JP2008007693A - Tackifying resin emulsion, its production method and aqueous adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tackifying resin emulsion emulsified without an evaporable organic solvent and effective for improving s holding force, constant load peelability and curved surface adhesiveness, and to provide a water-based adhesive composition which uses the emulsion, is excellent in the above-mentioned characteristics, and reduces environmental loads. <P>SOLUTION: This tackifying resin emulsifier is characterized in that the solid content excluding an emulsifier comprises 65 to 99 wt.% of a polymerized rosin-based ester resin (A) having a softening point of 130 to 180°C and 1 to 35 wt.% of an ester group-free liquid hydrocarbon polymer having a weight-average mol.wt. of 300 to 2,000 and excluding the component (A) [the total amount of the components (A) and (B) is 100 wt.%], and the tackifying resin emulsifier does not use an organic solvent, and is prepared by phase inversion emulsification. <P>COPYRIGHT: (C)2008,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 containing the tackifying resin emulsion.

  In recent years, due to environmental considerations, water-based adhesives / adhesives having a low content of volatile organic solvents and the like and having reduced environmental loads have been demanded. Therefore, tackifiers used in the production of water-based adhesives / adhesives are also required to be those that do not use volatile organic solvents, especially for tackifier resin emulsions used in water-based adhesives / adhesives. What is emulsified without using any organic solvent is required.

By the way, although the adhesive / adhesive is used for various applications, in recent years, those having particularly excellent holding power, constant load peelability, and curved surface adhesiveness have been demanded. In general, it is preferable to use a tackifying resin with a high softening point in order to improve these performances, but it is difficult to emulsify a tackifying resin with a high softening point without using a solvent or the like, and various studies have been conducted. It has been broken.
For example, it has been proposed to mix and emulsify a resin having a specific viscosity with a tackifier resin (see Patent Document 1). However, although the resins having specific viscosities exemplified are compatible with the terpene phenol resin having a softening point of 130 ° C. and the aliphatic petroleum resin having a softening point of 85 ° C., which are mentioned in the examples, it is much higher. Poor compatibility with polymerized rosin ester resins with excellent softening point, especially retention strength, constant load peelability, and curved surface adhesion, so stable emulsions cannot be obtained, and retention strength and constant load There was a problem that the peelability and curved surface adhesiveness deteriorated. Further, a method of emulsifying a resin having a high softening point by using an acrylic oligomer has been proposed (see Patent Document 2). According to this method, although compatibility is improved, transesterification proceeds when melt-mixed with a polymerized rosin ester resin at a high temperature, which greatly increases holding power, constant load peelability, and curved surface adhesion. There has been a problem that excessive reduction has occurred, and further improvement has been demanded.
The present applicant has proposed a method for producing a tackified resin water-based emulsion by adding a polymer having a specific glass transition temperature to the emulsification step (see Patent Document 3). It requires a partial concentration, and there has been a demand for improving the degree of freedom of use.

JP-A-56-125431 JP 2005-330436 A JP 2001-49227 A

  An object of the present invention is to provide a tackifying resin emulsion emulsified without using a volatile organic solvent, which is particularly effective for improving holding power, constant load peelability, and curved surface adhesion.

  As a result of intensive studies to solve the above problems, the present inventor can produce a tackifier resin emulsion without using a volatile organic solvent by using a specific liquid polymer, and the adhesive. It has been found that the use of the imparting resin emulsion can particularly improve the holding power, constant load peelability, and curved surface adhesion, and the present invention has been completed.

That is, the present invention
Liquid hydrocarbon not containing ester groups having a solid content excluding the emulsifier component of 65 to 99% by weight of polymerized rosin ester resin (A) having a softening point of 130 to 180 ° C. and a weight average molecular weight other than (A) of 300 to 2000 A tackifier resin emulsion comprising 1 to 35% by weight of the polymer (B) [the sum of the components (A) and (B) is 100% by weight], and the amount of the organic solvent contained in the emulsion is 50 ppm or less . Mixing the component (A), the component (B), an emulsifier and water without using an organic solvent to form an emulsion in which the component (A) and the component (B) are continuous phases and water is a dispersed phase. The method for producing a tackifying resin emulsion as described above, wherein water is added and the emulsion is phase-inverted so that the component (A) and the component (B) are dispersed phases and water is a continuous phase emulsion. A water-based adhesive / adhesive composition containing the tackifying resin emulsion described above.

