JP2020023596A - Tackifier resin aqueous dispersion, aqueous adhesive and adhesive sheet - Google Patents

Abstract

To provide a tackifier resin aqueous dispersion that has an extremely small content of an organic solvent, and gives excellent storage stability, mechanical stability, coatability, workability, adhesiveness, curved surface adhesiveness, moist heat resistance, constant load peelability, and base material adhesion, and provide an aqueous adhesive and an adhesive sheet.SOLUTION: A tackifier resin aqueous dispersion has, based on a tackifier resin (A) with a softening point of 100-180°C of 100 pts.mass, a copolymer resin (B) of 0.5-50 pts.mass, having the organic solvent content of 1000 ppm or less, satisfying the following (1) and (2). (1) The copolymer resin (B) is obtained by modifying a copolymer (X) with a compound (b3) having an alkylene oxide unit. (2) The copolymer (X) at least has, as constituent monomers, at least one compound (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide and diolefin, and a dibasic acid having an unsaturated group or an anhydride thereof (b2-1).SELECTED DRAWING: None

Description

  The present invention relates to an aqueous dispersion of a tackifying resin, and an aqueous pressure-sensitive adhesive and a pressure-sensitive adhesive sheet using the same.

  BACKGROUND ART Adhesives are widely used from industrial fields such as packaging, construction, building materials, automobiles, and electronic components to ordinary households. The most common laminated structure of the pressure-sensitive adhesive sheet is “base sheet / pressure-sensitive adhesive layer / peel sheet” (single-sided pressure-sensitive sheet) or “peel sheet / pressure-sensitive adhesive layer / base sheet / pressure-sensitive adhesive layer / peel sheet”. (Double-sided adhesive sheet). At the time of use, the release sheet is peeled off, and the pressure-sensitive adhesive layer is attached to the adherend. The pressure-sensitive adhesive sheet is used for various uses, and the required adhesive strength is also various.

  In recent years, from the viewpoint of protecting the global environment (suppressing the emission of volatile organic compounds), improving the working environment, and effectively using resources, water-based emulsion-based adhesives (hereinafter referred to as "water-based adhesives") have been used as alternatives to solvent-based adhesives. (Abbreviated as) has been studied. However, the water-based pressure-sensitive adhesive has a drawback that, as compared with the solvent-based pressure-sensitive adhesive, the adhesiveness to a substrate sheet and the adhesive force to a polyolefin-based adherend such as polyethylene and polypropylene are extremely poor. It has also been required to have a sufficient adhesive strength to hardly adherents such as adherends.

  In addition, in automotive applications and building material applications, there is a concern about sick car problems and sick house problems, and aqueous adhesives are widely used. In automotive applications, for example, in the case of interior parts, the temperature inside the vehicle becomes extremely high in summer, while in building materials, the temperature increases in an environment exposed to direct sunlight in summer. The agent is required to have heat resistance at such a high temperature, wet heat resistance, and heat resistance holding power.

  In recent years, substrate sheets have also been diversified. In particular, in automotive applications, sheet-like foams having irregularities on the surface, such as urethane foam, are porous, and therefore have a substantial contact area with the pressure-sensitive adhesive layer. Therefore, it was difficult to ensure the adhesion of the pressure-sensitive adhesive layer to the sheet-like foam. The sheet-like foam is thicker than a general base sheet such as a plastic film or paper, and has a large force to return to a flat state against bending, that is, a large restoring force. However, an adhesive sheet using a sheet-like foam as a base sheet is often attached to an adherend having an uneven surface or a curved surface as described above. Therefore, if the adhesiveness of the pressure-sensitive adhesive layer to the sheet-like foam is insufficient, the sheet-like foam cannot be stuck to the adherend against the restoring force of the sheet-like foam. That is, peeling occurs between the sheet-like foam and the pressure-sensitive adhesive layer, and the sheet-like foam peels from the adherend in a state where the pressure-sensitive adhesive layer remains on the adherend.

  On the other hand, even if the adhesiveness of the pressure-sensitive adhesive layer to the sheet-shaped foam is sufficient, if the adhesive force of the pressure-sensitive adhesive layer to the adherend is insufficient, the pressure between the adherend and the pressure-sensitive adhesive layer is reduced. Peeling occurs, and the sheet-like foam becomes integral with the pressure-sensitive adhesive layer and peels off from the adherend.

  As the aqueous pressure-sensitive adhesive, an acrylic polymer resin dispersion, a styrene-butadiene copolymer latex, a natural rubber latex, a chloroprene latex, and the like as a base polymer for improving heat resistance and adhesive strength, and a rosin-based resin, It is known that it is used as an aqueous adhesive obtained by mixing an aqueous dispersion of a tackifier resin such as a petroleum resin, a terpene resin, a phenol resin, a ketone resin, or a polyolefin resin. Usually, in such a tackifier resin aqueous dispersion, an aqueous dispersion of a rosin-based resin, a terpene-based resin, and a petroleum-based resin is widely used because of good compatibility with a base polymer and good adhesive properties. ing.

