical property of (A) component is about 70-180 degreeC from the point which is excellent in water-resistant adhesive force and adhesive performance. In addition, in this invention, a softening point is the value measured by the ring-ball method (JISK5902).

Component (B) is a structural unit 1 (hereinafter, structural unit 1) derived from the aromatic vinyl compound (b1) (hereinafter also referred to as (b1) component) and α,β-unsaturated dicarboxylic acids (b2) (hereinafter, ( b2) It is a polymer containing the structural unit 2 (henceforth structural unit 2) derived from component).

(b1) As long as it is an aromatic vinyl compound, various well-known things can be used without restriction|limiting as a component. Here, the aromatic vinyl compound means a compound having an aromatic ring and a portion of a vinyl group. What has a substituent may be sufficient as the said aromatic ring, and the thing which does not have a substituent may be sufficient as it. The component (b1) includes, for example, styrenes such as styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, and hydroxystyrene; vinyltoluenes such as vinyltoluene and chlorovinyltoluene; allylbenzene Allyltoluenes, such as , p-allyltoluene and o-allyltoluene, vinylnaphthalene, vinylanthracene, etc. are mentioned. (b1) From the point of being excellent in emulsification property, water-resistant adhesive force, and mechanical stability, styrene is preferable and styrene is more preferable.

As the component (b2), various known compounds can be used without limitation as long as they are α, β-unsaturated dicarboxylic acids. Here, α, β-unsaturated dicarboxylic acids means at least one selected from the group consisting of α, β-unsaturated dicarboxylic acids, α, β-unsaturated dicarboxylic acid anhydrides, and α, β-unsaturated dicarboxylic acid halfesters.

Examples of the α,β-unsaturated dicarboxylic acid include fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, and muconic acid. Examples of the α,β-unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. As the α,β-unsaturated dicarboxylic acid halfester, for example, a monoester obtained by reacting the α,β-unsaturated dicarboxylic acid (or the α,β-unsaturated dicarboxylic acid anhydride) with a monoalcohol at a molar ratio of 1/1 can be heard The monoalcohol is, for example, methanol, ethanol, propanol, isopropanol, butanol, 3-methoxybutanol, 4-methoxybutanol, 1-ethoxybutanol, 2-ethoxybutanol, 4-ethoxybutanol, and pentanol. and monohydric alcohols having an alkyl group having 1 to 18 carbon atoms, such as hexanol, heptanol, octanol and stearyl alcohol. The component (b2) 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 excellent emulsification properties, water resistance and mechanical stability.

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

The molar ratio of the structural unit 1 and the structural unit 2 in the component (B) is the molar ratio of the carboxylate structure (COOM) contained in the structural unit 1 and the structural unit 2 in the neutralized salt of the component (B) (structural unit 1) What is necessary is just to set so that the number of moles of / mole number of the carboxylate structure contained in structural unit 2) may be 1/1 to 3/1. The said carboxylate structure is formed by neutralizing the said dicarboxylic acid structure contained in structural unit 2 of (B) component, an acid anhydride ring, and a half-ester structure. Specifically, when a dicarboxylic acid structure or an acid anhydride ring is contained in structural unit 2, two carboxylate structures are formed per one structural unit 2, and similarly, when a half ester structure is contained in structural unit 2, structural unit 2 One carboxylate structure is formed per one.

The molar ratio of the structural unit 1 and the structural unit 2 in the component (B) may be set in consideration of the molar ratio in the neutralized salt of the component (B) and the number of the carboxylate structures formed in the structural unit 2. (B) The molar ratio of the structural unit 1 and the structural unit 2 in the component (the number of moles of the structural unit 1 / the number of moles of the structural unit 2) is the α, β-unsaturated dicarboxylic acid or the α, β-unsaturated dicarboxylic acid When it is derived from an anhydride, it is about 2/1 to 6/1, preferably about 2/1 to 4/1, and when the structural unit 2 is derived from an α, β-unsaturated dicarboxylic acid halfester, it is about 1/1 to About 3/1, Preferably it is about 1/1 - 2/1.

In addition, in the manufacturing method of component (B) mentioned later, when using α,β-unsaturated dicarboxylic acid and/or α,β-unsaturated dicarboxylic acid anhydride for component (b2), monoalcohol is added to the polymer obtained by polymerization reaction. esterification reaction 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, and preferably about 1/1 to 2/1.

Other than components (b1) and (b2), other components (hereinafter also referred to as other components) that can be a structural unit of component (B) are not particularly limited, but as a result of intensive studies by the present inventors, as the other components, α, β-unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid and isocrotonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, normal butyl (meth)acrylate, (meth)acrylic acid Dodecyl, (meth)acrylic acid lauryl, (meth)acrylic acid stearyl, (meth)acrylic acid isobutyl, (meth)acrylic acid tertbutyl, (meth)acrylic acid-2-ethylhexyl, (meth)acrylic acid cyclohexyl, ( (meth)acrylic acid esters, such as (meth)acrylic acid cyclopentyl, (meth)acrylic acid isobornyl, (meth)acrylic acid polyethylene glycol ester, and (meth)acrylic acid polypropylene glycol ester, (meth)acrylamide, N, N'- When (meth)acrylamides, such as dimethyl acrylamide and N,N'- dimethylmethacrylamide, are used, since emulsification property and water-resistant adhesive force mainly tend to become inadequate, it is not preferable.