  According to the present invention, since a tackifier resin emulsion can be produced without using a volatile organic solvent, the environmental load can be reduced. Moreover, since the water-based adhesive / adhesive of the present invention has particularly excellent holding power, constant load peelability, and curved surface adhesiveness, it can be used in various applications.

In the present invention, a polymerized rosin ester resin having a solid content excluding an emulsifier component having a softening point of 130 to 180 ° C. (ring and ball method: JIS K 5902, hereinafter, the softening point is measured by the ring and ball method). A) (hereinafter referred to as the component (A)) 65 to 99% by weight and a liquid hydrocarbon polymer containing no ester group having a weight average molecular weight of 300 to 2000 other than (A) (B) (hereinafter referred to as (B) It is composed of 1 to 35% by weight [the sum of components (A) and (B) is 100% by weight), and the amount of organic solvent contained in the emulsion is 50 ppm or less. Features.

The component (A) used in the present invention is a polymerized rosin obtained by polymerizing rosin and / or a derivative thereof (hereinafter sometimes referred to as “polymerized rosin” as appropriate), and has a softening point. It will not specifically limit if it is 130-180 degreeC, A well-known thing can be used.
Specific examples include polymerized rosin, modified polymerized rosin, hydrogenated polymerized rosin, disproportionated polymerized rosin, esters of these polymerized rosins and alcohols, and the like.

The polymerized rosin is not particularly limited, and known ones can be used. The polymerized rosin is usually provided as a mixture of a rosin dimer and a rosin. However, it is preferable to use a rosin dimer having a content of 40% by weight or more in terms of holding power and constant load peelability. From the standpoint of improving curved surface adhesion. The modified polymer rosin is not particularly limited, and known ones can be used. Specifically, a polymerized rosin modified with an unsaturated carboxylic acid or a phenol modified with phenol can be used.

Examples of the unsaturated carboxylic acid used for producing the unsaturated carboxylic acid modified product of polymerized rosin include (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, and (meth) acrylic acid. . The production of the unsaturated carboxylic acid modified product of polymerized rosin is not particularly limited, and a known method may be adopted. Specifically, for example, the polymerized rosin and the unsaturated carboxylic acid may be reacted at about 150 to 300 ° C. for about 1 to 24 hours. The amount of each component used is not particularly limited, and is, for example, about 0.1 to 20 parts by weight of unsaturated carboxylic acid with respect to 100 parts by weight of polymerized rosin.

Examples of the phenols used when the polymerized rosin is modified with phenol include phenol and alkylphenol. The phenol-modified polymerized rosin can be produced by a known method. Specifically, for example, polymerized rosin and phenols may be reacted at about 150 to 300 ° C. for about 1 to 24 hours. In addition, although the usage-amount of each component is not specifically limited, For example, it is about 0.1-50 weight part of phenols with respect to 100 weight part of polymerization rosins.

The hydride of polymerized rosin is not particularly limited as long as it is a hydrogenated polymerized rosin, and known rosin can be used. Hydrogenation is not particularly limited, and may be performed by a known method. Usually, the reaction may be performed at about 0.1 to 30 MPa using a hydrogenation catalyst in the presence of a known hydrogen source as necessary. Examples of the hydrogen source include lithium aluminum hydride and the like in addition to hydrogen gas, and examples of the hydrogenation catalyst include Raney nickel and palladium carbon.

The disproportionate of the polymerized rosin is not particularly limited as long as it disproportionates the polymerized rosin, and known ones can be used. The disproportionation may be carried out by a known method. For example, the reaction may be carried out at normal pressure using a disproportionation catalyst in the presence of a known hydrogen source.