  Various attempts have been made to improve these problems. For example, a specific oxyalkylene group-containing monomer (a) and an ethylenically unsaturated monomer (b) having an anion group or an anion-forming group can be used. ) And an acrylic copolymer essentially comprising a copolymerizable hydrophobic monomer (c) as a polymer emulsifier, containing an aqueous resin dispersion of a rosin substance as an active ingredient and an aqueous resin dispersion of the resin. An aqueous sizing agent for papermaking is disclosed (see Patent Document 1). A homogeneous aqueous resin dispersion of a rosin substance can be obtained by using this polymer emulsifier, but when used as an aqueous adhesive by mixing with an aqueous acrylic resin, the storage stability over a long period of time. In addition, when a pressure-sensitive adhesive sheet is prepared, the adhesive sheet has both low-temperature adhesiveness and heat resistance, but not only has poor water resistance and wet heat resistance, but also has insufficient adhesion to a polyolefin-based adherend. Was.

  For example, a polymer having a glass transition temperature (Tg) of -80 ° C to 0 ° C other than the tackifier resin (A) having a nonvolatile content concentration of 65 to 99% by weight excluding the surfactant component and a tackifier resin (A) ( B) 1 to 35% by weight (provided that the total of the tackifying resin (A) and the polymer (B) is 100% by weight), and the organic solvent contained in the aqueous dispersion of the tackifying resin (A) An aqueous tackifier resin dispersion having an amount of 50 ppm or less is disclosed (see Patent Document 2). Since no organic solvent is used during the production of the tackifier resin aqueous dispersion, there is an advantage that no solvent is contained in the tackifier resin aqueous dispersion, but the tackifier resin aqueous dispersion is generally mixed with the acrylic resin. Since the pressure-sensitive adhesive sheet made from the water-based pressure-sensitive adhesive is low in glass transition temperature (Tg), heat resistance and heat-resistant holding power are extremely reduced.

  For example, the solid content excluding the emulsifier component is 65 to 99% by weight of a polymerized rosin-based ester resin (A) having a softening point of 135 to 180 ° C. and an acid value of 20 or less, and the acid value other than (A) is 50 to 100. Acrylic oligomer having an average molecular weight of 1,000 to 5,000 and having a carboxyl group (B) 1 to 35% by weight [the total of component (A) and component (B) is 100% by weight], and is contained in the aqueous dispersion. There is disclosed an aqueous dispersion of a tackifying resin having an amount of an organic solvent of 50 ppm or less (see Patent Document 3). Approximately an aqueous dispersion of tackifying resin is applied to minimize the content of organic solvent, so it is effective for environmental protection.However, an aqueous dispersion of a polymerized rosin ester resin is mixed with an acrylic resin to form an aqueous dispersion. As a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet prepared from a substantially water-based pressure-sensitive adhesive has insufficient adhesion to a polyolefin-based adherend, and when an attempt is made to produce a resin-based aqueous dispersion containing no solvent, an aqueous dispersion In some cases, there were problems such as high viscosity and difficulty in handling.

  For example, a tackifier resin having a softening point of 120 to 190 ° C and a weight average molecular weight of 500 to 50,000 in the presence of an acrylic oligomer, in the absence of a solvent and under pressure, and dispersed in water. An aqueous dispersion is disclosed (see Patent Document 4). Approximately the tackifier resin aqueous dispersion does not contain an organic solvent, so it is effective for environmental protection, etc.However, since a low molecular weight acrylic oligomer is used, unreacted acrylic monomer remains, so odor is generated. It tends to remain, and when the aqueous tackifier resin dispersion is mixed with an acrylic resin to form an aqueous pressure-sensitive adhesive, the storage stability decreases over a long period of time. Although it can have both adhesiveness and heat resistance, not only water resistance and wet heat resistance are remarkably inferior, but also adhesive strength to a polyolefin-based adherend is insufficient.

  Thus, when mixed with a base polymer to form an aqueous pressure-sensitive adhesive, it provides superior adhesive strength, heat resistance, wet heat resistance, and cohesion as compared with conventional pressure-sensitive adhesives, and uses an organic solvent. Thus, an aqueous dispersion of a tackifier resin having good storage stability has been desired.

JP-A-8-52340 JP 2007-002212 A JP 2008-195888 A JP 2005-330436 A

  From the viewpoint of contributing to environmental protection and occupational health, the present invention has a very low organic solvent content, excellent storage stability, mechanical stability, coating properties, workability, adhesion, curved surface adhesion, moisture and heat resistance, An object of the present invention is to provide an aqueous dispersion of a tackifying resin that gives constant load peelability and substrate adhesion, and an aqueous pressure-sensitive adhesive containing an aqueous dispersion of a general tackifying resin, and a pressure-sensitive adhesive sheet using the same. And

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned object can be achieved by the following tackifier resin aqueous dispersion, and have completed the present invention.

That is, an embodiment of the present invention includes a tackifying resin (A) and a copolymer resin (B) having a softening point of 100 to 180 ° C, and the above-mentioned tackifying resin (A) is used in an amount of 100 parts by mass. A tackifier resin aqueous dispersion containing 0.5 to 50 parts by mass of a copolymer resin (B), an organic solvent content of 1000 ppm or less, and satisfying the following (1) and (2): is there.
(1) The copolymer resin (B) is obtained by modifying the copolymer (X) with a compound (b3) having an alkylene oxide unit.
(2) The copolymer (X) is, as a monomer constituting the copolymer, at least one compound (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide, and diolefin. And at least a dibasic acid having an unsaturated group or an anhydride thereof (b2-1).

  Further, an embodiment of the present invention is the aqueous tackifier resin dispersion, wherein the compound (b3) having an alkylene oxide unit is a compound having an ethylene oxide unit.