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

The component (B) is obtained by polymerization-reacting the component (b1) and the component (b2) and, if necessary, the other components. As a method of a polymerization reaction, various well-known polymerization methods, such as solution polymerization and emulsion polymerization, are mentioned. Examples of the solvent used for solution polymerization include benzene, toluene, xylene, hexane, cyclohexane, methanol, ethanol, isopropyl alcohol, ethyl acetate, acetone, methyl isobutyl ketone, dioxane, dimethylformamide, and dimethyl sulfoxide. can do. In the case of emulsion polymerization, various known non-reactive low molecular weight emulsifiers include, for example, dialkylsulfosuccinic acid ester salts, alkanesulfonic acid salts, α-olefinsulfonic acid salts, polyoxyethylenealkylethersulfosuccinic acid ester salts, and poly anionic emulsifiers such as oxyethylene styrylphenyl ether sulfosuccinic acid ester salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, and polyoxyethylene alkyl phenyl ether sulfate ester salt; polyoxyethylene alkyl ether; Nonionic emulsifiers, such as polyoxyethylene styryl phenyl ether and polyoxyethylene sorbitan fatty acid ester, can be used suitably. In addition, the amount of the low molecular weight emulsifier to be used is not particularly limited, but from the viewpoint of water resistance, it is usually 5% by weight or less, preferably 0.1 to about 2% by weight.

In addition, during the polymerization reaction, benzoyl peroxide, tert-butyl peroxide, lauroyl peroxide, cumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, 2,2-azo Bis-(2,4-dimethylvaleronitrile), hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, 2,2'-azobis-(2-amidinopropane)-hydrochloride, redox initiator ( Hydrogen peroxide - ferrous chloride, ammonium persulfate - acid sodium sulfite, etc.), initiators such as peroxides, azo compounds, and redox, etc. It can be used in the range of about 0.1 to 10% by weight based on the total weight.

In addition, during the polymerization reaction, methanethiol, ethanethiol, propanethiol, butanethiol, octanethiol, dodecanethiol, benzenethiol, toluenethiol, α-naphthalenethiol, β-naphthalenethiol, mercaptomethanol, mercaptoethanol, mer A chain transfer agent such as captopropanol or mercaptobutanol may be used in an amount of about 0.1 to 5% by weight based on the total weight of the component (b1) and component (b2) and, if necessary, the other components.

In the method for producing component (B), when α,β-unsaturated dicarboxylic acid and/or α,β-unsaturated dicarboxylic acid anhydride are used as component (b2), a monoalcohol is further added to the polymer obtained by the polymerization reaction. may be subjected to an esterification reaction, and the structural unit 2 derived from component (b2) may be half-esterified. As for the usage-amount of monoalcohol, normally, the molar ratio of (b2) component and monoalcohol should just be about 1/1. The said monoalcohol is not specifically limited. The monoalcohol is, for example, methanol, ethanol, propanol, isopropanol, butanol, 3-methoxybutanol, 4-methoxybutanol, 1-ethoxybutanol, 2-ethoxybutanol, 4-ethoxybutanol, and pentanol. and monohydric alcohols having an alkyl group having 1 to 18 carbon atoms, such as hexanol, heptanol, octanol and stearyl alcohol. It does not specifically limit as a method of an esterification reaction, Various well-known methods are mentioned.

(B) The physical property of a component is not specifically limited. When the component (b2) is an α, β-unsaturated dicarboxylic acid and/or an α, β-unsaturated dicarboxylic acid anhydride, the component (B) has excellent emulsification properties and water-resistant adhesion, and an acid value of 140 to 450 mgKOH/g The degree is preferable, and about 190-450 mgKOH/g is more preferable. When the component (b2) is an α, β-unsaturated dicarboxylic acid half ester, the component (B) preferably has an acid value of about 90 to 300 mgKOH/g, and has an acid value of about 160 to 300 mgKOH/g from the viewpoint of excellent emulsification and water resistance adhesion. g is more preferable. In addition, an acid value is the value measured by the following method.

<Acid value measurement>

(B) To the acetone solution in which 0.3 g of component was dissolved in 50 ml of acetone, the solution which added 25 ml of 0.1 mol/L potassium hydroxide aqueous solution is prepared. The solution is left to stand for 10 minutes, and after adding 2 or 3 drops of phenolphthalein as an indicator, titration is performed with 0.1 mol/L hydrochloric acid. From a hydrochloric acid titration amount and the said weight of (B) component, the acid value of (B) component is computed by a following formula.