The ester of the polymerized rosin and / or derivative thereof and the alcohol is not particularly limited as long as it is an ester of the above-described polymerized rosin or the like and an alcohol, and known ones can be used. Examples of alcohols used include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetrahydric alcohols, and hexahydric alcohols. As monohydric alcohol, well-known things, such as methanol, ethanol, propanol, isopropanol, are mentioned, for example. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,6-hexanediol, and the like. Examples of the trihydric alcohol include glycerin, trimethylolpropane, trimethylolethane, triethylolethane, and the like. Examples of the tetrahydric alcohol include pentaerythritol and diglycerin. Examples of the hexavalent alcohol include dipentaerythritol. These alcohols may be amino alcohols having an amino group in the molecule.
Esterification is not particularly limited, and may be performed by a known method. Specifically, for example, when polymerized rosin or the like and alcohol are converted into a hydroxyl group equivalent ratio of the alcohol to a carboxyl group equivalent of the polymerized rosin, COOH / OH is about 1 / (0.2 to 2.0). And the reaction may be performed at about 150 to 300 ° C. for about 2 to 30 hours.

Component (B) used in the present invention may be a liquid hydrocarbon polymer containing no ester group having a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) other than component (A) of 300 to 2000. If it is not specifically limited, a well-known thing can be used. When the weight average molecular weight is less than 300, the holding power, constant load peelability, and curved surface adhesiveness decrease, which is not preferable. When it exceeds 2000, the compatibility with the component (A) deteriorates, This is not preferable because it causes a decrease in stability and performance of the resulting emulsion. Moreover, when it contains an ester group, when it melt-mixes with (A) component, since transesterification occurs and holding power, a constant load peelability, and curved surface adhesiveness fall, it is unpreferable. In addition to the liquid hydrocarbon polymer, the compatibility with the component (A) is deteriorated, which is not preferable.

Examples of the component (B) include olefin polymers, and liquid hydrocarbon polymers obtained by polymerizing unsaturated hydrocarbons having 4 to 5 carbon atoms are preferred from the viewpoint of compatibility. Examples of the unsaturated hydrocarbon having 4 to 5 carbon atoms include 1-butene, isobutene, 2-butene, butadiene, 1-pentene, 2-pentene, isopentene, and isoprene. The polymerization may be performed by a known method, and radical polymerization, cationic polymerization, and the like can be employed.
In addition, as (B) component, you may use a commercially available thing as it is. Examples of commercially available products include “Nisseki Polybutene LV-7”, “Nisseki Polybutene LV-10”, “Nisseki Polybutene LV-25”, “Nisseki Polybutene LV-50”, “Nisseki Polybutene LV-”. "100", "Nisseki Polybutene HV-15" (all manufactured by Nippon Oil Corporation), "Idemitsu Polybutene 15R", "Idemitsu Polybutene 0H", "Idemitsu Polybutene 5H", "Idemitsu Polybutene 10H-A", ""Idemitsu Polybutene 15H" (all manufactured by Idemitsu Kosan Co., Ltd.), "Nissan Polybutene 0N", "Nissan Polybutene 06N", "Nissan Polybutene 015N" (all manufactured by NOF Corporation), "Marca Clear V", "Marca “Clear H”, “Marca Clear L” (both manufactured by Maruzen Petrochemical Co., Ltd.) and the like.

The tackifying resin emulsion of the present invention is obtained by emulsifying the component (A) and the component (B).
When emulsifying the component (A) and the component (B), an emulsifier is usually used. It does not specifically limit as an emulsifier to use, A well-known emulsifier can be used. Specific examples include a high molecular weight emulsifier obtained by polymerizing a vinyl monomer, a low molecular weight anionic emulsifier, and a low molecular weight nonionic emulsifier. In the present invention, it is particularly preferable to use a high molecular weight emulsifier because adhesion performance (particularly holding power) and mechanical stability can be improved.

Examples of the monomer used for the production of the polymer emulsifier include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. Alkyl (meth) acrylate monomers such as butyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; Monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, carboxylic acid vinyl monomers such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, muconic acid and other dicarboxylic acid monomers; vinyl sulfonic acid, styrene sulfone Acid, 2-acrylamido-2-methylpropanesulfonic acid Organic sulfonic acid vinyl monomers; phosphoric acid vinyl monomers such as 2- (meth) acryloyloxyethyl acid phosphate; and alkali metal salts such as sodium salts and potassium salts of these various organic acids, alkaline earth metal salts , Ammonium salts, salts of organic bases, amide monomers such as (meth) acrylamide and N-methylol (meth) acrylamide; nitrile monomers such as (meth) acrylonitrile; vinyl ester monomers such as vinyl acetate Hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; polyoxyalkylene Polyoxyalkylene (meth) acrylic acid ester such as monomer Monomers: Methyl vinyl ether, glycidyl (meth) acrylate, urethane acrylates, phosphate vinyl monomers such as diphenyl-2 (meth) acryloyloxyphosphate, α-olefins having 6 to 22 carbon atoms, vinylpyrrolidone and the like And those obtained by polymerizing one or more of them by a known method.