  An embodiment of the present invention is the aqueous dispersion of a tackifying resin, wherein the dibasic acid having an unsaturated group or an anhydride thereof (b2-1) is maleic anhydride.

  Further, an embodiment of the present invention is the above tackifier resin aqueous dispersion, wherein the copolymer resin (B) has a mass average molecular weight of 1,000 to 500,000.

  In an embodiment of the present invention, the tackifying resin (A) is at least one resin selected from the group consisting of a rosin resin, a terpene resin and a petroleum resin. It is a resin aqueous dispersion.

  Further, the embodiment of the present invention further includes a liquid resin (C) having a number average molecular weight of 300 to 50,000 (excluding the case of a tackifier resin (A) and a copolymer resin (B)). The above-mentioned aqueous dispersion of tackifier resin, characterized by comprising:

  Further, an embodiment of the present invention is the above aqueous tackifier resin dispersion, further comprising a surfactant (D).

  Further, an embodiment of the present invention is the aqueous tackifier resin dispersion in which the surfactant (D) contains at least one of an anionic surfactant and a nonionic surfactant.

  An embodiment of the present invention is the above-mentioned aqueous dispersion of a tackifying resin, which comprises a basic compound (E).

  Further, an embodiment of the present invention is the above tackifier resin aqueous dispersion, wherein the basic compound (E) is a tertiary amine.

  An embodiment of the present invention is an aqueous pressure-sensitive adhesive comprising the base polymer (P) and the above-mentioned aqueous dispersion of tackifier resin.

  An embodiment of the present invention is a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer formed from the above-mentioned aqueous pressure-sensitive adhesive on a substrate (G).

  In addition, an embodiment of the present invention relates to a method for producing a compound comprising at least one compound (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide and diolefin, and a dibasic acid having an unsaturated group or an anhydride thereof. (B2-1) in the first step of obtaining a copolymer (X) by copolymerization, the copolymer (X) is modified with a compound (b3) having an alkylene oxide unit to obtain a copolymer resin ( Production of an aqueous tackifier resin dispersion including a second step of obtaining B), and a third step of mixing the tackifier resin (A) having a softening point of 100 to 180 ° C with the copolymer resin (B). Is the way.

  The present invention provides excellent storage stability, mechanical stability, coating properties, processability, adhesion, curved surface adhesion, and heat and moisture resistance without reducing the compatibility with the base polymer without containing an organic solvent. , A pressure-sensitive adhesive resin aqueous dispersion and a water-based pressure-sensitive adhesive capable of providing a water-based pressure-sensitive adhesive having good constant-load releasability and substrate adhesion, and a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer formed from the water-based pressure-sensitive adhesive. Along with the provision, it has become possible to provide an aqueous dispersion of a tackifying resin having a high softening point and good filterability, pot stainability, mechanical stability and storage stability.

Hereinafter, embodiments of the present invention will be described.
In this specification,
Tackifying resin (A) having a softening point of 100 to 180 ° C., at least one compound (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide and diolefin, and other ethylenically unsaturated compounds (B2), a dibasic acid having an unsaturated group or an anhydride thereof (b2-1), a copolymerizable compound (b2-2) other than the compound (b1) and the compound (b2-1), and an alkylene oxide unit. Compound (b3), a compound (b3-1) having an ethylene oxide unit, a compound (b3-1-1) having an ethylene oxide unit and having at least one hydroxyl group in a molecule, and a compound (b3-1-1) having an ethylene oxide unit. A compound having at least one amino group in the molecule (b3-1-2); The compound (b3-2) having no unit and the compound (b4) having no alkylene oxide unit were respectively converted into a tackifier resin (A), a compound (b1), a compound (b2), a compound (b2-1), Abbreviated as compound (b2-2), compound (b3), compound (b3-1), compound (b3-1-1), compound (b3-1-2), compound (b3-2) and compound (b4). May be.

In addition, when described as “(meth) acryl”, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, respectively, `` acryl or methacryl '', `` acryloyl or methacryloyl '', `` acrylic or methacrylic acid '', `` acrylate or methacrylate '', `` acryloyloxy or methacryloyloxy '', and `` allyl or methacrylyl '' ].
Hereinafter, each component constituting the tackifier resin aqueous dispersion will be specifically described.

<Tackifying resin (A) having a softening point of 100 to 180 ° C>
Examples of the tackifying resin (A) having a softening point of 100 to 180 ° C include rosin-based resins, terpene-based resins, phenol-based resins, ketone-based resins, and petroleum-based resins.
Specific examples of rosin-based resins include modified rosins obtained by modifying rosins, hydrogenated rosins obtained by hydrogenating rosins, disproportionated rosins obtained by disproportionating rosins, rosin In addition to polymerized rosins obtained by polymerizing the compounds (these are collectively referred to as “raw material rosins”), rosin esters which are esterified products of these raw material rosins and alcohols, and the like are included. Examples of the modified rosins include unsaturated acid-modified rosins obtained by modifying rosins with unsaturated acids, and phenol-modified rosins obtained by modifying rosins with phenols. As the unsaturated acid used in the production of the unsaturated acid-modified rosins, for example, (meth) acrylic acid, fumaric acid, maleic acid and the like can be used. As phenols used for the phenol-modified rosins, for example, phenol, alkylphenol, and the like can be used. The modification method is not particularly limited, and a known method may be employed. Usually, a method of mixing a rosin with an unsaturated acid or a phenol and heating the mixture is employed.