Acid value (mgKOH/g) = ｛25 - Hydrochloric acid titration amount (ml) x 5.611/(B) Weight of component (g)

The component (B) preferably has a weight average molecular weight of about 5,000 to 30,000, more preferably 8,000 to 28,000, from the viewpoint of excellent emulsification, water resistance, mechanical stability and holding power. In addition, the weight average molecular weight is a polystyrene conversion value by gel permeation chromatography (GPC) method.

(B) As a commercial item of the component, SMA (trademark) 2000, SMA (trademark) 3000, SMA (trademark) EF-30, SMA (trademark) EF-40, SMA (registered trademark) EF- 60, SMA (registered trademark) 1440, SMA (registered trademark) 2625, SMA (registered trademark) 3840 (above, manufactured by Cray Valley), etc., but are not limited thereto.

(B) The neutralization salt of component is used in order to emulsify the said (A) component in water in the tackifying resin emulsion of this invention. Conventional tackifying resin emulsions are obtained by emulsifying them using known anionic or nonionic emulsifiers, but in some cases, it is difficult to obtain those having excellent emulsification properties, water resistance adhesion and mechanical stability. Moreover, when a well-known polymer emulsifier is used, the thing excellent in mechanical stability was obtained, but it was inferior in emulsification property, and it was also a thing with insufficient water-resistance adhesive force. It became clear that the tackifying resin emulsion of this invention is excellent in emulsification property, water-resistant adhesive force, and mechanical stability with a good balance by using the neutralization salt of (B) component which has a specific structure. Moreover, it became clear that the tackifying resin emulsion containing the said neutralization salt is excellent in the holding power in the aqueous|water-based adhesive agent containing it.

The neutralization salt of (B) component is obtained by neutralizing the said (B) component with various alkaline substances by various well-known methods. The alkaline substance is not particularly limited. Examples of the alkaline substance include hydroxides of alkali metals, hydroxides of alkaline earth metals, oxides of alkaline earth metals, ammonia, alkylamines, and alkanolamines.

It is preferable that the said alkaline substance is a nitrogen-containing compound (alpha) (henceforth a (alpha) component) whose boiling point is -35-120 degreeC. By using the (α) component for neutralization of the component (B), the aqueous point/adhesive composition containing the tackifying resin emulsion of the present invention is more excellent in water-resistant adhesive force. Although the details are not clear, the component (α) having the above boiling point is easily separated from the coating film into the atmosphere in the process of drying the water-based point/adhesive composition applied to the substrate, and as a result, the hydrophobicity of the coating film is increased, so that the water-resistant adhesive strength is further improved. It is estimated.

The component (α) is more preferably a compound represented by the following general formula (1) from the viewpoint of excellent emulsification properties and water-resistant adhesive force.

(1)

(One)

(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 is, for example, ammonia; methylamine, ethylamine, propylamine, isopropylamine, butylamine, s-butylamine, t-butylamine, isobutylamine, pentylamine, t-pentylamine, iso monoamines such as pentylamine; diamines such as dimethylamine, diethylamine, dipropylamine, and diisopropylamine; and triamines such as trimethylamine and triethylamine. The component (α) is preferably at least one selected from the group consisting of ammonia, monoamines, diamines and triamines, and more preferably ammonia, from the viewpoint of excellent emulsification properties and water-resistant adhesion.

(α) The usage-amount of a component is not specifically limited. The usage-amount of component ((alpha)) should just be about 50-500 mol% with respect to 100 mol% of moles of the carboxylate structure (COOM) formed by neutralization in (B) component normally.

(B) The neutralization salt of the component is a molar ratio of the carboxylate structure (COOM) contained in the structural unit 1 and the structural unit 2 in the neutralizing salt (the number of moles of the structural unit 1 / the number of moles of the carboxylate structure contained in the structural unit 2) ) must be between 1/1 and 3/1. Here, M represents an alkali metal, alkaline earth metal, ammonium, primary ammonium, secondary ammonium, tertiary ammonium or quaternary ammonium. (B) As for the neutralized salt of component, when the said molar ratio is 1/1 - 3/1, the balance of hydrophobicity and hydrophilicity in the said neutralized salt becomes favorable, and the emulsification and mechanical stability of a tackifying resin emulsion, and water system It becomes a thing excellent in the water-resistant adhesive force of an adhesive agent. (B) When the molar ratio of the component (B) is less than 1/1, the emulsification property of the tackifying resin emulsion and the water-resistant adhesive force of the water-based point/adhesive are poor, and when the molar ratio exceeds 3/1, the tackifying resin emulsion the emulsification property of (B) The molar ratio is preferably about 1/1 to 3/1, and more preferably about 1/1 to 2/1, from the viewpoint of excellent emulsification properties and water-resistant adhesive strength.

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

(B) The usage-amount of the neutralization salt of a component is not specifically limited. The neutralization salt of component (B) is preferably about 1 to 10 parts by weight, more preferably about 2 to 5 parts by weight, based on 100 parts by weight of component (A) in terms of solid content, in terms of solid content, from the viewpoint of excellent emulsification properties and water-resistant adhesion. do. (B) When the amount of the neutralization salt of the component is 1 part by weight or more, the tackifying resin emulsion is excellent in emulsification, and by setting it to 10 parts by weight or less, the water-based adhesive agent containing the emulsion has a water-resistant adhesive strength. becomes excellent.

