JP2008231275A - Tackifier resin emulsion, its preparation, and water-based adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tackifier resin emulsion for providing an adhesive composition with various preferable adhesion characteristics such as a heat resistance sustainment without lowering the compatibility with a base polymer while reducing the organic solvent content, an adhesive composition, and a tackifier resin emulsion with a high yield, a preferable storage stability and a high softening point safely in the production work without use of an organic solvent. <P>SOLUTION: The tackifier resin emulsion includes as the solid component except an emulsifier component 60-99 wt.% of a polymerized rosin ester resin (A) of 135-180°C softening point and 20 or less acid number, 1-40 wt.% of a liquid hydrocarbon polymer (B) having a carboxyl group or an acid anhydride group with a 5-100 acid number of other than (A) and 300-30,000 weight average molecular weight [based on the sum of the component (A) and the component (B) as 100 wt.%]. The amount of the organic solvent included in the emulsion is 50 ppm or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a tackifying resin emulsion, a method for producing the same, and a water-based adhesive / adhesive composition.

  In recent years, consumers' interest in the environment has been improved, and adhesives and adhesives that have a reduced environmental burden have been required. Under such circumstances, adhesives and adhesives that have been prepared using organic solvents are now being replaced with water-soluble adhesives and emulsion-type adhesives. Since there is a problem that the type of sticky / adhesive has poor water resistance, an emulsion-type sticky / adhesive has attracted attention.

  Emulsion-type adhesives / adhesives have been conventionally prepared by mixing an acrylic resin with a tackifying resin emulsion. However, in recent years, it has been required to prepare a tackifying resin emulsion without using an organic solvent. .

  However, when a resin having a high softening point (one at 130 ° C. or higher) is used as the tackifying resin, it is difficult to prepare a tackifying resin emulsion without using an organic solvent. Then, the tackifying resin emulsion and adhesive composition which do not use an organic solvent are proposed by adding a low molecular weight acrylic oligomer to the tackifying resin of high softening point (refer patent documents 1 and 2). These propose a method for preparing a tackifying resin emulsion without using an organic solvent. However, since the tackifying resin and a low molecular weight acrylic oligomer are used in combination, the heat-resistant holding power of the obtained pressure-sensitive adhesive is improved. There has been a demand for tackifying resin emulsions and pressure-sensitive adhesive compositions that can reduce the heat-resistant holding power.

  On the other hand, as a technique for improving the heat resistance retention force, a tackifying resin emulsion in which a rosin-based tackifying resin having a low softening point and an acid value of 5 to 130 and a cross-linking agent reactive to a carboxyl group has been proposed. (See Patent Document 3). This proposes a technique for increasing the heat-resistant retention by increasing the molecular weight of the tackifier resin component by reacting a rosin resin, which is a tackifier resin, with a crosslinking agent during the manufacture or use of the adhesive. In the case of using a rosin resin having an acid value of 5 to 130, particularly 20 or more, even if a crosslinking reaction is carried out at the time of production or use of the pressure-sensitive adhesive, a decrease in compatibility with the base polymer is inevitable and required. It was insufficient to satisfy the level of compatibility and heat resistance. Further, in this method, when an attempt is made to prepare a tackifying resin emulsion without using an organic solvent, there is a problem that it cannot be applied to those having a softening point of the tackifying resin exceeding 130 to 135 ° C. In order to improve the heat resistance without lowering the compatibility, an emulsion of a polymerized rosin ester tackifying resin having a softening point of 135 ° C. or higher has been demanded.

JP 2005-330436 A JP 2006-56936 A JP 2005-1113016 A

  The present invention relates to a tackifying resin emulsion and an adhesive that can provide an adhesive composition having good adhesive properties such as heat retention without reducing the content of the organic solvent and reducing compatibility with the base polymer. In addition to providing a composition, an object is to provide a tackifying resin emulsion having a high softening point and a high yield and good storage stability safely in production operations without using an organic solvent.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using specific liquid hydrocarbon polymer and tackifying resin, and completed the present invention. It was.

