JP6098821B2 - Tackifier for water-based adhesive / adhesive, tackifier resin emulsion, and water-based adhesive / adhesive composition - Google Patents

Description

The present invention relates to a tackifier for an aqueous sticky / adhesive, a tackifying resin emulsion, and an aqueous sticky / adhesive composition.

In general, foams such as urethane foam are widely used as a heat insulating material or a structural material in architectural applications, household appliances such as refrigerators, automobiles, and the like. Since the surface of the foam that is in contact with the adhesive / adhesive layer has irregularities or has pores, the substantial contact area is reduced. As a result, compared with a substrate having a smooth surface, peeling between the substrate and the adhesive / adhesive layer tends to occur. For this reason, adhesives and adhesives used in the field of automobiles and building materials are required to have sufficient adhesion to rough surfaces having irregularities on the surface such as urethane foam.

On the other hand, polyolefin resins such as polyethylene and polypropylene used for the packaging of food packaging and electronic and electrical products have no functional groups and are not polar, so they have poor affinity with polar molecules, Adhesion and wettability are very weak and easy to peel off. For this reason, a method is generally used in which a primer is applied to the adherend surface to modify the sticky / adhesive surface, but without using a primer, a sticky / adhesive having sufficient adhesion to polyolefin resins is strong. It has been demanded.

By the way, for difficult-to-adhere substrates such as urethane foam and polyolefin resin, when moving from room temperature to a storage room such as a refrigerator or when used at both low and normal temperatures, There is a demand for a sticky / adhesive having sufficient adhesive strength when moving to low temperatures or when used in both areas.

Further, in recent years, there has been a demand for water-based adhesives / adhesives with a low content of volatile organic solvents and the like, with reduced environmental loads, in consideration of the environment and the safety of the human body. However, when the organic solvent-based adhesive / adhesive is changed to water-based, there is a problem that the adhesive force at low temperature to room temperature on the rough surface or polyolefin resin becomes insufficient.

For rough surfaces, for example, the amount of radicals calculated based on the amount of polymerization initiator used is controlled within a specific range, and an acrylic polymer in which an epoxy compound is cross-linked to a linear acrylic polymer with few branched structures. A water-based aqueous pressure-sensitive adhesive has been proposed (see Patent Document 1). This was insufficient in adhesion to rough surfaces and polyolefin resins from low temperature to normal temperature.

Also, water-dispersed acrylic pressure-sensitive adhesives having a specific high shear viscosity, low shear viscosity and the like have been proposed for rough surfaces (see Patent Document 2). This is because deformation such as urethane foam tends to occur according to the unevenness of the surface, the initial adhesiveness is good, and the peeling resistance and the holding property are excellent. The adhesive strength to the surface and polyolefin resin was not sufficient.

On the other hand, for polyolefin resins, for example, a compound having a structure in which a carboxyl group of a rosin having a specific acid value and an acid value of 2 to 340 is metallated with a metal compound is emulsified. A tackifying resin emulsion obtained by emulsification in the presence of is proposed (see Patent Document 3). This has good heat resistance and good adhesion to polyolefins, but from low to ordinary temperatures, further improvement was required for the adhesion to rough surfaces such as polyolefins and urethane foam.

Furthermore, (meth) acrylic acid alkyl ester (a) having 1 to 14 carbon atoms in the alkyl chain (a) 70 to 99.8% by weight, hydroxyalkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl chain (b) An aqueous dispersion of a resin composition containing the above has been proposed (see Patent Document 4). Although this aqueous dispersion has a high adhesive force to polyolefin adherends, it provides an aqueous pressure-sensitive adhesive having excellent tack, heat resistance, curved surface adhesion, and good substrate adhesion to a sheet-like substrate. However, it cannot be said that there is sufficient adhesion to the rough surface, and there is a demerit that the type of acrylic is limited.

Thus, various water-based adhesives / adhesives have been proposed as substitutes for organic solvent-based adhesives / adhesives, but they are excellent even at low to normal temperatures on both rough surfaces and olefinic resin surfaces. Water-based adhesives / adhesives that have adhesive properties such as holding power and constant load peelability while satisfying the adhesive strength and are not limited by the type of acrylic polymer emulsion have not been developed yet.

JP 2007-217594 A JP 2008-115315 A JP 2000-309771 A Japanese Patent Application Laid-Open No. 2008-081691

The present invention has a holding force and a constant load peeling while satisfying an excellent adhesive force from a low temperature to a normal temperature to a substrate having a rough surface such as urethane foam or polypropylene foam, particularly a foam substrate and an olefin resin surface. It is an object to provide a tackifier for water-based viscose / adhesives, a tackifier resin emulsion, and an aqueous viscose / adhesive composition that have adhesive properties such as properties and excellent mechanical stability.

As a result of intensive studies to solve the above problems, the inventors of the present invention have 95 to 99.9% by weight of the polymerized rosin compound (A), an alkyl group or an alkylene group, and 1 to 40 carbon atoms. And the monovalent or divalent carboxylic acid (a), an alkyl group or an alkenyl group, and an ester (B) of 1 to 6-valent alcohol (b) having 1 to 40 carbon atoms is 0.1 to 5 weights. %, And a compression dynamic elastic modulus (G ′) at −10 to 5 ° C. of a tackifier layer having a thickness of 0.4 to 1.0 mm is 1.0 × 10 ^{5 to} 1.0 × 10 ⁹ Pa. It has been found that the above-mentioned problems can be solved by using a tackifier for an aqueous adhesive / adhesive, and the present invention has been completed.

That is, the present invention 1 has a polymerized rosin compound (A) and an alkyl group or an alkylene group, and has 1 to 40 carbon atoms and a monovalent or divalent carboxylic acid (a) and an alkyl group or an alkenyl group. And an ester (B) of a 1-6 valent alcohol (b) having 1 to 40 carbon atoms in a ratio by weight of (A) :( B) of 95-99.9: 0.1-5. contained, compression dynamic modulus at -10 to 5 ° C. tackifier layer having a thickness of 0.4 to 1.0 mm (G') is ^{1.0 × 10 5 ~1.0 × 10 9} Pa aqueous It is a tackifier for sticky / adhesives.