The tackifying resin emulsion of the present invention contains, if necessary, an emulsifier (C) (hereinafter also referred to as (C) component) for the purpose of improving the emulsification properties of the emulsion, as long as the desired properties of the present invention are not impaired. good to do In addition, (C)component is a thing different from (B)component.

The component (C) is not particularly limited as long as the desired properties of the present invention are not impaired, and various known emulsifiers can be used. Specific examples 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 individual or may combine 2 or more types. Among these, a low molecular weight anionic emulsifier is preferable at the point which is excellent in emulsification property.

Examples of the monomer used in the production of the high molecular weight emulsifier include (meth)acrylic acid ester-based monomers such as (meth)methyl acrylate and (meth)ethyl acrylate; (meth)acrylic acid, monocarboxylic acid-based vinyl such as crotonic acid Monomers; Dicarboxylic acid-based vinyl monomers such as maleic acid and maleic anhydride; Sulfonic acid-based vinyl monomers such as vinylsulfonic acid and styrenesulfonic acid; And alkali metal salts, alkaline earth metal salts, ammonium salts, and salts of organic bases of these various organic acids; (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; ( (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, etc. hydroxyl group-containing (meth)acrylic acid ester monomers; methyl vinyl ether, glycidyl (meth)acrylate, urethane acrylate, carbon number 6 and other monomers such as α-olefin of ~22 and vinylpyrrolidone. These may be used individually or in combination of 2 or more types.

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

Although the weight average molecular weight of the high molecular weight emulsifier thus obtained is not particularly limited, it is usually preferable to set it to about 1,000 to 500,000 from the viewpoint of the adhesive properties of the resulting tackifying resin emulsion. The weight average molecular weight referred to herein is a polystyrene conversion value by the gel permeation chromatography (GPC) method.

Examples of reactive emulsifiers other than the high molecular weight emulsifier include 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 having a carbon-carbon double bond in the molecule.

Examples of the low molecular weight anionic emulsifier include dialkylsulfosuccinic acid ester salts, alkanesulfonic acid salts, α-olefinsulfonic acid salts, alkylbenzenesulfonic acid salts, polyoxyethylene alkylethersulfosuccinic acid ester salts, and polyoxyethylene styrylphenyl ethersulfo salts. Succinic acid ester salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene dialkyl ether sulfate ester salt, polyoxyethylene trialkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, etc. can be heard

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

An emulsifier other than the high molecular weight emulsifier may be used alone or two or more may be appropriately selected for use.

(C) The amount of the component used is preferably about 1 to 10 parts by weight, more preferably about 2 to 8 parts by weight, based on 100 parts by weight of the component (A), in terms of solid content, from the viewpoint of excellent emulsification and water-resistant adhesion. .

The tackifying resin emulsion of the present invention may contain, if necessary, an antifoaming agent, a thickener, a filler, an antioxidant, a waterproofing agent, a film forming aid, a pH adjuster such as aqueous ammonia or sodium hydrogen carbonate, etc., as long as the desired properties are not impaired.

The tackifying resin emulsion of the present invention is formed by emulsifying component (A) in the presence of component (B) and optionally component (C) (hereinafter, collectively referred to as “emulsifier”), and is used as tackifying resin. can be

It does not specifically limit as said emulsification method, Well-known emulsification methods, such as a high pressure emulsification method and an inversion emulsification method, are employable.

The high-pressure emulsification method is a method in which component (A) is in a liquid state, premixed with an emulsifier and water, finely emulsified using a high-pressure emulsifier, and the solvent is removed if necessary. (A) As for the method of making a component into a liquid state, even if it heats after melt|dissolving in a solvent only by heating, although nonvolatile substances, such as a plasticizer, may be mixed and heated, it is preferable to carry out only by heating. Moreover, as a solvent, the organic solvent which can melt|dissolve (A) components, such as toluene, xylene, methylcyclohexane, and ethyl acetate, is mentioned.

The phase inversion emulsification method is a method of inverting the component (A) by heating and dissolving, adding an emulsifier and water while stirring, first forming a W/O emulsion, and then inverting it into an O/W emulsion by adding water or changing the temperature. .

Although the density|concentration of the tackifying resin emulsion obtained in this way is not specifically limited, Usually, it adjusts suitably so that solid content may become about 20 to 70 weight% and is used. Moreover, the volume average particle diameter of the obtained tackifying resin emulsion is about 0.1-2 micrometers normally, Although most are uniformly disperse|distributed as 1 micrometer or less particle|grains, it is preferable to set it as 0.7 micrometer or less from the point of storage stability. Moreover, (A) component shows a white thru|or milky white external appearance, and a viscosity is about 10-1,000 mPa*s normally (temperature 25 degreeC, density|concentration 50 weight%). Moreover, although pH is usually about 2-10, if necessary, inorganic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid; Alkanolamines, such as monomethylamine, monoethanolamine, diethanolamine, diisopropanolamine; Ethylamine, n- Aliphatic amines such as butylamine and triethylamine; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide may be appropriately added to adjust the pH.