  That is, in the present invention, the solid content excluding the emulsifier component is a polymerized rosin ester resin (A) having a softening point of 135 to 180 ° C. and an acid value of 20 or less (A) and an acid value other than (A) of 5 to 5. 100, a liquid hydrocarbon polymer having a carboxyl group or an acid anhydride group having a weight average molecular weight of 300 to 30000 (B) 1 to 40% by weight [total of component (A) and component (B) is 100% by weight A tackifying resin emulsion in which the amount of the organic solvent contained in the emulsion is 50 ppm or less; a polymerized rosin ester resin (A) having a softening point of 135 to 180 ° C. and an acid value of 20 or less, and an acid value of 5 The liquid hydrocarbon polymer (B) having a carboxyl group or an acid anhydride group having a weight average molecular weight of 300 to 30,000 and an emulsifier are mixed without using an organic solvent. The combined rosin ester resin (A) and the liquid hydrocarbon compound (B) having a carboxyl group or acid anhydride group form an emulsion in which water is a dispersed phase and water is added, and then water is added to phase the emulsion. A method for producing the tackifier resin emulsion, wherein the emulsion is inverted to form a polymerized rosin ester resin (A) and a liquid hydrocarbon compound (B) having a carboxyl group or an acid anhydride group as a dispersed phase and water as a continuous phase emulsion; The present invention relates to a water-based adhesive / adhesive composition comprising a tackifier resin emulsion and a crosslinking agent having reactivity to a carboxyl group.

  According to the present invention, a tackifier resin emulsion, an aqueous tacky / adhesive composition capable of reducing the content of an organic solvent and suppressing particularly a decrease in heat resistance without reducing compatibility with the base polymer. Can be provided.

  The tackifier resin emulsion of the present invention has a polymer rosin ester resin (A) (hereinafter referred to as component (A)) 60 to 99 having a solid content excluding an emulsifier component and a softening point of 135 to 180 ° C. and an acid value of 20 or less. Liquid hydrocarbon polymer (B) (hereinafter referred to as component (B) having a carboxyl group or an acid anhydride group having an acid value of 5 to 100 and a weight average molecular weight of 300 to 30000 other than% by weight and component (A) 1) to 40% by weight [the sum of the component (A) and the component (B) is 100% by weight), and the amount of the organic solvent contained in the emulsion is 50 ppm or less.

  The component (A) used in the present invention is not particularly limited as long as it is a polymerized rosin ester having a softening point of about 135 to 180 ° C. (preferably 150 to 170 ° C.) and an acid value of 20 or less. Can be used. Specific examples include those obtained by reacting a polymerized rosin with a known polyol. If the softening point is less than 135 ° C, the heat resistance holding force when the pressure sensitive adhesive is reduced is not preferable, and if the softening point exceeds 180 ° C, the compatibility of the pressure sensitive adhesive with the base polymer is deteriorated. It is not preferable. On the other hand, when the acid value exceeds 20, the polymerized rosin ester portion becomes high molecular weight due to the reaction with the crosslinking agent, so that the compatibility with the base polymer is deteriorated and the adhesiveness is lowered. As the polymerized rosin, a polymerized rosin modified with an unsaturated carboxylic acid such as (anhydrous) maleic acid, fumaric acid or (meth) acrylic acid or phenols may be used. You may use what processed. Examples of the polyol include ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, dihydric alcohols such as 1,3-butanediol and 1,6-hexanediol, glycerin, trimethylolpropane, and trimethylolethane. , Trihydric alcohols such as triethylolethane, tetrahydric alcohols such as pentaerythritol and diglycerin, hexavalent alcohols such as dipentaerythritol, or triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine, N -Amino alcohols such as normal butyl diethanolamine. The ratio of the rosins and polyalcohol used is about COOH / OH (molar ratio) = 1 / (0.2 to 2.0) in terms of the hydroxyl group equivalent ratio of the alcohol to the carboxyl group equivalent of the rosin. What is necessary is just to carry out for about 2 to 30 hours at about 150-300 degreeC.

  The component (B) used in the present invention has an acid value of 5 to 100, a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of 300 to 30000, and a liquid having a carboxyl group or an acid anhydride group. If it is a hydrocarbon polymer, it will not specifically limit and a well-known thing will be used. When the acid value is less than 5, it is not preferable because the heat-resistant holding power of the pressure-sensitive adhesive is lowered, and when the acid value exceeds 100, the yield and storage stability of the tackifier resin emulsion are lowered, which is not preferable. Moreover, when the weight average molecular weight is less than 300, the heat resistance retention is reduced, which is not preferable. When it exceeds 30000, it is not preferable because emulsification cannot be performed without using an organic solvent.