The present invention 2 is the tackifier for the aqueous tackiness / adhesive used in the difficult-to-adhere substrate at -10 to 5 ° C. in the present invention 1.

The present invention 3 is a tackifier for water-based adhesives / adhesives in which the weight average molecular weight of the tackifier of the present invention 1 or 2 is 200 to 3500.

The present invention 4 is a tackifier for an aqueous adhesive / adhesive agent in which the polymerized rosin compound (A) of any one of the present inventions 1 to 3 is a polymerized rosin ester.

The present invention 5 is for an aqueous adhesive / adhesive obtained by reacting the polymerized rosin ester of the present invention 4 with a polymerized rosin and an alcohol having 1 to 40 carbon atoms and 1 to 3 valences. It is a tackifier.

This invention 6 is an aqueous | water-based adhesive / adhesive composition containing the tackifier for the aqueous | water-based adhesives / adhesives in any one of this invention 1-5.

The present invention 7 is a water-based adhesive / adhesive composition further containing an acrylic polymer emulsion.

This invention 8 is the tackifying resin emulsion obtained by emulsifying the tackifier in any one of this invention 1-5 with an emulsifier.

In the present invention 9, the emulsifier in the present invention 8 is a molar ratio of the hydrophilic monomer (c-1) and the hydrophobic monomer (c-2) (c-1) :( c-2) = 45 to 75:25. 55 is a tackifying resin emulsion for water-based adhesive / adhesive containing a (meth) acrylic copolymer (C) obtained by copolymerization at 55.

The present invention 10 is a water-based adhesive / adhesive containing the tackifying resin emulsion of the present invention 8 or 9.

According to the present invention, the adhesive strength of a foam base material such as urethane foam or polypropylene foam and the surface of an olefin resin is excellent while having excellent adhesive strength at a low temperature of about 5 ° C. to a normal temperature of about 40 ° C. Further, it is possible to provide a tackifier for water-based adhesives / adhesives satisfying adhesive properties such as constant load peelability and excellent mechanical stability. Moreover, the kind of acrylic polymer emulsion is not limited, The tackifier for water-system adhesives / adhesives which can contain any acrylic polymer emulsion can be provided.

The tackifier for an aqueous adhesive / adhesive of the present invention has a polymerized rosin compound (A) (hereinafter referred to as component (A)) and an alkyl group or an alkylene group, and has 1 to 40 carbon atoms. A monovalent or divalent carboxylic acid (a) (hereinafter referred to as component (a)), an alkyl group or an alkenyl group, and a 1 to 6-valent alcohol (b) having 1 to 40 carbon atoms (hereinafter referred to as (b ) Component)) (B) (hereinafter referred to as component (B)) in a weight ratio of (A) :( B) of 95 to 99.9: 0.1 to 5, and a thickness of 0. The compression dynamic elastic modulus (G ′) at −10 to 5 ° C. of the tackifier layer of 4 to 1.0 mm is 1.0 × 10 ^{5 to} 1.0 × 10 ⁹ Pa.

The component (A) is a polymerized rosin obtained by polymerizing rosin and a derivative thereof (hereinafter referred to as “polymerized rosin” as appropriate).

Specific examples of the polymerized rosin include polymerized rosin, modified polymerized rosin, hydrogenated polymerized rosin, disproportionated polymerized rosin, and polymerized rosin ester which is an ester of these polymerized rosin and alcohols. It is done. Among these, a polymerized rosin ester is preferable in terms of adhesion to a difficult-to-adhere substrate and improvement of holding power and constant load peelability.

The polymerized rosin is not particularly limited, and known ones can be used. Specific examples include tall oil-based polymerized rosin (for example, trade name “Silbatac 140”, manufactured by Arizona Chemical Co.), wood-based polymerized rosin (for example, product name “Dimalex”, manufactured by Hercules), gum-based polymerized rosin ( For example, trade name “polymerized rosin B-140”, manufactured by Shinshu (Buhei) Hayashi Chemical Co., Ltd.) and the like can be mentioned. 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 with a content of 60% by weight or more of rosin. It is preferable from the viewpoint of improving force and constant load peelability.

As a method for producing the polymerized rosin, a known method can be adopted. Specifically, for example, a raw material rosin resin acid monomer such as gum rosin, tall oil rosin, and wood rosin as a raw material, and a solvent such as toluene and xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, and titanium tetrachloride. Among them, a method of reacting at a temperature of about 40 to 160 ° C. for about 1 to 5 hours may be mentioned.

The modified polymer rosin is not particularly limited, and known ones can be used. Specifically, an unsaturated carboxylic acid modified product obtained by modifying a polymerized rosin with an unsaturated carboxylic acid, and a phenol modified product obtained by modifying a polymerized rosin with phenol can be used.

Examples of the unsaturated carboxylic acid used in the production of the unsaturated carboxylic acid modified product of the polymerized rosin include (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, (meth) acrylic acid and the like. It is done. 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. In addition, although it does not specifically limit as the usage-amount of each component, For example, it is about 0.1-20 weight part of unsaturated carboxylic acid with respect to 100 weight part of superposition | polymerization rosins.

Examples of the phenols used in the production of the phenol modified product of the polymerized rosin include phenol and alkylphenol. The production of the phenol-modified product of polymerized rosin is not particularly limited, and 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 it does not specifically limit as the usage-amount of each component, For example, it is about 0.1-50 weight part of phenols with respect to 100 weight part of superposition | polymerization rosins.

The hydride of the above polymerized rosin is not particularly limited as long as the polymerized rosin is hydrogenated, and a known rosin can be used. The method of hydrogenation is not particularly limited, and may be performed by a known method. Usually, in the presence of a known hydrogen source, a hydrogenation catalyst may be used as necessary, and the reaction may be performed at about 0.1 to 30 MPa. . 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 polymerized rosin disproportionate is not particularly limited as long as the polymerized rosin is disproportionated, and known ones can be used. The disproportionation method may also be carried out by a known method. For example, the disproportionation catalyst is usually used in the presence of a known hydrogen source, and the reaction is carried out at normal pressure.