  Specific examples of terpene-based resins include terpene-based resins obtained by polymerizing known terpenes such as α-pinene, β-pinene, and dipentene, or terpene phenols obtained by copolymerizing terpenes and phenols Resins and terpene phenol resins obtained by increasing the molecular weight can also be used. These terpene-based resins may be hydrogenated.

  As a specific example of the phenolic resin, a phenol-formaldehyde resin that is a condensate of phenols and formaldehyde can be used. Examples of the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and the like.Resole obtained by addition reaction of these phenols and formaldehyde with an alkali catalyst or condensation reaction with an acid catalyst is used. And the like can be exemplified. Further, a phenol-acetylene resin obtained by a Reppe reaction using phenols and acetylene as a catalyst and zinc naphthenate or cadmium naphthenate as a catalyst can also be exemplified.

  Examples of the ketone resin include methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and / or a condensate of methylcyclohexanone with formaldehyde.

  Examples of the petroleum-based resin include, among cracked oils other than olefins having 2 to 4 carbon atoms such as ethylene, propylene and butadiene in naphtha cracking, carbons obtained from pentene, pentadiene, isoprene, cyclopentadiene, dicyclopentadiene and the like. Aliphatic, alicyclic and aromatic compounds such as C5 petroleum resins obtained from C5 petroleum resins of several or more and indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, etc. And resins obtained by polymerizing residual olefins of the above. Other examples include C5-C9 copolymer petroleum resins obtained from the above various monomers, coumarone-based resins composed of polymers of coumarone and indene which are fractions of coal tar, resins such as dammers and copals.

Among these tackifying resins, the tackifying resin used in the present invention has a softening point in the range of 100 to 180 ° C, more preferably in the range of 120 to 170 ° C, and particularly preferably in the range of 140 to 170 ° C. When the softening point is less than 100 ° C., not only is the adhesive strength not improved when contained in the pressure-sensitive adhesive, but also the heat-resistant holding power is unfavorably reduced, and when the softening point exceeds 180 ° C., the pressure-sensitive adhesive is Not only deteriorates the compatibility with the base polymer and the like, but also decreases the tackiness (also referred to as "tack") and the curved surface adhesion.
In addition, the softening point in the present invention is a temperature at which a substance softens due to a rise in temperature and starts to deform, and is a value measured by a ring and ball method (JIS K5902).
Among these tackifying resins, known resins can be used without any particular limitation as long as the softening point is in the range of 100 to 180 ° C., but rosin is used because of the compatibility of the base polymer and the development of good adhesion. A resin, a terpene resin, or a petroleum resin is preferable, and among them, a rosin resin is particularly preferable in terms of curved surface adhesion, water resistance, and heat and humidity resistance.

<Copolymer resin (B)>
The copolymer resin (B) contains one or more compounds (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide and diolefin as monomers constituting the copolymer, A copolymer (X) containing at least a dibasic acid having a saturated group or its anhydride (b2-1) is modified with a compound (b3) having an alkylene oxide unit.

<<< one or more compounds (b1) selected from the group consisting of α-olefins, styrene, vinyl ether, vinyl sulfide, and diolefins >>>
Compound (b1) is one or more compounds selected from the group consisting of α-olefins, styrene, vinyl ether, vinyl sulfide, and diolefin.
Specific examples of the α-olefin include 1-butene, isobutene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, diisobutylene, 1-nonene, 1-decene, 1-dodecene, Α-olefins such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, and the like, preferably having a linear or branched alkyl group having 4 to 22 carbon atoms α-olefins, more preferably α-olefins having a straight-chain alkyl group having 6 to 22 carbon atoms. Preferably, it is an α-monoolefin. In addition, the α-olefin referred to in the present specification excludes a diolefin described later.

  Specific examples of styrene include styrene and its derivatives, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α- Methyl styrene, α-methyl-p-methyl styrene, a mixture thereof and the like can be mentioned.

  Specific examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, octadecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, and tetraethylene glycol monovinyl ether. Linear or branched aliphatic alkyl vinyl ethers such as trimethylolpropane monovinyl ether and the like, and mixtures thereof.

  Specific examples of vinyl sulfide include methyl vinyl sulfide, ethyl vinyl sulfide, butyl vinyl sulfide, and the like, and mixtures thereof.

  Specific examples of the diolefin include butadiene, isoprene, neoprene, chloroprene, and the like, and a mixture thereof.

  In addition, the compound (b1) may be used alone or as a mixture of two or more. By selecting two or more compounds (b1), the glass transition temperature (Tg), melting point (Tm) and the like of the copolymer resin (B) can be easily controlled to desired values. In particular, in consideration of the emulsion stability of the copolymer resin (B), it is preferable to use an α-olefin having high lipophilicity.

<< other ethylenically unsaturated compounds (b2) >>
Other ethylenically unsaturated compounds (b2) refer to ethylenically unsaturated compounds other than the compound (b1). Compound (b2) is a dibasic acid having an unsaturated group or its anhydride (b2-1) (compound (b2-1)), and a compound that is another ethylenically unsaturated compound other than compound (b2-1) (B2-2).

  Specific examples of the compound (b2-1) include maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Although two or more kinds may be used as a mixture, maleic anhydride is industrially advantageous.