Examples of the copolymerization method include solution polymerization, suspension polymerization, emulsion polymerization using a reactive emulsifier other than the polymer emulsifier described below, and a non-reactive emulsifier other than the polymer emulsifier.

The weight average molecular weight of the thus obtained polymer emulsifier is not particularly limited, but it is usually preferably about 1000 to 500,000 in terms of emulsifying ability and the performance of the resulting tackifier resin emulsion. In addition, it is preferable to use a (meth) acrylamide polymer obtained by using 50 mol% or more of a (meth) acrylamide monomer in terms of the coating performance of the pressure-sensitive adhesive and the initial adhesiveness of the adhesive.

Examples of the reactive emulsifier other than the polymer emulsifier include a surfactant having a hydrophilic group and a hydrophobic group, and having a carbon-carbon double bond in the molecule. Examples of the carbon-carbon double bond include functional groups such as a (meth) allyl group, 1-propenyl group, 2-methyl-1-propenyl group, vinyl group, isopropenyl group, and (meth) acryloyl group. . Specific examples of the reactive emulsifier include, for example, a polyoxyethylene alkyl ether having at least one functional group in the molecule, a sulfosuccinic acid ester salt of polyoxyethylene alkyl ether having at least one functional group in the molecule, Sulfate ester salt of polyoxyethylene alkyl ether having at least one functional group in the molecule, polyoxyethylene phenyl ether having at least one functional group in the molecule, poly having at least one functional group in the molecule A sulfosuccinic acid ester salt of oxyethylene phenyl ether, a sulfate ester salt of polyoxyethylene phenyl ether having at least one functional group in the molecule, a polyoxyethylene alkyl phenyl ether having at least one functional group in the molecule, A sulfosuccinic acid ester salt of polyoxyethylene alkylphenyl ether having at least one functional group in the molecule, a sulfate ester salt of polyoxyethylene alkylphenyl ether having at least one functional group in the molecule, and the functional group in the molecule A polyoxyethylene aralkylphenyl ether having at least one functional group, a sulfosuccinic acid ester salt of polyoxyethylene aralkylphenyl ether having at least one functional group in the molecule, and a polyoxyethylene aralkyl having at least one functional group in the molecule Sulfate ester salt of phenyl ether, polyoxyethylene alkylphenyl ether phosphate ester salt having at least one functional group in the molecule, polyoxyethylene having at least one functional group in the molecule Alkyl phenyl ether aliphatic or aromatic carboxylates, acidic phosphoric acid (meth) acrylate ester emulsifiers, acid anhydride modified products of rosin glycidyl ester acrylate (see JP-A-4-256429), JP-A Examples thereof include various emulsifiers described in JP-A 63-23725, JP-A 63-240931, and JP-A 62-104802.

Furthermore, what replaced polyoxyethylene in the said reactive emulsifier with polyoxypropylene or the block copolymerization or random copolymerization of polyoxyethylene and polyoxypropylene is mentioned. Examples of these commercially available products include “KAYAMER PM-1”, “KAYAMER PM-2”, “KAYAMER PM-21” (trade name, manufactured by Nippon Kayaku Co., Ltd.), “SE-10N”, “NE-10”, “NE-20”, “NE-30”, “Adekalia Soap SR-10”, “Adekalia Soap SR-20”, “Adekalia Soap ER-20” (trade name, (stock) ) Made by ADEKA), "New Frontier A229E", "New Frontier N117E", "New Frontier N250Z", "Aquaron RN-10", "Aquaron RN-20", "Aquaron RN-50", "Aquaron HS-10" , “AQUALON KH-05”, “AQUALON KH-10” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Eminol JS-2” (product) , Manufactured by Sanyo Chemical Industries Co., Ltd.), "Raterumu K-180" (trade name, manufactured by Kao Corp.), and the like can be cited as a typical example.