As a method for producing the polymerized rosin ester, an esterification catalyst is added to the polymerized rosin and alcohol in the presence or absence of a solvent as necessary, and the mixture is heated and dehydrated at about 250 to 280 ° C. for about 1 to 8 hours. According to the method.

Examples of the alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetrahydric alcohols, and hexahydric alcohols. As monohydric alcohol, well-known things, such as methanol, ethanol, propanol, isopropanol, lauryl alcohol, stearyl alcohol, isostearyl alcohol, are mentioned, for example. Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,6-hexanediol, and dimer diol. Can be mentioned. 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. You may use these 1 type or in mixture of 2 or more types. These alcohols may be amino alcohols containing an amino group in the molecule, glycidyl alcohols containing a glycidyl group in the molecule, or silyl alcohols containing a silyl group. From the viewpoint of adhesive strength at low temperatures, a divalent alcohol is preferred. More preferred is a monohydric alcohol.

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

The component (B) is an ester of the component (a) and the component (b).

The component (a) is not particularly limited as long as it has an alkyl group or an alkylene group and has 1 to 40 carbon atoms and a monovalent or divalent carboxylic acid. Specifically, formic acid, acetic acid, propionic acid , Butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, pentadecylic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, dimer acid, olein Acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid An acid etc. are mentioned. Of these, stearic acid and isostearic acid are preferable from the viewpoint of improving the adhesive strength at low temperature to a difficult-to-adhere substrate.

The component (b) is not particularly limited as long as it has an alkyl group or an alkenyl group and is an ester of a 1 to 6-valent alcohol (b) having 1 to 40 carbon atoms. Examples thereof include known ones such as methanol, ethanol, propanol, isopropanol, 2-ethylhexanol, stearyl alcohol, and isostearyl alcohol. Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,6-hexanediol, and dimer diol. Can be mentioned. 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. You may use these 1 type or in mixture of 2 or more types. Stearyl alcohol or isostearyl alcohol is preferable from the viewpoint of improving the adhesive strength at low temperature to a difficult-to-adhere substrate. More preferred is stearyl alcohol.

(B) The esterification method of a component adds (a) component and (b) component in presence or absence of a solvent, and adds an esterification catalyst as needed, and is about 250-280 degreeC, and is 1 to 8 hours. A method of performing a heat dehydration reaction to a certain extent may be used.

The tackifier for the water-based adhesive / adhesive of the present invention contains at least (A) and (B) at a weight ratio of (A) :( B) of 95 to 99.9: 0.1 to 5. To do. When the ratio of the component (A) is less than 95, the holding power and the constant load peelability are lowered, and when it exceeds 99.9, the adhesive strength at a low temperature is lowered. When the ratio of the component (B) is less than 0.1, the adhesive strength at low temperatures is lowered, and when it exceeds 5, the holding force and the constant load peelability are insufficient. In addition, the tackifier of this invention can contain a various additive as needed not only (A) component and (B) component. Examples of the additive include an antioxidant and a light stabilizer. Examples of the antioxidant include phenolic antioxidants, sulfur antioxidants, and phosphorus antioxidants. Examples of the light stabilizer include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and hindered amine stabilizers.

The tackifier of the present invention has a compression dynamic elastic modulus (G ′) of 1.0 × 10 ⁵ to 1 at −10 to ⁵ ° C. when the tackifier layer has a thickness of about 0.4 to 1.0 mm. 0.0 × 10 ⁹ Pa. Thereby, it can have the adhesive force which was excellent with respect to the difficult-to-adhere base material at low temperature. If the pressure layer is less than 1.0 × 10 ⁵ Pa at −10 to ⁵ ° C., the adhesive layer is too soft to cause cohesive failure even if it is in close contact with the substrate, and 1.0 × 10 ⁹ Pa at −10 to 5 ° C. If it exceeds, the pressure-sensitive adhesive layer is hard, so that it is difficult to adhere to the substrate, and the adhesive strength at low temperatures is reduced. Preferably, the compression elastic modulus (G ′) is 1.0 × 10 ^{6 to} 1.0 × 10 ⁸ Pa at −10 to 5 ° C.

The compressive dynamic elastic modulus (G ′) can be measured under the following measurement conditions by producing a tackifier layer having a thickness of about 0.4 to 1.0 mm.
Measuring device: EXSTAR TMA / SS6000 manufactured by Seiko Instruments
Measurement sample: 6 mm × 7 mm × 450 μm
Measurement conditions: minimum tension / compression force = 1000 mN, tension / pressure gain = 1.5, initial force amplitude = 100 mN, frequency = 10 Hz, temperature change program = −50 to 50 ° C., heating rate = 3 ° C./min

The tackifier layer may be produced by applying a melted liquid sample on a release paper using a 500 μm applicator, cooling to room temperature, and then cutting the resin into an arbitrary size. After dissolving in a soluble solvent such as toluene, a 700 μm applicator may be used for coating on release paper, and the solvent may be evaporated before cutting into an arbitrary size. Alternatively, a mold of an arbitrary size may be placed on the release paper, and the molten resin may be poured between the release papers and allowed to cool to room temperature for use in the test.

The weight-average molecular weight of the tackifier is preferably 200 to 3500 in order to balance low-temperature adhesion to a difficult-to-adhere substrate, holding power, and constant load peelability. More preferably, it is 260-3000, More preferably, it is 600-3000.

The weight average molecular weight (Mw) can be calculated as a polystyrene conversion value obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC). The GPC method was measured under the following conditions.
Analyzer: HLC-8120 (manufactured by Tosoh Corporation)
Column: TSKgelSuperHM-L × 3 eluent: tetrahydrofuran injection Sample concentration: 5 mg / mL
Flow rate: 0.6mL / min
Injection volume: 100 μL
Column temperature: 40 ° C
Detector: RI

The tackifier of the present invention is for an aqueous adhesive / adhesive. This water-based adhesive / adhesive means both an aqueous solution-based adhesive / adhesive that can be dissolved in water from the viewpoint of environmental protection, or an aqueous dispersion-based adhesive / adhesive that is stably dispersed in water. To do.