  The compound (b2-2) is appropriately selected depending on desired physical properties, viscosity control, and the like, and is not particularly limited as long as it can be copolymerized with the compound (b1) and the compound (b2-1). Specific examples of the compound (b2-2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, ( Cetyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxypolyoxyethylene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) ) (Meth) acrylic esters such as 4-hydroxybutyl acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and sulfophenoxyethyl (meth) acrylate;

  Vinyl esters such as vinyl acetate and vinyl propionate; N-substituted vinyl compounds such as N-vinyl pyridine, N-vinyl carbazole, N-vinyl-2-pyrrolidone, N-vinyl phthalimide; (meth) acrylamide, dimethyl (meth) ) Acrylamides such as acrylamide; (meth) acrylonitrile and the like. These may be used alone or as a mixture of two or more.

<< copolymer (X) >>
The copolymer (X) is a copolymer containing at least the compound (b1) and the compound (b2-1) as monomers constituting the copolymer, and further contains a compound (b2- 2) may be included. As the copolymer (X), a commercially available product can also be used. For example, Diacarna 30 (α-olefin / maleic acid copolymer, mass average molecular weight (may be abbreviated as “Mw”) = 9,000, acid value (may be abbreviated as “AV”) = 95 mg KOH / g) [all manufactured by Mitsubishi Chemical Corporation];
SMA1000 (styrene / maleic acid copolymer, Mw = 4,000, AV = 480 mg KOH / g), SMA2000 (styrene / maleic acid copolymer, Mw = 7,000, AV = 360 mg KOH / g), SMA3000 (styrene / maleic acid) Maleic acid copolymer, Mw = 10,000, AV = 290 mg KOH / g), SMAEF80 (styrene / maleic acid copolymer, AV = 120) [all manufactured by Kawahara Yuka Co., Ltd.];
Gantrez AN119 (methyl vinyl ether / maleic acid copolymer, Mw = 200,000, AV = 320 mg KOH / g), Gantrez AN139 (methyl vinyl ether / maleic acid copolymer, Mw = 500,000, AV = 156 mg KOH / g), GANTREZ AN179 (methyl vinyl ether / maleic acid copolymer, Mw = 2,000,000, AV = 95 mg KOH / g) [all manufactured by Ashland Japan Co.];
Ricon 130MA8 (maleic acid-modified polybutadiene, Mw = 2,700, acid value AV = 46 mg KOH / g), Ricon 130MA20 (maleic acid-modified polybutadiene, Mw = 3,000, AV = 120 mg KOH / g), Ricon 131MA17 (maleic acid-modified) (Polybutadiene, Mw = 5,400, AV = 97 mgKOH / g)
[The above is made by CRAY VALLEY].
The “maleic acid-modified polybutadiene” is obtained by modifying polybutadiene with maleic anhydride. In the present specification, polybutadiene obtained by adding two or more maleic anhydrides to one molecule of polybutadiene is also referred to as maleic acid-modified polybutadiene. And is included in the copolymer (X).

<<< compound (b3) having alkylene oxide unit >>>
The compound (b3) having an alkylene oxide unit is a compound having two or more repeating unit ether bonds in the molecule. Here, the alkylene oxide unit represented by the compound (b3) is a repeating unit (also referred to as an addition mole number) of an alkylene oxide (AO, an alkylene oxide unit unit may be abbreviated as “AO”). Indicates 2 or more.
The addition mole number of the alkylene oxide unit (AO) is preferably 2 to 100, more preferably 4 to 80, and still more preferably 4 to 60. When the number of moles of AO added is in the above range, the copolymer resin (B) has flexibility, so that it is possible to improve the curved surface adhesion.

In addition, the compound (b3) having an alkylene oxide unit includes a compound (b3-1) in which the alkylene oxide unit is an ethylene oxide unit and a compound (b3-2) in which the alkylene oxide unit is an alkylene oxide unit other than the ethylene oxide unit. Separated. Further, the compound (b3-1) includes a compound (b3-1-1) having one or more hydroxyl groups in the molecule, a compound (b3-1-2) having one or more amino groups in the molecule, and a compound (b3 -B-1-3) and the compound (b3-1-3) other than the compound (b3-1-2).
When the compound (b3-1) having an ethylene oxide unit has at least one of a hydroxyl group and an amino group in the molecule, the compound (b3-1) contains a carboxyl group or an acid anhydride contained in the copolymer (X). It is possible to obtain the copolymer resin (B) through a modification reaction of the ester group, esterification, amidation or imidation.
Here, the ethylene oxide unit in the compound (b3-1) is a repeating unit (also referred to as an addition mole number) of ethylene oxide (EO, a unit unit of ethylene oxide may be abbreviated as “EO”). Is 2 or more.
By performing the modification reaction as described above, the acid value, molecular weight, viscosity, and softening point of the copolymer resin (B) can be controlled, so that the aqueous dispersion of the tackifier resin (A) can be performed. It will be easier. In addition, the tackifier resin aqueous dispersion containing the copolymer resin (B) also has improved compatibility with the base polymer (P) described below, and the aqueous tackifier containing the approximately tackifier resin aqueous dispersion is: Various physical properties such as good adhesive strength, various resistances, and flexibility can be appropriately controlled.