  Examples of the component (B) include an olefin polymer into which a carboxyl group or an acid anhydride group has been introduced. The acrylic polymer emulsion, rubber latex, and the like used when making an adhesive composition From the viewpoint of compatibility with synthetic resin emulsions, those obtained by introducing a carboxyl group or an acid anhydride group into a liquid hydrocarbon polymer obtained by polymerizing an unsaturated hydrocarbon having 4 to 5 carbon atoms are preferred. Commercially available products include, for example, “NISSO-PB C-1000”, “NISSO-PB CI-1000” (trade name, manufactured by Nippon Soda Co., Ltd.), “Maleinized PB” (trade name, Nippon Oil & Fat Co., Ltd.) Product), “LIR-403”, “LIR-410” (trade name, manufactured by Kuraray Co., Ltd.), and the like.

  The tackifying resin emulsion of the present invention is obtained by mixing and emulsifying the component (A) and the component (B). In emulsification, an emulsifier is usually used.

It does not specifically limit as an emulsifier to use, A well-known emulsifier can be used. Specifically, for example, an anionic emulsifier and a nonionic emulsifier can be used. Examples of the anionic emulsifier include dialkyl sulfosuccinate, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate, naphthalene sulfonate formalin. Examples include condensates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, etc. Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene sorbitan fatty acid esters Examples thereof include reactive emulsifiers in which a vinyl group, an allyl group or a propenyl group is introduced into these emulsifiers. These emulsifiers can be used by appropriately selecting one kind or two or more kinds.

As the emulsifier, a polymer emulsifier obtained by polymerizing various monomers may be used. Examples of the monomer used for the production of the polymer emulsifier include ionic monomers, hydrophobic monomers, and other monomers.

As an ionic monomer, if it is a monomer which has an ionic functional group in a molecule | numerator, it will not specifically limit, A well-known thing can be used. Specific examples include an anionic monomer having an anionic functional group and a cationic monomer having a cationic functional group. Examples of the anionic monomer include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, muconic acid, citraconic acid, maleic anhydride and other vinyl monomers having a carboxyl group, vinyl sulfonic acid, styrene sulfonic acid, (Meth) acrylic acid sulfoethyl, (meth) acrylic acid sulfopropyl, (meth) allylsulfonic acid, monomers having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl (meth) acrylate, Examples thereof include monomers having a phosphate group such as acid phosphooxypropyl (meth) acrylate and acid phosphooxypolyethylene glycol (meth) acrylate, and salts of these monomers (for example, sodium salt, potassium salt, amine salt, etc.). As the cationic monomer, a vinyl monomer having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, triallylamine, or the like It can be obtained by reacting a salt of inorganic acid or organic acid such as hydrochloric acid, sulfuric acid, acetic acid, or the like, or a quaternizing agent such as methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin and the like. And vinyl monomers containing a quaternary ammonium salt. These anionic monomers and cationic monomers may be used alone or in combination of two or more. When the base polymer of the adhesive / adhesive is anionic, it is preferable to use more anionic monomer than cationic monomer. When the base polymer is cationic, more cationic monomer than anionic monomer is used. It is preferable to use it. Usually, anionic polymers are often used as the base polymer, so that it is preferable to use a lot of anionic monomers.

Specific examples of the hydrophobic monomer include (meth) acrylic acid alkyl esters such as ethyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate ( Styrenes such as styrene, α-methylstyrene, and styrene compounds having an alkyl group having 1 to 4 carbon atoms in the aromatic ring of these styrenes. Examples thereof include vinyl monomers, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, α-olefins having 6 to 22 carbon atoms, alkyl vinyl ethers having 1 to 22 carbon atoms, and vinylpyrrolidone. Among these, (meth) acrylic acid ester, styrene monomer, carboxylic acid vinyl ester and the like are particularly preferable from the viewpoint of emulsification. These may be used alone or in combination of two or more.

Examples of the monomer other than the ionic monomer and the hydrophobic monomer include (meth) acrylamide. These may be used alone or in combination of two or more.

The polymer emulsifier is obtained by polymerizing these components by a known method. Although the usage-amount of each component is not specifically limited, Usually, ionic monomer: hydrophobic monomer: monomers other than an ionic monomer and a hydrophobic monomer are 1-80 mol%: 1-80 mol%: 0-90 mol% Degree.