As for the tackifier for water-based adhesives / adhesives of this invention, it is preferable that water-based adhesives / adhesives are used for a difficult-to-adhere substrate. Examples of the hardly adhesive substrate include a foam substrate, an olefin resin, PET (polyethylene terephthalate resin), and nylon. The tackifier for water-based adhesives / adhesives of the present invention exhibits excellent adhesive strength against difficult-to-adhere substrates.

The foam base material is a base material having pores such as polyurethane foam, polyolefin foam, vinyl chloride foam, etc., and the surface is a rough surface having irregularities.

Examples of the polyurethane foam include soft polyether, soft polyester, hard polyether, and hard polyester. Among these, a soft polyether type and a soft polyester type are preferable, and a soft polyether type is particularly preferable.

The flexible polyether-based urethane foam is obtained by mixing a polyisocyanate and a polyol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming the resin while forming a resin. The pores are open-celled and have a resilience to the load.

The flexible polyester urethane foam is obtained by mixing a polyisocyanate and a polyester diol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming while forming a resin. The pores are open-celled and have a resilience to the load.

The rigid polyether-based urethane foam is obtained by mixing a polyisocyanate and a polyol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming while forming a resin. A void is a single bubble, which has no resilience to a load.

The rigid polyester-based urethane foam is obtained by mixing a polyisocyanate and a polyester diol with a foaming agent, a foaming aid, a catalyst, a colorant, and the like, and foaming while forming a resin. A void is a single bubble, which has no resilience to a load.

Examples of the olefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene, ethylene and propylene. And a polymer having a diene component of 50% by weight or less in any ratio (for example, a cyclic copolymer such as ethylene-propylene-diene terpolymer, polymethylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene). And a random copolymer or block copolymer of polyolefin, ethylene or propylene and 50% by weight or less of a vinyl compound. Among these, polypropylene, polyethylene, and polyisobutylene are preferable, and polypropylene is particularly preferable.

The present invention is also a tackifying resin emulsion obtained by emulsifying a tackifier for water-based adhesive / adhesive with an emulsifier.

The emulsifier is not particularly limited as long as it is a polymer emulsifier obtained by polymerizing monomers, and a known emulsifier can be used.

The said monomer is not specifically limited, A hydrophilic monomer, a hydrophobic monomer, etc. are mentioned. These may be used alone or in combination.

Specific examples of the hydrophilic monomer include, for example, (1) monocarboxylic acid vinyl monomers such as (meth) acrylic acid and crotonic acid, alkali metal salts such as sodium salts and potassium salts thereof, and alkaline earth metals. Salts, ammonium salts, salts of organic bases, (2) dicarboxylic acid vinyl monomers such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, muconic acid, and alkali metal salts such as sodium salts and potassium salts thereof, Alkaline earth metal salts, ammonium salts, salts of organic bases, (3) organic sulfonic acid vinyl monomers such as vinyl sulfonic acid, styrene sulfonic acid, methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid And alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salt, ammonium salt, organic Group salts, phosphate vinyl monomers such as phosphate ester vinyl monomers such as (4) 2- (meth) acryloyloxyethyl acid phosphate, diphenyl-2 (meth) acryloyloxyphosphate and sodium salts thereof, potassium Alkali metal salts such as salts, alkaline earth metal salts, ammonium salts, salts of organic bases, (5) (meth) acrylamide monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, (6) Nitrile monomers such as (meth) acrylonitrile, (7) Vinyl ester monomers such as vinyl acetate, (8) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Hydroxy group-containing (meth) acrylic such as 2-hydroxybutyl acrylate Ester monomers, (9) methyl vinyl ether, glycidyl (meth) acrylate, urethane acrylate, and other monomers such as vinyl pyrrolidone. From the viewpoint of mechanical stability of the emulsion, (1) and (3) are preferred. More preferred are (meth) acrylic acid in (1), sodium salt of (meth) acrylic acid, and sodium salt of styrene sulfonic acid and methallyl sulfonic acid in (3).

Specific examples of the hydrophobic monomer include (1) methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, polyoxyalkylene (meth) acrylate (Meth) acrylic acid ester monomers such as styrene, (2) styrene monomers such as styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, chlorovinyltoluene, (3) C6-C22 α-olefin, etc. Other monomers are mentioned. (1) and (2) are preferable from the viewpoint of adhesive performance (particularly holding power) and emulsification. More preferred are methyl (meth) acrylate in (1) and styrene in (2).

The emulsifier has a molar ratio (c-1) of the hydrophilic monomer (c-1) and the hydrophobic monomer (c-2) in that the adhesion performance (particularly the holding power) and the mechanical stability can be improved. : (C-2) = 45-75: It is preferable that it is a (meth) acrylic-type copolymer (C) obtained by making it copolymerize by 25-55.

In addition, the said emulsifier can contain various additives other than (c-1) component, (c-2) component, etc. as needed. Examples of the additive include a reactive emulsifier, a polymerization initiator, and a chain transfer agent described later. Examples of the polymerization initiator include peroxide compounds and azo compounds. Examples of the chain transfer agent include α-methylstyrene dimer, carbon tetrachloride, thiol compounds, and the like.

Examples of the polymerization method in the production method of the emulsifier include solution polymerization, suspension polymerization, and emulsion polymerization using a reactive emulsifier other than the polymer emulsifier.