The aqueous adhesive composition of the present invention contains the tackifying resin emulsion of the present invention and a base polymer. Moreover, the aqueous adhesive composition of this invention can be used as a water-based adhesive agent. In addition, in this specification, it clarifies that any one or both of an adhesive and an adhesive agent are included with "a point/adhesive agent".

Examples of the base polymer include acrylic polymer emulsion, rubber latex and synthetic resin emulsion, and each may be used in combination. or a pH adjuster such as sodium bicarbonate or the like can also be used. Moreover, you may use a well-known tackifying resin emulsion further. The density|concentration of these aqueous adhesive composition is about 40 to 70 weight% of solid content normally, Preferably it is 55 to 70 weight%. It is good to use at least 1 type or more of a base polymer.

As the acrylic polymer emulsion, those generally used for various acrylic adhesives and adhesives can be used, and a batch input polymerization method of monomers such as (meth)acrylic acid ester, a monomer sequential addition polymerization method, an emulsified monomer sequential addition polymerization method, and a seed It can manufacture easily by well-known emulsion polymerization methods, such as a polymerization method.

Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acrylic acid. 2-hydroxyethyl etc. are mentioned, These are used individually or in mixture of 2 or more types. Moreover, in order to provide storage stability to the emulsion obtained, you may use (meth)acrylic acid instead of a part of the said (meth)acrylic acid ester. Further, if desired, copolymerizable monomers such as vinyl acetate and styrene can be used in combination to the extent that the adhesive properties of the (meth)acrylic acid ester 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 amount used is about 0.1 to 5 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester polymer in terms of solid content, preferably Usually 0.5 to 3 parts by weight.

Although the content ratio of the said acrylic polymer emulsion and the tackifying resin emulsion is not specifically limited, The effect of modification by the tackifying resin emulsion can fully be expressed, and also suitable for excessive use which does not cause a decrease in retention, stickiness, etc. As a usage range, it is good to make about 2-40 weight part of tackifying resin emulsion normally with respect to 100 weight part of acrylic polymer emulsion in conversion of solid content.

As said rubber latex, various well-known things used for the aqueous adhesive composition can be used. For example, natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex, etc. are mentioned.

The content ratio of the rubber-based latex and the tackifying resin emulsion is not particularly limited, but the effect of modification by the tackifying resin emulsion can be sufficiently expressed, and a suitable range of use that does not cause a decrease in adhesion, stickiness, etc. due to excessive use As such, in terms of solid content, the amount of the tackifying resin emulsion is usually about 10 to 150 parts by weight with respect to 100 parts by weight of the rubber latex.

As said synthetic resin emulsion, various well-known things used for water-based adhesive composition can be used, For example, synthetic resin emulsions, such as a vinyl acetate type emulsion, an ethylene-vinyl acetate copolymer emulsion, and a urethane type emulsion, are mentioned.

The content ratio of the synthetic resin-based emulsion and the tackifying resin emulsion is not particularly limited, but the effect of modifying the tackifying resin emulsion can be sufficiently expressed, and an appropriate range of use that does not cause a decrease in adhesive strength, stickiness, etc. due to excessive use In terms of solid content, the amount of the tackifying resin emulsion is usually about 2 to 40 parts by weight based on 100 parts by weight of the synthetic resin emulsion.

The aqueous adhesive composition of the present invention is obtained by mixing the tackifying resin emulsion and the base polymer. It does not specifically limit as a mixing method, Various well-known methods can be used.

The point/adhesive sheet of the present invention is to include a point/adhesive layer and a base material made of the water-based point/adhesive composition. The point/adhesive sheet of the present invention may be a point/adhesive sheet with a substrate in the form of having the point/adhesive layer on one or both sides of the substrate, and the point/adhesive layer may be grasped as a release liner (a substrate having a release surface) ) may be a point/adhesive sheet without a description such as a form in which it is inserted. The concept of the point/adhesive sheet referred to herein may include what is called a point/adhesive tape, a point/adhesive label, a point/adhesive film, and the like.

Examples of the substrate include a polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.) film, a polyester (polyethylene terephthalate, etc.) film, a vinyl chloride-based resin film, a vinyl acetate-based resin film, and a polyvinyl chloride-based resin film. Mid-based resin film, polyamide-based resin film, fluorine-based resin film, and other plastic films such as cellophane; Japanese paper, kraft paper, glassine paper, fine paper, synthetic paper, topcoat paper ; Fabrics such as woven or nonwoven fabrics made of various fibrous materials alone or by blending, etc.; Rubber sheets made of natural rubber and butyl rubber; Metal foils, such as copper foil; These composites, etc. can be used.