As the polymer emulsifier, it is preferable to use a (meth) acrylamide polymer obtained by copolymerizing (meth) acrylamide, an ionic monomer and a hydrophobic monomer from the viewpoint of improving the heat resistance retention. In addition, the usage-amount of (meth) acrylamide, an ionic monomer, and a hydrophobic monomer should use what is obtained by copolymerizing in the ratio of about 50-90 mol%: 1-40 mol%: 1-40 mol%. Is preferred.

As the emulsifier, the anionic emulsifier, the nonionic emulsifier, and the polymer emulsifier may be used alone or in combination, but the polymer emulsifier may be used so as to be 80% by weight or more of the emulsifier. preferable.

In the tackifying resin emulsion of the present invention, the component (A), the component (B) and the emulsifier are mixed without using an organic solvent, and the component (A) and the component (B) are a continuous phase and water is a dispersed phase. An emulsion is formed, water is then added, and the emulsion is phase-inverted to form an emulsion in which component (A) and component (B) are dispersed and water is a continuous phase. In addition, emulsification ((A) component, (B) component and an emulsifier are mixed without using an organic solvent to form an emulsion in which (A) component and (B) component are a continuous phase and water is a dispersed phase, Next, the step of adding water to invert the emulsion to make the emulsion of component (A) and component (B) a dispersed phase and water a continuous phase) is carried out under pressurized conditions. The temperature can be increased to 100 ° C. or higher, which is preferable in that an emulsion having a high yield and good storage stability can be obtained.

The solid content concentration of the tackifying resin emulsion thus obtained is not particularly limited, but is usually adjusted appropriately so as to be about 35 to 65% by weight. Moreover, the volume average particle diameter of the obtained emulsion is usually about 0.1 to 2 μm, and most of them are uniformly dispersed as particles of 1 μm or less, but the volume average particle diameter is 0.7 μm or less. It is preferable from the viewpoint of storage stability. The emulsion has a white to milky white appearance, has a pH of about 2 to 10, and a viscosity (measured with a B-type viscometer) is usually about 10 to 1000 mPa · s (at 25 ° C. and a solid content concentration of 50%). It is.

The water-based adhesive / adhesive composition of the present invention comprises the tackifying resin emulsion and a crosslinking agent having reactivity with a carboxyl group.

The crosslinking agent having reactivity with the carboxyl group is not particularly limited, and known ones can be used. Specifically, carbodiimide compounds, oxazoline compounds, aziridine compounds, vinyl ether compounds, epoxy compounds Etc. The carbodiimide compound is not particularly limited as long as it has at least two carbodiimide groups in one molecule, and known compounds can be used. Specifically, for example, “Carbodilite” (trade name, manufactured by Nisshinbo Industries, Inc.) and the like are listed as commercial products.

The oxazoline-based compound is not particularly limited as long as it has at least two oxazoline groups in one molecule, and known compounds can be used. Specifically, for example, “Epocross” (trade name, manufactured by Nippon Shokubai Co., Ltd.) is listed as a commercially available product.

The aziridine compound is not particularly limited as long as it has at least two aziridine groups in one molecule, and known compounds can be used. Specifically, for example, “Chemite” (trade name, manufactured by Nippon Shokubai Co., Ltd.), “TAZM”, “TAZO” (trade name, manufactured by Mutual Yakuhin Co., Ltd.) and the like are listed as commercial products.

The vinyl ether compound is not particularly limited as long as it has at least two vinyl ether groups in one molecule, and known compounds can be used. Specifically, for example, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, Pentaerythritol tetravinyl ether, polyethylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 5,9-bis- (vinyloxy) tricyclo [5.2.1.0 ^2,6 ] decane, 5,9-bis- (vinyloxy) Methyl) tricyclo [5.2.1.0 ^2,6 ] decane, 4,10-bis- (vinyloxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadecane, 4,10-bis - (Binirokishimechiru) pentacyclo [6.5.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,13 ] pentadecane and the like.

As an epoxy-type compound, if it has at least two or more epoxy groups in 1 molecule, it will not specifically limit, A well-known thing can be used. Specific examples include “Denacol” (trade name, manufactured by Nagase ChemteX Corporation).
The cross-linking agent having reactivity to the carboxyl group is preferably a water-soluble cross-linking agent or a water-dispersed cross-linking agent from the viewpoint of stability when blended with an aqueous adhesive / adhesive.

In addition, acrylic polymer emulsion, rubber latex, and synthetic resin emulsion can be used for the water-based adhesive / adhesive composition of the present invention.