Examples of reactive emulsifiers other than the high molecular weight emulsifier include surfactants 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 carbon-carbon in the molecule. It has a double bond. 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, polyoxyethylene alkyl ether having at least one functional group in the molecule, polyoxyethylene phenyl ether having at least one functional group in the molecule, and sulfosuccinic acid thereof. And polyoxyethylene alkylphenyl ethers having at least one of the above functional groups in the molecule, and sulfosuccinic acid ester salts, sulfuric acid ester salts, phosphoric acid ester salts, and fats thereof. Amino acid or aromatic carboxylate, acidic phosphoric acid (meth) acrylate ester emulsifier, acid anhydride modified product of rosin glycidyl ester acrylate (see JP-A-4-256429), JP-A-63- No. 23725, JP-A 63-24093 JP, include the various emulsifiers such as described in JP-A-62-104802.

Furthermore, what replaced polyoxyethylene in the said reactive emulsifier with what block-copolymerized or random-copolymerized polyoxypropylene or polyoxyethylene and polyoxypropylene is mentioned. In addition, as these commercial items, for example, “KAYAMER PM-1”, “KAYAMER PM-2”, “KAYAMER PM-21” (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" (above, ADEKA Corporation) Manufactured), "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 (above, Daiichi Kogyo Seiyaku Co., Ltd.), Eleminor JS-2 (Sanyo) Adult Kogyo Co., Ltd.), "Latemul K-180" (manufactured by Kao Corporation) and the like as a typical example.

As reactive emulsifiers other than these high molecular weight emulsifiers, polyoxyethylene alkyl ethers are preferred from the viewpoint of polymerizability and the emulsifying properties of the resulting high molecular emulsifier, and have at least one (meth) allyl group in the molecule. It is particularly preferable to use a sulfate ester salt of polyoxyethylene alkyl ether. As these commercial products, “ADEKA rear soap SR-10”, “ADEKA rear soap SR-20” (trade name, manufactured by ADEKA Corporation), “AQUARON KH-05”, “AQUARON KH-10” (No. 1) Ichi Kogyo Seiyaku Co., Ltd.) is preferable.

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 superposition | polymerization rosin esters, Preferably it is 2-8 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 emulsification method is not particularly limited, and a known emulsification method such as a high pressure emulsification method or a phase inversion emulsification method can be employed.

The high-pressure emulsification method is a method in which the tackifier is in a liquid state, the emulsifier and water are premixed, finely emulsified using a high-pressure emulsifier, and then the solvent is removed as necessary. The method of bringing the tackifier into a liquid state can be heated only, dissolved in a solvent and then heated, or mixed with a non-volatile substance such as a plasticizer, but heated without using a solvent. Only is preferred. In addition, as a solvent, the organic solvent which can melt | dissolve tackifier components, such as toluene, xylene, methylcyclohexane, and ethyl acetate, is mentioned.

In the phase inversion emulsification method, a tackifier resin (tackifier) is heated and melted, and then an emulsifier and water are added while stirring to form a W / O emulsion. This is a method of phase inversion to W emulsion.

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 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 0.7 μm or less is storage stable. From the viewpoint of sex. The tackifying resin emulsion has a white to milky white appearance, has a pH of about 2 to 10, and a viscosity of usually about 10 to 1000 mPa · s (at 25 ° C. and a solid concentration of 50%).

The present invention is also an aqueous tacky / adhesive composition containing at least the tackifier for the aqueous sticky / adhesive. The water-based adhesive / adhesive composition can be further mixed with a base polymer. Further, the aqueous sticky / adhesive composition of the present invention can be used as an aqueous sticky / adhesive.

Examples of the base polymer include acrylic polymer emulsions, rubber latexes and synthetic resin emulsions, and can be used in combination with each other. Further, a crosslinking agent, an antifoaming agent, a thickening agent, and a filler are added as necessary. Agents, antioxidants, water resistance agents, film-forming aids, and the like can also be used. Moreover, you may use a well-known tackifier. The solid content concentration of these water-based adhesive / adhesive compositions is usually about 40 to 70% by weight, preferably 55 to 70% by weight. Although at least one base polymer may be used, it is preferable to use an acrylic polymer emulsion from the viewpoint of good weather resistance and light resistance.

The mixing method is not particularly limited, and the tackifier may be emulsified and mixed as a tackifier resin emulsion, or the tackifier may be added to the base polymer and mixed using a high shear rotary mixer. An aqueous dispersion in which a tackifier is dispersed in a base polymer may be used. When an aqueous dispersion in which a tackifier is dispersed in a base polymer using a high shear rotary mixer, the water resistance is good, and foam base materials such as urethane foam and polypropylene foam, and olefinic resins It becomes a sticky / adhesive that satisfies adhesive properties such as holding power and constant load peelability while having excellent adhesive strength at a low temperature of about 5 ° C. to a normal temperature of about 40 ° C. with respect to the surface.

As the above-mentioned acrylic polymer emulsion, those generally used for various acrylic pressure-sensitive adhesives can be used, such as a batch charging polymerization method of monomers such as (meth) acrylic acid ester, a monomer sequential addition polymerization method, and an emulsion monomer sequential step. It can be easily produced by a known emulsion polymerization method such as an 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 resulting 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 tackifier is not particularly limited, but the adhesive effect of the tackifier on the foam base material and the olefin resin can be sufficiently expressed, and the holding power is reduced by excessive use. As an appropriate range of use that does not cause odor, the tackifier is usually about 1 to 50 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-based latex and the tackifier is not particularly limited, but the effect of the modification by the tackifier can be sufficiently exhibited, and the holding power, the constant load peelability, and the curved surface adhesiveness decrease due to excessive use. As an appropriate range of use that does not cause the problem, the tackifier 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).

As the synthetic resin emulsion, various known ones used in aqueous adhesive / adhesive compositions can be used. For example, synthetic resin emulsions such as vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, and urethane emulsion can be used. can give.

The use ratio of the synthetic resin emulsion and the tackifier is not particularly limited, but the effect of modifying the tackifier can be sufficiently expressed, and the retention force, constant load peelability, curved surface adhesiveness due to excessive use can be expressed. As an appropriate use ratio that does not cause a decrease, the tackifier 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 synthetic resin emulsion.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “part” mean “% by weight” and “part by weight” unless otherwise specified.