As reactive emulsifiers other than these polymer emulsifiers, polyoxyethylene phenyl ether type is preferable from the viewpoint of polymerizability and emulsifiability of the resulting polymer emulsifier, and has a structure in which 5 to 20 moles of alkylene oxide chains are polymerized. It is particularly preferred to use unsaturated sulfonates. As these commercially available products, “Adekaria Soap SR-10”, “Adekaria Soap SR-20” (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), “Aquaron KH-05”, “Aquaron KH-10” (Trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is preferable.

Examples of non-reactive emulsifiers other than polymer emulsifiers include dialkyl sulfosuccinic acid ester salts, alkane sulfonic acid salts, α-olefin sulfonic acid salts, polyoxyethylene alkyl ether sulfosuccinic acid ester salts, polyoxyethylene styryl phenyl ether sulfosuccinic acid esters. Anionic emulsifiers such as salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan Nonionic emulsifiers such as fatty acid esters are exemplified.

These emulsifiers can be used alone or in appropriate combination of two or more. Among these, anionic emulsifiers and nonionic emulsifiers are preferably used from the viewpoints of compatibility with the base polymer used in the adhesive / adhesive composition and mixing stability. Further, it is preferable to use at least 10% by weight or more, preferably 80% by weight or more of the emulsifier component as a polymer emulsifier because the holding power, constant load peelability and curved surface adhesion can be improved.

In addition, the usage-amount of an emulsifier is about 1-10 weight part normally in conversion of solid content with respect to 100 weight part of tackifying resin compositions, Preferably it is 1-6 weight part. When the amount of the emulsifier used is 1 part by weight or more, reliable emulsification can be performed, and when it is 10 parts by weight or less, high water resistance and adhesive performance can be ensured.

  The tackifying resin water-based emulsion of the present invention can be produced by phase inversion emulsification of a melted tackifying resin composition in the presence of the emulsifier. The melting conditions can be determined as appropriate in consideration of the softening point of the tackifying resin composition to be dispersed, but it is usually preferable to set the temperature at about 20 ° C. higher than the softening point of the tackifying resin composition. Usually, by setting it to 180 ° C. or less, a tackifier resin emulsion tends to be easily obtained.

The tackifying resin water-based emulsion of the present invention is produced, for example, as follows. An emulsion in which the emulsifier and water are added in predetermined amounts while the components (A) and (B) are melted and stirred at about 150 to 180 ° C., and the tackifying resin composition is a continuous phase and water is a dispersed phase. And then adding water to invert the emulsion to obtain an emulsion in which the tackifying resin composition is a dispersed phase and water is a continuous phase. The stirring conditions and the conditions for adding the emulsifier and water can be determined as appropriate.

The solid content concentration of the thus obtained tackifying resin water-based emulsion is not particularly limited, but is usually adjusted appropriately so as to be about 20 to 70% 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, pH is about 2 to 10, viscosity is usually about 10 to 1000 mPa · s (at 25 ° C., solid content concentration 50%), and organic solvent content is less than 50 ppm. It is. The film forming temperature of the tackifying resin water-based emulsion is usually about 100 ° C. or less.

The water-based adhesive / adhesive composition of the present invention is obtained by blending the tackifier resin emulsion with at least one base polymer selected from the group consisting of an acrylic polymer emulsion, a rubber latex and a synthetic resin emulsion. The solid content concentration of these aqueous adhesive / adhesive compositions is usually about 40 to 70% by weight, preferably 55 to 70% by weight.

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

The use ratio of the acrylic polymer emulsion and the tackifying resin water-based emulsion is not particularly limited, but the effect of the modification by the tackifying resin water-based emulsion can be sufficiently expressed, and the retention force due to excessive use, constant load peelability, An appropriate range of use that does not cause a decrease in curved surface adhesiveness is 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 of the acrylic polymer emulsion (in terms of solid content). It is good to do.

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 ratio of rubber latex and tackifying resin aqueous emulsion used is not particularly limited, but the effect of modification by tackifying resin aqueous emulsion can be fully expressed, and retention force, constant load peelability, curved surface adhesion due to excessive use As an appropriate range of use that does not cause deterioration in properties, the amount of the tackifying resin water-based emulsion is usually about 10 to 150 parts by weight (in terms of solids) with respect to 100 parts by weight of rubber latex (in terms of solids). Good.