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

Examples of the (meth) acrylic acid ester used for the production of the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples thereof include glycidyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, and these are used alone or in admixture of two or more. Moreover, in order to provide storage stability to the obtained acrylic polymer emulsion, a small amount of (meth) acrylic acid may be used together with the (meth) acrylic acid ester. Further, for example, a copolymerizable monomer such as vinyl acetate or styrene can be used in combination so long as the adhesive properties of the acrylic polymer are not impaired. In addition, an anionic emulsifier, a partially saponified polyvinyl alcohol, or the like can be used as an emulsifier used in the acrylic polymer emulsion, and the amount used is usually about 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymer. Preferably it is 0.5-3 weight part.

The use ratio of the acrylic polymer emulsion and the tackifying resin emulsion is not particularly limited, but the effect of the modification by the tackifying resin water-based emulsion can be sufficiently exhibited, and the heat resistance holding force, tack, etc. are reduced by excessive use. As an appropriate range of use that does not cause, the tackifier resin aqueous emulsion is usually about 2 to 40 parts by weight (in terms of solid content) with respect to 100 parts by weight (in terms of solid content) of the acrylic polymer emulsion.

Moreover, as rubber latex, various well-known things used for an aqueous | water-based adhesive / adhesive composition can be used. Examples thereof include natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex and the like. The use ratio of the rubber latex and the tackifying resin water emulsion is not particularly limited, but the effect of modification by the tackifying resin water emulsion can be fully expressed, and the heat retention strength, constant load peelability, curved surface due to excessive use As an appropriate range of use that does not cause a decrease in adhesiveness, the amount of tackifying resin water-based emulsion is usually about 10 to 150 parts by weight (in terms of solid content) with respect to 100 parts by weight of rubber latex (in terms of solid content). Is good.

As the synthetic resin emulsion, various known ones used in aqueous adhesive compositions other than the acrylic polymer emulsion and rubber latex can be used. For example, vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, Examples thereof include synthetic resin emulsions such as urethane emulsions.

The use ratio of the synthetic resin emulsion and the tackifier resin water emulsion is not particularly limited, but the effect of the modification of the tackifier aqueous emulsion can be sufficiently expressed, and the retention force due to excessive use, constant load peelability, Appropriate use ratios that do not cause a decrease in curved surface adhesion are usually about 2 to 40 parts by weight (in terms of solid content) of the tackifier resin aqueous emulsion with respect to 100 parts by weight (in terms of solid content) of the synthetic resin emulsion. It is good to do.

In the water-based adhesive / adhesive composition of the present invention, at least one base polymer selected from the group consisting of an acrylic polymer emulsion, a rubber latex and a synthetic resin emulsion can be used in combination, and if necessary, the composition can be erased. Foaming agents, thickeners, fillers, antioxidants, water resistance agents, film-forming aids, and the like can also be used. The solid content concentration of the water-based adhesive / adhesive composition is usually about 40 to 70% by weight, preferably 55 to 70% by weight.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, all parts and percentages are by weight unless otherwise specified. The obtained polymer emulsifier and adhesive resin emulsion were analyzed by the following method.

(Weight average molecular weight)
The obtained polymer emulsifier was measured by gel permeation chromatography (trade name “HLC-8120” manufactured by Tosoh Corporation, column: manufactured by Tosoh Corporation, trade name “TSKgelSuperHM-Lx” 3 pieces), polystyrene. The weight average molecular weight was determined by conversion.

(Yield of tackifying resin emulsion)
The yield of the obtained tackifying resin emulsion was determined by the following formula.

(Solvent content in tackifying resin emulsion)
The solvent in the emulsion was measured by gas chromatography (manufactured by Shimadzu Corporation, trade name “GC-14A”, column: J & W, trade name “DB-5”), and a calibration curve using an aqueous solution of known solvent concentration. The content was determined.

(Volume average particle diameter)
Using a laser diffraction particle size analyzer (manufactured by Shimadzu Corporation, trade name “SALD-2000”), the measurement was performed under the conditions of a refractive index of 1.70-0.20i and an absorbance of 0.06.