The pressure-sensitive adhesive sheet of the present invention can be produced by a known method. First, the water-based point/adhesive composition is applied to one or both surfaces of a substrate to form an application layer made of the water-based point/adhesive composition. As the coating method, a known method can be applied, and examples include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silkscreen process method, and a gravure coater method. Next, by heating or drying the coating layer, a point/adhesive layer composed of the water-based point/adhesive composition is formed. The conditions at the time of heating or drying can be suitably set by the thickness of a point, adhesive layer, etc., temperature is 10-120 degreeC, for example, and time is 0.1-10 hours, for example. Although the thickness (thickness after drying) of the said point and adhesive layer changes with a use, Preferably it is 5-200 micrometers.

Since the point/adhesive sheet of the present invention contains a point/adhesive layer made of the water-based point/adhesive composition, it has a high water-resistant adhesive force, for example, a use in which water resistance is required for building materials, automobile interior members, film labels, etc. It is very suitable as a point/adhesive sheet in In addition, the point/adhesive sheet of the present invention is also excellent in adhesive performance such as holding force.

<Example>

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. In Examples, "parts" and "%" are by weight unless otherwise specified.

[Production of base polymer]

Preparation Example 1

In a reaction vessel equipped with a stirring device, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, under a nitrogen gas stream, 43.4 parts of water and polyoxyethylene alkyl ether sulfate ester ammonium salt (anionic emulsifier: trade name "Hitenol LA-" 16", an aqueous solution consisting of 0.92 parts of Daiichi Kogyo Pharmaceutical Co., Ltd. was added, 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 parts of potassium persulfate (polymerization initiator), 0.11 parts of sodium hydrogencarbonate (pH adjuster), and 8.83 parts of water. 1/10 amount was added to the reaction vessel, and a prepolymerization reaction was performed at 70° C. for 30 minutes under a nitrogen gas stream. Next, the remaining 9/10 amount of the mixture and the aqueous initiator solution were added to the reaction vessel over 2 hours to conduct emulsion polymerization, and then, the mixture was maintained 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 concentration of 47.8%.

[Preparation of polymerized rosin ester]

Preparation 2

100 parts of polymerized rosin (acid value of 145 mgKOH/g, softening point of 140 ° C.) and 14 parts of pentaerythritol were placed in a reaction vessel equipped with a stirring device, condenser, thermometer, and nitrogen inlet tube and water vapor inlet tube, and then at 250 ° C. under a nitrogen gas stream. After reacting for 2 hours, the temperature was further raised to 280° C. and reacted at the same temperature for 12 hours to complete esterification. Thereafter, moisture and the like were removed under reduced pressure to obtain a polymerization rosin ester having a softening point of 160°C (hereinafter referred to as component (A-1)).

[Production of rosin phenolic resin]

Preparation 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 put, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was added, and 3 hours under a nitrogen gas stream. reacted. 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. After that, water and the like were removed to obtain a rosin phenol resin having a softening point of 150°C (hereinafter referred to as (A-2) component).

[Production of Gum Rosin Ester]

Preparation 4

In the same reaction vessel as in Production Example 2, 100 parts of gum rosin (acid value 160 mgKOH/g, softening point 70° C.) and 1 part fumaric acid were put, and then heated under a stream of nitrogen gas until the internal temperature of the system reached 220° C. for 1 hour. reacted. Then, after adding 13 parts of pentaerythritol, after reacting at 250° C. for 2 hours, the temperature was further raised to 280° C. and reacted at the same temperature for 12 hours to complete esterification. Thereafter, moisture and the like were removed under reduced pressure to obtain a gum rosin ester having a softening point of 100°C (hereinafter referred to as component (A-3)).

[Production of neutralized salt of polymer (B)]

Preparation 5

To 65 g of 25% aqueous ammonia solution, styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) 2000", manufactured by CRAY VALLEY, molar ratio of styrene/maleic anhydride: 2/1) (hereinafter, (B-1) component) 50 g of water and 150 g of water were added and stirred at 80° C. for 1 hour, followed by neutralization of a styrene/maleic anhydride copolymer (molar ratio of styrene/carboxylate structure: 1/1, weight average molecular weight: 10,000, solid content concentration) 20%) to obtain 265 g.

production example 6

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

production example 7

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

production example 8

To 85 g of 25% aqueous ammonia solution, styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) 1000", manufactured by CRAY VALLEY, styrene/maleic anhydride molar ratio: 1/1) (hereinafter (B'-1) 50 g of the component) and 200 g of water were added and stirred at 80° C. for 1 hour, followed by neutralization of a styrene/maleic anhydride copolymer (molar ratio of styrene/carboxylate structure: 1/2, weight average molecular weight: 7,000, solid content) Concentration 15%) 335 g was obtained.

production example 9

To 80 g of 25% aqueous ammonia solution, styrene/maleic anhydride copolymer (trade name "SMA (registered trademark) EF80", manufactured by CRAY VALLEY, molar ratio of styrene/maleic anhydride: 8/1) (hereinafter (B'-2) 50 g of a component) and 200 g of water were added and stirred at 80° C. for 1 hour, followed by neutralization of a styrene/maleic anhydride copolymer (molar ratio of styrene/carboxylate structure: 4/1, weight average molecular weight: 15,000, solid content) Concentration 15%) 330 g was obtained.

production example 10

To 15 g of 25% aqueous ammonia solution, 50 g of isobutylene/maleic anhydride copolymer (trade name "Isoban 600", Kurare Co., Ltd.) (hereinafter referred to as (B'-3) component) and 200 g of water were added , and stirred at 80°C for 1 hour to obtain 265 g of a neutralized salt of an isobutylene/maleic anhydride copolymer (weight average molecular weight: 6,000, solid content concentration: 20%).