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

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.

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). The weight average molecular weight was determined by polystyrene 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. The detection limit (nd) of the organic solvent by this measurement is 10 ppm.

(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 fumaric acid-modified polymerized rosin ester]
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube is equipped with 100 parts of a gum-based polymerized rosin containing 66% of resin acid dimer (resin consisting of 34 parts of gum rosin and 66 parts of resin acid dimer of gum rosin). After charging the acid), the system was heated under a nitrogen gas stream until the system temperature reached 220 ° C., and 3 parts of fumaric acid was added and reacted for 1 hour. Then, after adding 14 parts of pentaerythritol and reacting at the same temperature for 2 hours, the temperature was further raised to 280 ° C. and reacted at the same temperature for 7 hours. Thereafter, the low-boiling fraction was removed under reduced pressure to obtain a pentaerythritol ester (tackifier resin) of a fumaric acid-modified polymerized rosin. The softening point was 168 ° C., the acid value was 11.8, the hydroxyl value was 49, and the color tone (Gardner) was 11.

Production Example 2 [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 50,000 was obtained.

Production Example 3 [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 4 [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]
A polymerized rosin ester having a softening point of 160 ° C. as a tackifier resin (trade name “Pencel D-160”, manufactured by Arakawa Chemical Industries, Ltd.) is added to a pressure reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel. 85 parts of polybutene having a weight average molecular weight of 900 (trade name “Nisseki Polybutene LV-100”, manufactured by Nippon Oil Corporation) was melted at 200 ° C. for about 1 hour, and a resin mixture having a softening point of 125 ° C. Obtained. 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 2-9
A tackifying resin emulsion was obtained in the same manner as in Example 1 except that the tackifying resin (A), liquid hydrocarbon polymer (B) and emulsifier used were changed as shown in Table 1.

Comparative Examples 1-5
A tackifying resin emulsion was obtained in the same manner as in Example 1 except that the tackifying resin (A), the liquid hydrocarbon polymer (B) and the emulsifier used were changed as shown in Table 1.

Comparative Example 6
100 parts of a polymerized rosin ester (trade name “Pencel D-160”, manufactured by Arakawa Chemical Industries, Ltd.) having a softening point of 160 ° C. was dissolved in 60 parts of toluene at 100 ° C. for about 1 hour, and then cooled to 80 ° C. Anionic emulsifier (trade name “Neohaitenol F-13”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added with 3 parts (in terms of solid content) and 160 parts of water, and stirred vigorously at 75 ° C. for 1 hour. Pre-emulsification was performed. 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 6 except that the emulsifier used was changed as shown in Table 1.

(Evaluation method of aqueous adhesive composition)
To the preparation obtained by mixing 100 parts (solid part) of the acrylic polymer emulsion obtained in Production Example 4 with 10 parts (solid part) of the tackifying resin emulsion obtained in the above Examples and Comparative Examples, the viscosity was further increased. 0.5 part of an agent (trade name “Primal ASE-60”, manufactured by Nippon Acrylic Chemical Co., Ltd.) was added to obtain an adhesive composition.

(Adhesion performance test)
The above 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.). The film was applied to a certain degree, and then dried for 5 minutes in a circulating dryer at 105 ° C. to prepare a film for a sample tape. The adhesive properties were evaluated by the following test methods. The evaluation results are shown in Table 2.

(1) Holding power A sample tape (width 25 mm × length 25 mm) was prepared from the sample tape film, attached to a stainless steel plate, a load of 1 kg was applied at 60 ° C., and the drop time (hours) was measured. .
(2) Constant load peelability A sample tape (width 25 mm × length 150 mm) is prepared from the film for sample tape, and this is bonded to a polypropylene plate by reciprocating twice with a 2 kg roller, and a load of 200 g is applied to the end of the tape. It was fixed so as to be 90 ° peeled, and the peel distance (mm) per hour was measured at 23 ° C.
(3) Curved surface adhesion A sample tape (width 20 mm × length 28 mm) was prepared from the film for the sample tape, and this was bent and pasted on a polypropylene cylinder having a diameter of 12 mm, and the tape after 3 days at 40 ° C. The float (mm) of was measured.