(Evaluation of storage stability of emulsion)
The obtained tackifying resin emulsion was allowed to stand at 25 ° C. for 10 days, and the presence or absence of sediment was visually determined. The results are shown in Table 1.
○: Good △: Small amount of sediment ×: Large amount of sediment

Production Example 1 (Production of unsaturated carboxylic acid-modified polymerized rosin ester resin)
Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of polymerization rosin was charged and heated under a nitrogen gas stream until the system temperature reached 180 ° C. Three parts were added and reacted for 1 hour. Thereafter, 14 parts of pentaerythritol was added, the temperature was raised to 280 ° C., and the mixture was reacted at the same temperature for 9 hours. Thereafter, the low-boiling fraction was removed under reduced pressure to obtain a fumaric acid-modified polymerized rosin ester (tackifying resin) having a softening point of 168 ° C. and an acid value of 16.

Production Example 2 (Production of unsaturated carboxylic acid-modified rosin ester resin)
After charging 100 parts of gum rosin into the same reaction apparatus as in Production Example 1, the system was heated in a nitrogen gas stream until the system temperature reached 180 ° C., and 5 parts of maleic anhydride was added and reacted for 1 hour. Thereafter, 12 parts of pentaerythritol was added, the temperature was raised to 280 ° C., and the reaction was carried out at the same temperature for 5 hours. Thereafter, the low-boiling fraction was removed under reduced pressure to obtain a maleic acid-modified rosin ester (tackifying resin) having a softening point of 120 ° C. and an acid value of 50.

Production Example 3 (Production of styrene polymer emulsifier)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, a polyoxyethylene phenyl ether-based reactive emulsifier (trade name “AQUALON RN-50”: Daiichi Kogyo Seiyaku Co., Ltd.) in a nitrogen gas stream. (Made by Co., Ltd.) is charged with 25 parts in terms of solid content, 12.5 parts of styrene, 12.5 parts of methyl methacrylate, 40 parts of methacrylic acid and 10 parts of sodium styrene sulfonate, and further 20 parts of water is added. The ingredients were transparent and homogeneous. Next, 1 part of dodecanethiol, 2 parts of benzoyl peroxide and 300 parts of water were mixed with this to initiate polymerization. After stirring at 65 ° C. for 2 hours, 29 parts of 28% aqueous ammonia was added, and the mixture was further stirred at 65 ° C. for 6 hours to complete the polymerization, and then cooled to room temperature. An aqueous solution of a copolymer having a nonvolatile content of 22.5% and a weight average molecular weight of 50000 was obtained.

Production Example 4 (Production of acrylamide polymer emulsifier)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 57.7 parts of acrylamide (73 mol% of the total molar amount of monomers, the same applies hereinafter), 21.7 parts of itaconic acid ( 15 mol%), 2-acrylamido-2-methylpropanesulfonic acid 9.2 parts (4 mol%), butyl acrylate 11.4 parts (8 mol%), lauryl mercaptan 5 parts, polyoxyethylene alkyl ether sulfate Sodium salt (anionic emulsifier: trade name “Hytenol 073”: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 5 parts of ammonium persulfate and 400 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours. An aqueous solution of the polymer was obtained. Thereafter, the mixture was cooled, and 2-acrylamido-2-methylpropanesulfonic acid and equimolar sodium hydroxide were added at 60 ° C. and stirred for 1 hour to obtain an aqueous solution of a copolymer having a concentration of 15% and a weight average molecular weight of 40000. .

Production Example 5 (Production of base polymer emulsion)
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 43.4 parts of water and polyoxyethylene alkyl ether sulfate sodium salt (anionic emulsifier: trade name) under a nitrogen gas stream An aqueous solution consisting of 0.92 part of “Hitenol 073” (Daiichi Kogyo Seiyaku Co., Ltd.) was charged and the temperature was raised to 70 ° C. Next, a mixture comprising 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 part of pH adjusting agent (bicarbonate) and water 1/10 amount of each 8.83 parts of the initiator aqueous solution was added to the reaction vessel, and prepolymerization 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 was added to the reaction vessel over 2 hours to carry out emulsion polymerization, and then held at 70 ° C. for 1 hour to complete the polymerization reaction. The acrylic polymer emulsion thus obtained was cooled to room temperature and then filtered using a 100 mesh wire net to obtain an acrylic polymer emulsion having a solid content of 47.8%.