Examples of the compound (b3-1-1) having an ethylene oxide unit and having at least one or more hydroxyl group in the molecule include an ethylene oxide skeleton such as polyethylene glycol and polyethylene propylene glycol (ethylene oxide / propylene oxide copolymer). And ether-type or ether-ester type nonionic surfactants in addition to polyether polyols having
Specific examples of the ether type nonionic surfactant include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol mono 2-ethylhexyl ether, and tetraethylene glycol monomethyl. Ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol mono 2-ethylhexyl ether, tetraethylene glycol monononyl ether, tetraethylene glycol monododecyl ether, tetraethylene glycol oleyl ether , Tetraethylene glycol steer Ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene Myristyl ether, polyoxyethylene octyl dodecyl ether, polyoxyethylene isodecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene branched decyl ether, polyoxyethylene castor oil ether, polyoxyethylene phenyl ether, polyoxyethylene cumylphenyl Ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene chlorophenyl Alkyl, such as polyester, polyoxyethylene styrenated phenyl ether, polyoxyethylene benzyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonylpropenyl phenyl ether, Or aryl polyoxyethylene ether;

  Specific examples of the ether ester type nonionic surfactant include polyoxyethylene caproate, diethylene glycol enanthate, ethylene glycol caprylate, polyoxyethylene caprylate, diethylene glycol 2-ethylcaproate, and dipropylene 2-ethylcaproate. Glycol, polyoxyethylene laurate, polyoxyethylene myristate, polyoxyethylene stearate, polyoxyethylene oleate, polyoxyethylene linoleate, polyoxyethylene linolenate, polyoxyethylene such as polyoxyalkylene glycol rosinate Fatty acid monoester;

  For example, 2-ethylcaproic acid polyoxyethylene monoglyceride, pelargonic acid monoglyceride, capric acid polyoxyethylene monoglyceride, lauric acid polyoxyethylene monoglyceride, lauric acid polyoxyethylene monoglyceride, myristic acid polyoxyethylene monoglyceride, palmitic acid polyoxyethylene monoglyceride Polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monoglyceride stearate, polyoxyethylene monoglyceride crotonic acid, polyoxyethylene monoglyceride palmitoleate, polyoxyethylene monoglyceride linoleate, polyoxyethylene monoglyceride linolenate, polyoxyethylene monoglyceride oleate, etc. ;

  For example, polypolyoxyethylene trimethylol propane caproate, polyoxyethylene trimethylol propane 2-ethylcaproate, polyoxyethylene trimethylol propane laurate, polyoxyethylene trimethylol propane myristate, polyoxyethylene trimethylol propane stearate, Polyoxyethylene trimethylol propane oleate, polyoxyethylene trimethylol propane linoleate, polyoxyethylene trimethylol propane linolenate, polyoxyethylene trimethylol propane di-2-ethylcaproate, polyoxyethylene trimethylol propane dilaurate, dilaurate Polyoxyethylene trimethylolpropane myristate, polyoxyethylene trimethyloyl distearate Trimethylolpropane dioleate polyoxyethylene trimethylolpropane, dilinoleate polyoxyethylene trimethylol propane, polyoxyethylene fatty acid trimethylol propane, such Jirinoren polyoxyethylene trimethylol propane;

  For example, polyoxyethylene pentaerythritol caproic acid, polyoxyethylene pentaerythritol 2-ethylcaproate, polyoxyethylene pentaerythritol caprate, polyoxyethylene pentaerythritol laurate, polyoxyethylene pentaerythritol myristate, polyoxyethylene palmitate Pentaerythritol, polyoxyethylene pentaerythritol stearate, polyoxyethylene pentaerythritol isostearate, polyoxyethylene pentaerythritol dicaproate, polyoxyethylene pentaerythritol di-2-ethylcaproate, polyoxyethylene pentaerythritol dicaprate, poly dilaurate Oxyethylene pentaerythritol, dimyristate pen Erythritol, polyoxyethylene pentaerythritol dipalmitate, polyoxyethylene pentaerythritol distearate, polyoxyethylene pentaerythritol diisostearate, polyoxyethylene pentaerythritol tricaproate, polyoxyethylene pentaerythritol tri-2-ethylcaproate, poly tricaprate Oxyethylene pentaerythritol, polyoxyethylene pentaerythritol trilaurate, polyoxyethylene pentaerythritol trimyristate, polyoxyethylene pentaerythritol tripalmitate, polyoxyethylene pentaerythritol tristearate, polyoxyethylene pentaerythritol triisostearate, etc. Polyoxyethylene fatty acid Data erythritol;

  For example, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbite di-2-ethylcaproate, dilaurate Polyoxyethylene sorbit, polyoxyethylene sorbit trimyristate, polyoxyethylene sorbit tripalmitate, polyoxyethylene sorbit tristearate, polyoxyethylene sorbit tetraoleate, polyoxyethylene sorbite tetralinoleate, polyoxytetralinolenate And polyoxyethylene sorbitol fatty acid esters such as ethylene sorbit. These can be used alone or in combination of two or more.

  Specific examples of the compound (b3-1-2) having an ethylene oxide unit and having at least one amino group in the molecule include methoxytriethylene glycolamine, methoxytetraethylene glycolamine, methoxypolyethylene glycolamine, Polyoxyethylene meta-xylene diamine, α, ω-bis (3-aminopropyl) diethylene glycol ether, α, ω-bis (3-aminopropyl) polyethylene glycol ether and the like can be mentioned. Commercially available products include Jeffamine M-600, Jeffamine M-1000, Jeffamine M-2005, Jeffamine M-2070, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED2003 (all manufactured by Huntsman) Manufactured). It is not particularly limited to these, and they can be used alone or as a mixture of two or more.