In the table, the mixture softening point represents the softening point (ring ball method, JIS K 5902) of the molten mixture of the component (A) and the component (B) (the component not using the component (B) is the softening of the component (A) alone. Point). n. d. Indicates that it is below the detection limit (10 ppm).
(A) -1: Polymerized rosin ester having a softening point of 160 ° C. (trade name “Pencel D-160”, manufactured by Arakawa Chemical Industries, Ltd.)
(A) -2: Polymerized rosin ester having a softening point of 135 ° C. (trade name “Pencel D-135”, manufactured by Arakawa Chemical Industries, Ltd.)
(A) -3: Polymerized rosin ester having a softening point of 125 ° C. (trade name “Pencel D-125”, manufactured by Arakawa Chemical Industries, Ltd.)
(B) -1: Polybutene having a weight average molecular weight of 900 (trade name “Nisseki Polybutene LV-100”, manufactured by Nippon Oil Corporation)
(B) -2: Polybutene having a weight average molecular weight of 1100 (trade name “Nisseki Polybutene HV-15”, manufactured by Nippon Oil Corporation)
(B) -3: Polyisopentane having a weight average molecular weight of 400 (trade name “Marcaclear V”, manufactured by Maruzen Petrochemical Co., Ltd.)
(B) -4: Polybutene having a weight average molecular weight of 2200 (trade name “Nisseki Polybutene HV-100”, manufactured by Nippon Oil Corporation)
(B) -5: Polyisoprene having a weight average molecular weight of 24,000 (trade name “Kuraprene LIR-30”, manufactured by Kuraray Co., Ltd.)
(B) -6: Acrylic oligomer having a weight average molecular weight of 1100 (trade name “ARUFON UP-1041”, manufactured by Toagosei Co., Ltd.)
Emulsifier a: Anionic emulsifier (trade name “Neohaitenol F-13”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Claims (10)

  Liquid hydrocarbon not containing ester groups having a solid content excluding the emulsifier component of 65 to 99% by weight of polymerized rosin ester resin (A) having a softening point of 130 to 180 ° C. and a weight average molecular weight other than (A) of 300 to 2000 A tackifier resin emulsion comprising 1 to 35% by weight of the polymer (B) [the sum of the components (A) and (B) is 100% by weight], and the amount of the organic solvent contained in the emulsion is 50 ppm or less .   The tackifying resin emulsion according to claim 1, wherein the liquid hydrocarbon polymer (B) is a liquid hydrocarbon polymer obtained by polymerizing an unsaturated hydrocarbon having 4 to 5 carbon atoms.   The tackifier resin emulsion according to claim 1 or 2, comprising 10% by weight or more of a polymer emulsifier in the emulsifier component.   The tackifier resin emulsion according to any one of claims 1 to 3, comprising 80% by weight or more of a polymer emulsifier in the emulsifier component.   The tackifier resin emulsion according to claim 3 or 4, wherein the polymer emulsifier has a weight average molecular weight of 1,000 to 500,000.   The tackifier resin emulsion according to any one of claims 3 to 5, wherein the polymer emulsifier is a (meth) acrylamide polymer.   Polymerized rosin ester resin (A), liquid hydrocarbon polymer (B) not containing an ester group having a weight average molecular weight of 300 to 2,000 other than (A), an emulsifier and water are mixed without using an organic solvent. A polymerized rosin ester resin (A) and a liquid hydrocarbon polymer (B) to form an emulsion in which water is a dispersed phase, and then water is added to phase-invert the emulsion to polymerize rosin. The method for producing a tackifying resin emulsion according to any one of claims 1 to 6, wherein the ester resin (A) and the liquid hydrocarbon polymer (B) are dispersed phases and water is a continuous phase emulsion.   The method for producing a tackifying resin emulsion according to claim 7, wherein emulsification is performed under a pressurized condition.   A water-based adhesive / adhesive composition comprising the tackifying resin emulsion according to claim 1. The water-based adhesive / adhesive composition according to claim 9, comprising at least one base polymer selected from the group consisting of acrylic polymer emulsions, rubber latexes, and synthetic resin emulsions.