Example 1 (Production of tackifying resin emulsion)
In a pressure reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel, a polymerized rosin ester having a softening point of 160 ° C. and an acid value of 13 (trade name “Pencel D-160”, Arakawa Chemical Industries, 85 parts) and 15 parts of maleated polybutene having a weight average molecular weight of 2500 and an acid value of 82 (trade name “Maleinized PB”, manufactured by Nippon Oil & Fats Co., Ltd.) were melt-mixed at 200 ° C. for about 1 hour. Thereafter, the mixture was cooled to 160 ° C., and then 5 parts of an anionic emulsifier (trade name “Neohaitenol F-13”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added with stirring under pressure. Then, while maintaining the inside of the system at 140 ° C., 15 parts of hot water was added from the dropping funnel to obtain a creamy water-in-oil emulsion. Next, 54 parts of hot water was added with vigorous stirring to invert the phase to obtain an oil-in-water emulsion, and further diluted with hot water to a concentration of 50%. The emulsion was cooled to 25 ° C. and filtered through a 250 mesh wire mesh to obtain a tackifying resin emulsion.

Examples 2-10
Adhesion in the same manner as in Example 1 except that the tackifying resin (A), the liquid hydrocarbon compound (B) having a carboxyl group or an acid anhydride group, and the type and amount of the emulsifier were changed as shown in Table 1. An imparted resin emulsion was obtained.

Comparative Examples 1-5
Adhesion in the same manner as in Example 1 except that the tackifier resin (A), the liquid hydrocarbon compound (B) having a carboxyl group or an acid anhydride group, and the type and amount of the emulsifier were changed as shown in Table 1. An imparted resin emulsion was obtained.

Comparative Example 6
After dissolving 100 parts of a polymerized rosin ester having a softening point of 160 ° C. and an acid value of 13 (trade name “Pencel D-160”, manufactured by Arakawa Chemical Industries, Ltd.) in 60 parts of toluene at 100 ° C. for about 1 hour, 80 ° C. 3 parts of an anionic emulsifier (trade name “Neohaitenol F-13”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 160 parts of water are added, and the mixture is added at 75 ° C. for 1 hour. The mixture was vigorously stirred and pre-emulsified. The obtained preliminary emulsion was high-pressure emulsified with a high-pressure emulsifier (mantongaurin) at a pressure of 30 MPa to obtain an emulsion. Next, the emulsion was charged into a vacuum distillation apparatus, and vacuum distillation was performed for 6 hours under conditions of 50 ° C. and 130 hPa, to obtain a tackifier resin emulsion having a solid content of 50%.

Comparative Example 7
A tackifying resin emulsion was obtained in the same manner as in Comparative Example 7 except that the emulsifier used was changed as shown in Table 1.

(Evaluation method of aqueous adhesive composition)
As shown in Table 2, 100 parts (solid part) of the acrylic polymer emulsion obtained in Production Example 5 were mixed with 20 parts (solid part) of the tackifying resin emulsion obtained in the above Examples and Comparative Examples and a crosslinking agent. Furthermore, 0.5 part of a thickener (trade name “Primal ASE-60”, manufactured by Nippon Acrylic Chemical Co., Ltd.) was added to obtain an adhesive composition. The obtained water-based pressure-sensitive adhesive composition is dried on a polyester film (trade name “S-100”, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) with a thickness of 38 μm using a dice-type applicator (manufactured by Otsugi Equipment Co., Ltd.). Was applied in a circulating drier at 105 ° C. for 5 minutes to prepare a sample tape film, and various tests were conducted by the following performance evaluation methods.

(Adhesion performance test)
The adhesive properties were evaluated by the following test methods. The evaluation results are shown in Table 2.

(1) Heat-resistant holding force When a sample tape (width 25 mm x length 25 mm) is prepared from the film for the sample tape, this is attached to a stainless steel plate, loaded with 1 kg at 80 ° C, and 24 hours have passed. The deviation width (mm) or the drop time (min) was measured.