Production Example 1 [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 nitrogen gas flow 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 sodium bicarbonate (pH adjuster) and water 1/10 amount of the initiator aqueous solution consisting of 8.83 parts 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 initiator aqueous 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%.

Production Example 2 [Production of Polymerized Rosin Ester 1 (Component (A))]
In a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube, 100 parts of polymerized rosin (resin acid dimer 65%, acid value 140, softening point 140 ° C.), stearyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) After charging 33.7 parts, the mixture was reacted at 250 ° C. for 2 hours under a nitrogen gas stream, and further heated to 275 ° 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 polymerized rosin ester 1.

Production Example 3 [Production of Polymerized Rosin Ester 2 (Component (A))]
In the same reaction vessel as in Production Example 2, 100 parts of polymerized rosin (same as in Production Example 2), dimer diol (Cropa PRIPOL 2033: aliphatic diol having 36 carbon atoms obtained by complete hydrogenation of dimer acid) ) Production was carried out in the same manner except that 68.3 parts were charged to obtain polymerized rosin ester 2.

Production Example 4 [Production of Polymerized Rosin Ester 3 (Component (A))]
Production was carried out in the same manner except that 100 parts of polymerized rosin (same as in Production Example 2) and 47.5 parts of diethylene glycol were charged into the same reaction vessel as in Production Example 2, and polymerized rosin ester 3 was obtained.

Production Example 5 [Production of Polymerized Rosin Ester 4 (Component (A))]
Production was carried out in the same manner except that 100 parts of polymerized rosin (same as in Production Example 2) and 23.3 parts of lauryl alcohol were charged in the same reaction vessel as in Production Example 2, and polymerized rosin ester 4 was obtained.

Production Example 6 [Production of Polymerized Rosin Ester 5 (Component (A))]
Production was carried out in the same manner except that 100 parts of polymerized rosin (same as in Production Example 2) and 14 parts of pentaerythritol were charged in the same reaction vessel as in Production Example 2, and polymerized rosin ester 5 was obtained.

Production Example 7 [Production of Polymerized Rosin Ester 6 (Component (A))]
Production was carried out in the same manner except that 100 parts of polymerized rosin (same as in Production Example 2) and 67.5 parts of stearyl alcohol were charged in the same reaction vessel as in Production Example 2, and polymerized rosin ester 6 was obtained.

Production Example 8 [Production of Polymerized Rosin Ester 7 (Component (A))]
Production was carried out in the same manner except that 100 parts of polymerized rosin (same as in Production Example 2) and 16.9 parts of stearyl alcohol were charged in the same reaction vessel as in Production Example 2, and polymerized rosin ester 7 was obtained.

Production Example 9 [Production of rosin ester 1 (component (A))]
A rosin ester 1 was obtained in the same manner as in Production Example 2 except that 100 parts of disproportionated rosin (acid number 160, softening point 75 ° C.) and 54 parts of diethylene glycol were charged.

Production Example 10 [Production of rosin ester 2 (component (A))]
Production was carried out in the same manner except that 100 parts of hydrogenated rosin (acid value 150, softening point 65 ° C.) and 54 parts of diethylene glycol were charged in the same reaction vessel as in Production Example 2 to obtain rosin ester 2.

Production Example 11 [Production of rosin ester 3 (component (A))]
Production was carried out in the same manner except that 100 parts of gum rosin (acid value 170, softening point 70 ° C.) and 54 parts of diethylene glycol were charged in the same reaction vessel as in Production Example 2 to obtain rosin ester 3.

Production Example 12 [Production of ester 1 (component (B))]
Manufactured in the same manner as in Production Example 2 except that 100 parts of stearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 95 parts of stearyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged in the same reaction vessel as in Production Example 2. Thus, ester 1 was obtained.

Production Example 13 [Production of ester 2 (component (B))]
Production was conducted in the same manner as in Production Example 2 except that 100 parts of acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 455.8 parts of dimer diol (same as Production Example 3) were charged in the same reaction vessel as in Production Example 2. Performed to give ester 2.

Production Example 14 [Production of ester 3 (component (B))]
Production was carried out in the same manner as in Production Example 2, except that 100 parts of dimer acid (PRIPOL 1017 manufactured by Croda) and 44 parts of 2-ethylhexanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged in the same reaction vessel as in Production Example 2. Ester 3 was obtained.

Production Example 15 [Production of emulsifier (C-1)]
In the same reaction vessel as in Production Example 1, 24 parts of styrene sulfonic acid soda as a hydrophilic monomer, 18 parts of methacrylic acid, 15 parts of acrylic acid, 11 parts of styrene as a hydrophobic monomer, 7 parts of methyl methacrylate, and polyoxyethylene 40 parts of phenyl ether reactive emulsifier (trade name “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was charged (in terms of solid content), and 10 parts of ion-exchanged water was added to obtain a monomer aqueous solution. . Next, 10 parts of 2,4-diphenyl-4-methyl-1-pentene, 2.4 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. Next, the temperature of the reaction system was raised to 85 ° C. and held for 2 hours to perform a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept warm for 1 hour. Thereafter, 18 parts of 48% sodium hydroxide aqueous solution was added to the reaction system, and the mixture was stirred well and cooled to room temperature. Thus, an aqueous solution of an emulsifier (C-1) having a solid content of 21.0% was obtained.

Production Example 16 [Production of Emulsifier (C-2)]
In a reaction vessel similar to Production Example 15, 15 parts of sodium styrene sulfonate, 10 parts of methacrylic acid, 20 parts of acrylic acid as hydrophilic monomers, 13 parts of styrene as hydrophobic monomers, 12 parts of methyl methacrylate, and polyoxyethylene 40 parts of phenyl ether reactive emulsifier (trade name “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was charged (in terms of solid content), and 10 parts of ion-exchanged water was added to obtain a monomer aqueous solution. . Next, 10 parts of 2,4-diphenyl-4-methyl-1-pentene, 2.4 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. Next, the temperature of the reaction system was raised to 85 ° C. and held for 2 hours to perform a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept warm for 1 hour. Thereafter, 18 parts of 48% sodium hydroxide aqueous solution was added to the reaction system, and the mixture was stirred well and cooled to room temperature. Thus, an aqueous solution of an emulsifier (C-2) having a solid content of 21.0% was obtained.