[Measurement of weight average molecular weight]

The weight average molecular weights of the neutralized salt of the component (B-1) to (B-3) and the neutralized salt of the component (B'-1) to (B'-3) are measured by gel permeation chromatography (manufactured by Tosoh Corporation). , trade name "HLC-8320", column: Tosoh Co., Ltd. product, brand name "TSK-GEL GMPWXL" and "TSK-GEL G2500PWXL" were connected), and calculated|required by polyethylene oxide conversion.

[Preparation of tackifying resin emulsion]

Example 1

After dissolving 100 parts of component (A-1) obtained in Production Example 2 in 80 parts of methylcyclohexane over 3 hours at 80°C, 5.0 parts of neutralized salt of component (B-1) obtained in Production Example 5 (in terms of solid content) and 140 parts of water was added and stirred for 1 hour. Next, high pressure emulsification was carried out at a pressure of 30 MPa with a high-pressure emulsifier (manufactured by Mantongaurin) to obtain an emulsified product. Next, vacuum distillation was performed on 70 degreeC and the conditions of 2.93x10 ^-2 MPa for 6 hours, and the tackifying resin emulsion of 50% of solid content concentration was obtained.

Example 2-3

In Example 1, it carried out similarly except having changed the neutralization salt of (B-1) component to the neutralization flame of (B-2) and (B-3) component obtained by manufacture examples 6 and 7, and tackifying resin emulsion (all are A solid content concentration of 50%) was obtained.

Example 4-5

In Example 1, it carried out similarly except having changed the (A-1) component to the (A-2) and (A-3) component obtained by manufacture examples 3 and 4, and tackifying resin emulsion (both solid content concentration 50%) got it

Example 6

In Example 1, (A-1) component 100 parts, (A-1) component 70 parts and C9-type petroleum resin (brand name "Neopolymer 140" manufactured by JXTG Energy Co., Ltd.) (hereinafter (A-4) It carried out similarly except having changed into the combined use of 30 parts of components), and the tackifying resin emulsion (all are 50% of solid content concentration) was obtained. In addition, the softening point at the time of using together 70 parts of (A-1) component and 30 parts of (A-4) component was 155 degreeC.

Example 7

In Example 1, the same procedure was performed except that the component (A-1) was replaced with terpene phenol (trade name "Dertophene T115" manufactured by DRT company, softening point 125°C) (hereinafter referred to as (A-5) component), and tackifying resin emulsion. (in all, 50% of solid content concentration) was obtained.

comparative example 1-3

In Example 1, it carried out similarly except having changed the neutralized flame of (B-1) component into the neutralized flame of (B'-1) - (B'-3) component obtained in Production Examples 8-10, and tackifying resin emulsion (in all, 50% of solid content concentration) was obtained.

comparative example 4

In Example 1, the same procedure was carried out except that the neutralization salt of component (B-1) was replaced with sodium dodecylbenzenesulfonate (hereinafter referred to as (C-1) component), and tackifying resin emulsion (both solid content concentration: 50%) got

[Evaluation of emulsification properties]

The volume average particle diameter of the tackifying resin emulsion of each Example and Comparative Example was measured using a laser diffraction particle size measuring apparatus (manufactured by Shimadzu Corporation, trade name "SALD-7500nano"), having a refractive index of 1.70-0.20i and an absorbance of 0.06. measured under the conditions. The following criteria evaluated the obtained volume average particle diameter. A result is shown in Table 1. The emulsification property and storage stability of a tackifying resin emulsion are so favorable that a volume average particle diameter is small.

○: Volume average particle diameter less than 0.7 μm

△: Volume average particle diameter of 0.7 µm or more and less than 1.5 µm

x: Volume average particle diameter 1.5 µm or more

Further, the tackifying resin emulsion of each Example and Comparative Example was filtered through a 400 mesh wire mesh (manufactured by Nippon Wire Mesh Industries Co., Ltd., eye size 34 µm), and the weight % of the obtained residue relative to the tackifying resin (A) was weighed. did. The weight % of the residue was evaluated according to the following criteria. A result is shown in Table 1. Generation|occurrence|production of the aggregate is suppressed in a tackifying resin emulsion, so that the weight % of a residue is small, and the emulsification property is favorable.

○: 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 tackifying resin emulsion of each Example and Comparative Example was subjected to a marron test (according to JIS K 6828), the generation rate of aggregates ((aggregate amount/initial solid content) × 100) was calculated, and the following criteria for mechanical stability was evaluated as A result is shown in Table 1. The higher the occurrence rate (ppm) of agglomerates, the lower the mechanical stability.