The number of moles of the ethylene oxide unit (EO) contained in the compound (b3-1) having an ethylene oxide unit is preferably 2 to 100, more preferably 4 to 80, and still more preferably 4 to 60. When the number of moles of EO added is in the above range, the copolymer resin (B) is easily emulsified in water, so that the aqueous dispersion of the tackifying resin (A) becomes easy, and the resin is left over time. The separation is also suppressed. Further, it is possible to further maintain water resistance and wet heat resistance.
Thus, among the compounds (b3-1) having an ethylene oxide unit, the compound (b3-1-1) having at least one of a hydroxyl group and an amino group in the molecule and the compound (b3-1-l) 2) is preferred. Further, in the compound (b3-1-1) and the compound (b3-1-2), it is more preferable that each of the compounds has only one hydroxyl group or one amino group. When there is only one hydroxyl group or amino group, the viscosity of the copolymer resin (B) can be reduced, and the viscosity of the tackifier resin aqueous dispersion can be reduced.

  In order to react the compound (b3-1-3) with the copolymer (X) to obtain the copolymer resin (B), the compound (b3-1-3) is contained in the copolymer (X). It preferably has a functional group capable of reacting with a carboxyl group or an acid anhydride group, and examples of such a functional group include an epoxy group, a mercapto group, and an isocyanate group. A compound having an epoxy group is preferably used in terms of stability, odor and the like. Specific examples include triethylene glycol glycidyl ether and tetraethylene glycol glycidyl ether. Commercial products include Denacol EX-171 (lauryl alcohol polyoxyethylene glycidyl ether), denacol EX-850L (diethylene glycol diglycidyl ether), denacol EX-821 (tetraethylene glycol diglycidyl ether), and denacol EX-861 (polyethylene glycol). Diglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether) [all manufactured by Nagae ChemteX Corporation].

Among the compounds (b3) having an alkylene oxide unit, specific examples of the compound (b3-2) include a propylene oxide unit (PO, a unit unit of propylene oxide may be abbreviated as "PO"). Butylene oxide unit (BO, butylene oxide unit may be abbreviated as “BO”), tetraethylene oxide unit (TO, tetraethylene oxide unit may be abbreviated as “TO”). ) And the like.
The compound (b3-2) preferably has a functional group capable of reacting with a carboxyl group or an acid anhydride group contained in the copolymer (X). Examples of such a functional group include a hydroxyl group and an amino group. , An epoxy group, a mercapto group, an isocyanate group and the like. It is preferable that the functional group has a hydroxyl group or an amino group in terms of adhesiveness and curved surface adhesiveness.

  Specific examples of the compound (b3-2) include, for example, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene ether glycol, dipropylene glycol methyl ether, and tripropylene glycol methyl ether Hydroxyl-containing compounds such as, dipropylene glycol propyl ether, tripropylene glycol ethyl ether, polypropylene glycol methyl ether, tripropylene glycol butyl ether, polybutylene glycol ethyl ether, tetramethylene ether glycol methyl ether;

  For example, 1-([1-{(1-methoxypropan-2-yl) oxy} propan-2-yl] oxy) propan-2-amine, 4,7,10-trimethyl-2,5,8,11 -Tetraoxatetradecane-13-amine and the like. Commercially available products include Jeffamine D-400, Jeffamine D-600, and Huntsman. It is not particularly limited to these, and they can be used alone or as a mixture of two or more.

As the compound (b3), a compound (b3-1) that makes the copolymer resin (B) easily emulsified in water is preferable. Thereby, the storage stability and mechanical stability of the aqueous dispersion of the tackifier resin (A) are easily improved.
Further, in the compound (b3-1), from the viewpoint of improving the adhesion to the base material and maintaining water resistance and moist heat resistance under severe environments such as high temperature and high humidity conditions, at least one compound is present in the molecule. (B3-1-1) having a hydroxyl group and a compound (b3-1-2) having at least one amino group in the molecule are preferable, and at least one compound in the molecule is particularly preferable in terms of curved surface adhesion. The compound (b3-1-1) having the above hydroxyl group is more preferable.
Among the compounds (b3-1-1), the alkyl or aryl polyoxyethylene ethers represented by the above ether type nonionic surfactants are preferable, and the alkyl or aryl group preferably has 16 or less carbon atoms. When the number of carbon atoms of the alkyl or aryl group is 16 or less, the emulsion stability of the copolymer resin (B) is good, and the storage stability and mechanical stability of the aqueous tackifier resin dispersion are good. Become.

<<< compound (b4) having no alkylene oxide unit >>>
The compound (b4) having no alkylene oxide unit is appropriately selected as necessary in view of adhesive properties, adhesion properties, adhesive heat properties such as wet heat resistance, and emulsion stability, and is included in the copolymer (X). If it has a functional group which can react with a carboxyl group or an acid anhydride group, it can be used in combination with compound (b3) and used without any particular problem.
Like the compound (b3), the compound (b4) needs to have a functional group capable of reacting with a carboxyl group or an acid anhydride group contained in the copolymer (X), and has a hydroxyl group, an amino group, An epoxy group, a mercapto group, an isocyanate group, and the like are mentioned, and are appropriately selected according to desired physical properties, viscosity control, and the like, and are used in combination with the compound (b3). The functional group preferably has at least one hydroxyl group or amino group in the molecule.

  Specific examples of the compound having at least one hydroxyl group in the molecule include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2- Ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, α-oxybutyric acid, 12-hydroxystearic acid and the like and mixtures thereof are used. It is not particularly limited to these.