(2) Using a compatible spectrophotometer (trade name “U-3210 self-recording spectrophotometer” manufactured by Hitachi, Ltd.), the film for sample tape was irradiated with light of 500 nm, and the transmittance was measured. . From the obtained transmittance, the compatibility was evaluated as follows.
○: Transmittance of 70% or more Δ: Transmittance of 40% or more and less than 70% ×: Transmittance of less than 40%

In the table, n. d. Indicates that it is below the detection limit (10 ppm).
(A) -1: Polymerized rosin ester having a softening point of 160 ° C. and an acid value of 13 (trade name “Pencel D-160”, manufactured by Arakawa Chemical Industries, Ltd.)
(A) -2: Polymerized rosin ester having a softening point of 135 ° C. and an acid value of 13 (trade name “Pencel D-135”, manufactured by Arakawa Chemical Industries, Ltd.)
(A) -3: Polymerized rosin ester having a softening point of 125 ° C. and an acid value of 14 (trade name “Pencel D-125”, manufactured by Arakawa Chemical Industries, Ltd.)
(B) -1: maleated polybutene having a weight average molecular weight of 2500 and an acid value of 82 (trade name “Maleinized PB”, manufactured by NOF Corporation)
(B) -2: Polybutene having a weight average molecular weight of 1100 and an acid value of 0 (trade name “Nisseki Polybutene HV-15”, manufactured by Nippon Oil Corporation)
Emulsifier a: Anionic emulsifier (trade name “Neohaitenol F-13”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Crosslinking agent a: Carbodiimide type crosslinking agent (trade name “Carbodilite E-01”, manufactured by Nisshinbo Industries, Ltd.)
Crosslinking agent b: Oxazoline-based crosslinking agent (trade name “Epocross WS-500”, manufactured by Nippon Shokubai Co., Ltd.)
Cross-linking agent c: Aziridine-based cross-linking agent (trade name “TAZM”, manufactured by Mutual Pharmaceutical Co., Ltd.)
Cross-linking agent d: Epoxy-based cross-linking agent (trade name “Denacol EX-512”, manufactured by Nagase ChemteX Corporation)

Claims (10)

The solid content excluding the emulsifier component is a polymerized rosin ester resin having a softening point of 135 to 180 ° C. and an acid value of 20 or less (A) 60 to 99% by weight and an acid value other than (A) is 5 to 100, and the weight average molecular weight Consisting of 1 to 40% by weight of a liquid hydrocarbon polymer (B) having a carboxyl group or an acid anhydride group of 300 to 30,000 [the total of the component (A) and the component (B) is 100% by weight], A tackifying resin emulsion in which the amount of organic solvent contained in the emulsion is 50 ppm or less. The liquid hydrocarbon polymer (B) is a liquid hydrocarbon polymer obtained by introducing a carboxyl group or an acid anhydride group into a liquid hydrocarbon polymer obtained by polymerizing an unsaturated hydrocarbon having 4 to 5 carbon atoms. Item 4. The tackifier resin emulsion according to Item 1. The tackifier resin emulsion according to claim 1 or 2, comprising 80% by weight or more of a polymer emulsifier in the emulsifier component. The tackifier resin emulsion according to claim 3, wherein the polymer emulsifier is a (meth) acrylamide polymer. Polymerized rosin ester resin (A) having a softening point of 135 to 180 ° C. and an acid value of 20 or less, a liquid hydrocarbon having a carboxyl group or an acid anhydride group having an acid value of 5 to 100 and a weight average molecular weight of 300 to 30000 A polymer (B) and an emulsifier are mixed without using an organic solvent, and a polymerized rosin ester resin (A) and a liquid hydrocarbon polymer (B) having a carboxyl group or an acid anhydride group are water in a continuous phase. Is formed into a dispersed phase, and then water is added to invert the emulsion to give a polymerized rosin ester resin (A) and a liquid hydrocarbon polymer (B) having a carboxyl group or an acid anhydride group. The method for producing a tackifying resin emulsion according to any one of claims 1 to 4, wherein water is a continuous phase emulsion in a dispersed phase. The method for producing a tackifying resin emulsion according to claim 5, wherein emulsification is performed under a pressurized condition. A water-based adhesive / adhesive composition comprising the tackifier resin emulsion according to any one of claims 1 to 4 and a crosslinking agent having reactivity with a carboxyl group. The aqueous tackiness / adhesion according to claim 7, wherein the crosslinking agent having reactivity with a carboxyl group is at least one selected from the group consisting of carbodiimide compounds, oxazoline compounds, aziridine compounds, vinyl ether compounds, and epoxy compounds. Agent composition. The water-based adhesive / adhesive composition according to claim 7 or 8, wherein the crosslinking agent having reactivity with a carboxyl group is a water-soluble crosslinking agent or a water-dispersed crosslinking agent. The water-based adhesive / adhesive composition according to any one of claims 7 to 9, comprising at least one base polymer selected from the group consisting of an acrylic polymer emulsion, a rubber latex, and a synthetic resin emulsion.