Production Example 17 [Production of Emulsifier (C-3)]
A reaction vessel similar to Production Example 15 was charged with 8.5 parts of sodium methallyl sulfonate as a hydrophilic monomer, 16.7 parts of methacrylic acid, and 30 parts of methyl methacrylate as a hydrophobic monomer, and further polyoxyethylene phenyl ether. System reactive emulsifier (trade name “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 40 parts (in terms of solid content) and 10 parts of ion-exchanged water were added to obtain an aqueous monomer solution. Next, 10 parts of 2,4-diphenyl-4-methyl-1-pentene, 2.4 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. Next, the temperature of the reaction system was raised to 85 ° C. and held for 2 hours to perform a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept warm for 1 hour. Thereafter, 18 parts of 48% sodium hydroxide aqueous solution was added to the reaction system, and the mixture was stirred well and cooled to room temperature. Thus, an aqueous solution of an emulsifier (C-3) having a solid content of 21.0% was obtained.

Production Example 18 [Production of emulsifier (C-4)]
A reaction vessel similar to Production Example 15 was charged with 5 parts of sodium methallyl sulfonate as a hydrophilic monomer, 35 parts of methacrylic acid, and 25 parts of methyl methacrylate as a hydrophobic monomer, and further reacted with polyoxyethylene phenyl ether. 40 parts of emulsifier (trade name “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 10 parts of ion-exchanged water were added to obtain a monomer aqueous solution. Next, 10 parts of 2,4-diphenyl-4-methyl-1-pentene, 2.4 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. Next, the temperature of the reaction system was raised to 85 ° C. and held for 2 hours to perform a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept warm for 1 hour. Thereafter, 18 parts of 48% sodium hydroxide aqueous solution was added to the reaction system, and the mixture was stirred well and cooled to room temperature. Thus, an aqueous solution of an emulsifier (C-4) having a solid content of 21.0% was obtained.

Production Example 19 [Production of emulsifier (C-5)]
In a four-necked flask equipped with a nitrogen gas introduction tube, a thermometer, a reflux condenser and a stirrer, 20 parts of styrene sulfonic acid sodium as a hydrophilic monomer, 15 parts of methacrylic acid, 22 parts of acrylic acid, and styrene as a hydrophobic monomer 10 parts, 5 parts of methyl methacrylate, and 40 parts of polyoxyethylene phenyl ether-based reactive emulsifier (trade name “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (in terms of solid content) are charged. 10 parts of exchange water was added to make an aqueous monomer solution. Next, 10 parts of 2,4-diphenyl-4-methyl-1-pentene, 2.4 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. Next, the temperature of the reaction system was raised to 85 ° C. and held for 2 hours to perform a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept warm for 1 hour. Thereafter, 18 parts of 48% sodium hydroxide aqueous solution was added to the reaction system, and the mixture was stirred well and cooled to room temperature. Thus, an aqueous solution of an emulsifier (C-5) having a solid content of 21.0% was obtained.

Production Example 20 [Production of emulsifier (C-6)]
A reaction vessel similar to Production Example 15 was charged with 4 parts of sodium methallyl sulfonate as a hydrophilic monomer, 15 parts of methacrylic acid, and 30 parts of methyl methacrylate as a hydrophobic monomer, and further polyoxyethylene phenyl ether-based reactivity. 40 parts of emulsifier (trade name “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 10 parts of ion-exchanged water were added to obtain a monomer aqueous solution. Next, 10 parts of 2,4-diphenyl-4-methyl-1-pentene, 2.4 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. Next, the temperature of the reaction system was raised to 85 ° C. and held for 2 hours to perform a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept warm for 1 hour. Thereafter, 18 parts of 48% sodium hydroxide aqueous solution was added to the reaction system, and the mixture was stirred well and cooled to room temperature. Thus, an aqueous solution of an emulsifier (C-6) having a solid content of 21.0% was obtained.

Production Example 21 [Production of Tackifier 1]
In the same reaction vessel as in Production Example 2, 100 parts of the polymerized rosin ester 1 obtained in Production Example 2 and 2.6 parts of the ester 1 obtained in Production Example 12 (weight ratio (A): (B) = 97.5: 2.5) Charge, stir and mix at 100 ° C. for 2 hours to obtain tackifier 1.

The tackifiers 2 to 41 were produced by the same method as the tackifier 1 except that the composition was changed as shown in Table 1.

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) was calculated as a polystyrene conversion value obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC). The GPC method was measured under the following conditions. The results are shown in Table 2.
Analyzer: HLC-8120 (manufactured by Tosoh Corporation)
Column: TSKgelSuperHM-L × 3 eluent: tetrahydrofuran injection Sample concentration: 5 mg / mL
Flow rate: 0.6mL / min
Injection volume: 100 μL
Column temperature: 40 ° C
Detector: RI

(Manufacture of tackifier layer)
Using the tackifiers 1 to 41 obtained by the above method, the tackifier layers 1 to 41 are placed on a release paper with a 6 mm × 7 mm × 450 μm size mold, and the molten resin is poured into the release paper. The sample (tackifier layer) was obtained by sandwiching and allowing to cool to room temperature.
(Compressive dynamic modulus)
The compression dynamic elastic modulus at −10 to 5 ° C. of this tackifier layer was measured under the following conditions. The results are shown in Table 3.
Measuring device: EXSTAR TMA / SS6000 manufactured by Seiko Instruments
Measurement sample: 6 mm × 7 mm × 450 μm
Measurement conditions: minimum tension / compression force = 1000 mN, tension / pressure gain = 1.5, initial force amplitude = 100 mN, frequency = 10 Hz, temperature change program = −50 to 50 ° C., heating rate = 3 ° C./min

Production Example 22 [Preparation of tackifying resin emulsion 1]
After 100 parts of the tackifier 1 obtained in Production Example 21 was dissolved in 40 parts of toluene at 80 ° C. for 3 hours, the emulsifier (C-1) obtained in Production Example 15 was converted to solid content. 5 parts and 140 parts of water were added and stirred for 1 hour. Subsequently, high pressure emulsification was performed with a high pressure emulsifier (mantongaurin) at a pressure of 30 MPa to obtain an emulsion. Subsequently, vacuum distillation was performed for 6 hours under the conditions of 70 ° C. and 2.93 × 10 ⁻² MPa to obtain a tackifier resin emulsion 1 having a solid content of 50%.