○: Less than 250 ppm of agglomerate generation rate

(triangle|delta): generation rate of aggregates 250 ppm or more and less than 500 ppm

x: 500 ppm or more of the generation rate of aggregates

<Test conditions>

Sample: 30 g of tackifying resin emulsion (15 g of solid content)

Wire mesh: 200 mesh wire mesh (manufactured by Nippon Wire Mesh Industry Co., Ltd., eye size 76㎛)

Load: 10 kg

Rotation speed: 1000rpm

Rotation time: 10 minutes

[Production of water-based adhesive composition]

70 parts (in terms of solid content) of the acrylic polymer emulsion synthesized in Preparation Example 1 and 30 parts (in terms of solid content) of the tackifying resin emulsion of Example 1 were mixed to obtain an aqueous adhesive composition. It carried out similarly also about each tackifying resin emulsion of Examples 2-7 and Comparative Examples 1-4, and manufactured the water-system adhesive agent composition.

[Production of sample tape]

Using a die-type applicator (manufactured by Taiyu Machinery Co., Ltd.), the water-based adhesive composition was applied to a polyester film (trade name "S-100", manufactured by Mitsubishi Chemical Co., Ltd., thickness: 38 µm) to a thickness of 50 µm. It apply|coated so that it may become so and then, it was made to dry for 5 minutes with a 105 degreeC tail wind dryer, and the sample tape was produced.

[Evaluation of water-resistant adhesive strength]

The sample tape was cut to a width of 25 mm, and a 2 kg roller was applied to the adherend (stainless steel plate (SS)) in two reciprocating motions, and was left still for 1 day. Next, after leaving the adherend to which the sample tape was adhered in a thermo-hygrostat (60°C, 90%RH) for 7 days, the adherend was taken out from the thermo-hygrostat, and immediately subjected to a 180° peel test, a tensile rate of 300 mm/min, measurement It carried out on condition of the temperature of 23 degreeC, and the adhesive force (N/25mm) was measured. A result is shown in Table 1.

[Evaluation of holding power]

The sample tape (25 mm x 25 mm) was overlapped on a stainless steel plate, and was applied in one reciprocation with a roller weighing 2 kg. A load of 1.2 kg was applied to the sample tape at 60°C, and the time (h) until the sample tape fell was measured. A result is shown in Table 1. It can be said that holding power is strong when the time until fall is long.

※ Notes are as follows.

1) The number of moles of the structural unit 1 in the neutralized salt of the component (B) / the number of moles of the carboxylate structure of the structural unit 2 in the neutralized salt of the component (B)

2) Since a large amount of insoluble matter was generated during vacuum distillation of the resin emulsion and no tackifying resin emulsion was obtained, the water resistance adhesion, mechanical stability, and holding power could not be evaluated.

Claims (12)

Tackifying resin (A) and the neutralization salt of the polymer (B) containing the structural unit 1 derived from an aromatic vinyl compound (b1) and the structural unit 2 derived from the α, β-unsaturated dicarboxylic acids (b2) do,
The tackifying resin emulsion for water-system adhesive agents whose molar ratio of the carboxylate structure contained in the structural unit 1 and structural unit 2 in the neutralization salt of the said polymer (B) is 1/1 - 3/1. The method of claim 1,
The neutralizing salt of the said polymer (B) is a neutralizing salt of the said polymer (B) and a nitrogen-containing compound (α) having a boiling point of -35 to 120°C, The tackifying resin emulsion characterized in that it is. 3. The method of claim 1 or 2,
(A) The softening point of the component is 70-180 degreeC, The tackifying resin emulsion characterized by the above-mentioned. 3. The method of claim 1 or 2,
(A) A tackifying resin emulsion characterized in that the component is at least one selected from the group consisting of rosin-based resins (a1), petroleum resins (a2) and terpene-based resins (a3). 3. The method of claim 1 or 2,
(A) A tackifying resin emulsion characterized in that the component is a rosin ester and/or a rosin phenol resin. 3. The method of claim 1 or 2,
(b1) The component is styrene, The tackifying resin emulsion characterized by the above-mentioned. 3. The method of claim 1 or 2,
(b2) The tackifying resin emulsion, characterized in that the component is at least one selected from the group consisting of maleic acid, maleic anhydride and maleic acid half ester. 3. The method of claim 1 or 2,
(B) A tackifying resin emulsion, characterized in that the component has a weight average molecular weight of 5,000 to 30,000. 3. The method of claim 2,
A tackifying resin emulsion, characterized in that the component (α) is at least one selected from the group consisting of ammonia, monoamines, diamines and triamines. An aqueous adhesive composition comprising the tackifying resin emulsion according to claim 1 and a base polymer. 11. The method of claim 10,
The water-based adhesive composition, characterized in that the base polymer is an acrylic polymer emulsion. A point/adhesive sheet comprising a point/adhesive layer comprising the aqueous point/adhesive composition according to claim 10 or 11 and a base material.