The tackifier resin emulsions 2 to 45 were produced in the same manner as the tackifier resin emulsion 1 except that the composition was changed as shown in Table 4.

Example 1
(Preparation of aqueous adhesive composition 1)
80 parts of the acrylic polymer emulsion obtained in Production Example 1 (in terms of solid content) and 20 parts of the tackifier resin emulsion 1 obtained in Production Example 22 (in terms of solid content) were mixed, and the thickener Primal ASE-60. 0.5 part (made by Rohm and Haas) was added, an appropriate amount of aqueous ammonia was added, and the mixture was thickened to obtain an aqueous pressure-sensitive adhesive composition. About the obtained water-based adhesive composition, mechanical stability, adhesive force, holding power, and constant load peelability were evaluated by the following evaluation methods. The results are shown in Table 5.

(Mechanical stability of aqueous adhesive composition)
The aqueous pressure-sensitive adhesive composition 1 prepared in Example 1 was further adjusted to pH 8 and a non-volatile content of 30% with 28% ammonia water, and then subjected to a Marlon test, and the rate of occurrence of aggregates (%) = (aggregation) Product / initial solid content) × 100. The conditions of the Marlon test are: load: 10 kg, rotation speed: 1000 rpm, share time: 10 minutes.
Evaluation criteria ○: Aggregate generation rate 0.7% or less Δ: Aggregate generation rate 0.7 over less than 1.0% ×: Aggregation generation rate 1.0% or more

(Manufacture of sample film for adhesion evaluation)
Each water-based pressure-sensitive adhesive composition obtained by the above-described method is obtained by using a dice-type applicator (manufactured by Otsugi Equipment Co., Ltd.) to a polyester film (trade name “S-100”, Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 38 μm. The product was coated so that the dry film thickness was about 160 μm. Next, the film was dried for 5 minutes in an air circulation dryer at 105 ° C., and water in the pressure-sensitive adhesive composition was removed to prepare a sample film. Using this sample film, adhesive force, holding force, and constant load peeling were measured as follows. The results are shown in Table 5.

(Adhesive force)
A sample tape cut from the sample film to a width of 25 mm and a length of 150 mm was used as a sample tape, which was placed on a soft ether-based urethane foam or polypropylene (PP) plate, and a roll having a weight of 2 kg was attached by reciprocating once. 180 ° peeling was performed at 5, 23, and 40 ° C. at a peeling speed of 300 mm / min, and the adhesive force (g / 25 mm) per 25 mm width was measured.

(Holding power)
A sample tape cut from the sample film to a width of 25 mm and a length of 25 mm was used as a sample tape, which was superposed on a stainless steel plate and pasted together by a reciprocating roller with a weight of 2 kg. A load of 1.2 kg was applied at 40 ° C., and the time (second) of dropping was measured. The longer the time it takes to drop, the stronger the holding power.

(Constant load peeling)
A sample tape cut from the sample film to a width of 25 mm and a length of 100 mm was used as a sample tape. A load of 200 g was applied to the end of the sample tape, the sample tape was fixed so as to be peeled at 90 °, and the time (min) of dropping was measured.
Peeling mode: None is interface peeling, CF is cohesive failure.

For Examples 2 to 20 and Comparative Examples 1 to 25, the water-based adhesive composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 6. Mechanical stability and adhesive strength The holding power and the constant load peelability were evaluated.

Claims (10)

The polymerized rosin compound (A) has an alkyl group or an alkylene group, has 1 to 40 carbon atoms and has a monovalent or divalent carboxylic acid (a), an alkyl group or an alkenyl group, and has 1 carbon atom. The ester (B) of 1 to 6-valent alcohol (b) of ˜40 is contained at a ratio of (A) :( B) in a weight ratio of 95 to 99.9: 0.1 to 5 and a thickness of 0. The water-based viscosity, wherein the ⁴ to 1.0 mm tackifier layer has a compressive dynamic elastic modulus (G ′) at −10 to 5 ° C. of 1.0 × 10 ^{5 to} 1.0 × 10 ⁹ Pa.・ Tackifier for adhesives. The tackifier for water-based adhesives / adhesives according to claim 1, wherein the water-based adhesive / adhesives are used as a hard-to-adhere substrate at -10 to 5 ° C. The tackifier for water-based adhesives / adhesives according to claim 1 or 2, wherein the tackifier has a weight average molecular weight of 200 to 3,500. The tackifier for an aqueous adhesive / adhesive according to claim 1, wherein the polymerized rosin compound (A) is a polymerized rosin ester. The tackifier for an aqueous adhesive / adhesive according to claim 4, wherein the polymerized rosin ester is obtained by reacting a polymerized rosin and an alcohol having 1 to 40 carbon atoms and 1 to 3 carbon atoms. . An aqueous tacky / adhesive composition comprising the tackifier for the aqueous sticky / adhesive according to claim 1. The water-based adhesive / adhesive composition according to claim 6, further comprising an acrylic polymer emulsion. A tackifier resin emulsion obtained by emulsifying the tackifier according to any one of claims 1 to 5 with an emulsifier. The emulsifier is obtained by copolymerizing the hydrophilic monomer (c-1) and the hydrophobic monomer (c-2) at a molar ratio (c-1) :( c-2) = 45 to 75:25 to 55. The tackifying resin emulsion according to claim 8, comprising a (meth) acrylic copolymer (C). A water-based adhesive / adhesive composition containing the tackifier resin emulsion according to claim 8 or 9.