  Further, specific examples of the compound having one or more amino groups in the molecule are not particularly limited as long as the compound has an amino group of, for example, methylamine, ethylamine, propylamine, isopropylamine, Butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o-toluidine, 2-ethylaniline, 2-fluoroaniline, o-anisidine , M-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindane, aspartic acid, glutamic acid, γ-aminobutyric acid and the like, and mixtures thereof. Limit Not intended to be.

  The copolymer resin (B) can be produced, for example, by the following method. For example, a step (first step) of polymerizing a monomer mixture containing the compound (b1) and the compound (b2-1) and, if necessary, the compound (b2-2) to obtain a copolymer (X), The compound (b3) is reacted with the obtained copolymer (X) and, if necessary, the compound (b4) to obtain a copolymer resin (B) (a second step).

  First, the first step will be described. In the first step, the copolymer (X) obtained by polymerizing a monomer mixture containing the compound (b1), the compound (b2-1), and the compound (b2-2) has a weight average molecular weight (hereinafter, referred to as “ Mw ”may be in the range of 1,000 to 500,000, and the acid value (hereinafter may be abbreviated as“ AV ”) is in the range of 100 to 700. Is preferred. It is preferable that the mass average molecular weight (Mw) and the acid value (AV) are in the above ranges from the viewpoint of the modification reaction in the second step and the stable emulsification of the copolymer resin (B). The details of the mass average molecular weight (Mw) and the acid value (AV) will be described in Examples.

  Examples of the polymerization method for obtaining the copolymer (X) include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, high-pressure polymerization and the like, but those not particularly limited in these polymerization methods and reaction operations. However, bulk polymerization and high pressure polymerization are preferred. In the case of bulk polymerization, since a solvent is not used at all, a high polymerization reaction rate can be expected, and it is possible to avoid the incorporation of excessive additives which greatly affect the physical properties. In the case of high-pressure polymerization, although a pressure vessel is required, a high polymerization reaction rate is possible even with a reaction liquid having a remarkably high viscosity. In addition, the molecular weight and viscosity can be controlled by the reaction temperature or the amount of the polymerization initiator in the bulk polymerization method, and by the reaction temperature and the degree of pressure in the high-pressure polymerization method.

  When compound (b2-2) is used at the time of polymerization, the compounding ratio of compound (b1), compound (b2-1) and compound (b2-2) is 100 parts by mass of compound (b2-1) and compound (b2-1). The total amount of b1) and the compound (b2-2) is preferably from 40 to 300 parts by mass, more preferably from 50 to 200 parts by mass. According to a conventional method, the copolymer (X) is used in an amount of 0 based on a total of 100 parts by mass of the monomer mixture of the compound (b1) and the compound (b2-1), and if necessary, the compound (b2-2). It is synthesized using 0.001 to 20 parts by mass of a polymerization initiator.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 , 2'-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) Dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (1-acetoxy-1-phenylethane), 4,4'-azobis (4-cyanovaleric acid), 2,2'- Examples include azo compounds such as azobis (2-hydroxymethylpropionitrile) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane].

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-t-butyl peroxide, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydioxide Carbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide and dipropionyl peroxide And organic peroxides such as diacetyl peroxide.

  In addition, at the time of synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  Among these, from the viewpoint of controlling the molecular weight and controlling the molecular weight distribution, as the polymerization initiator, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 2,2 ′ 2'-azobisisobutyrate and dibenzoyldioxidane, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexylperoxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butylperoxy -2-ethylhexanoate and di-t-butyl peroxide are preferred.

  Compound (b1), compound (b2-1) or (b2-2) may remain in the copolymer (X) recovered by polymerization depending on the selected monomers and reaction conditions. As a method of removing these monomer components, for example, after the polymerization reaction, there is a method of removing by deaeration immediately under reduced pressure, and a method of washing the recovered copolymer using an appropriate organic solvent, It is preferable to perform degassing under reduced pressure without using an organic solvent. By degassing under reduced pressure, the organic solvent remaining in the raw material can be removed.

  Next, the second step will be described. In the second step, the copolymer (X) is mixed with the compound (b3) and, if necessary, the compound (b4) to form a carboxyl group derived from the compound (2-1) in the copolymer (X). And reacting with a compound having at least one or more hydroxyl groups in the molecule. In this step, the copolymer (X) is modified by a reaction such as addition, substitution, or condensation of the compound (b3) or the compound (b4) to obtain a copolymer resin (B).

  In the modification reaction for obtaining the copolymer resin (B), the reaction usually proceeds in the absence of a catalyst. However, a catalyst can be used as appropriate to make the reaction proceed more smoothly. Examples of the catalyst used include quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, sodium, potassium, calcium, tin, lead, titanium, iron, zinc, zirconium, and cobalt. Contained organometallic compounds, metal halides and the like.

In the second step, the mass ratio of the copolymer (X), the compound (b3), and the compound (b4) is determined by the following formula: the copolymer (X) / the total amount of the compound (b3) and the compound (b4) = 1/99 to 70/30 is preferable, and 5/95 to 50/50 is more preferable. Further, among 100 parts of the copolymer resin (B), the content of the compound (b3) is preferably in a range of at least 20 to 80 parts, more preferably 15 to 70 parts.
When the mass ratio of the total amount of the copolymer (X), the compound (b3) and the compound (b4), and the content of the compound (b3) are within the above ranges, the acid value of the copolymer resin (B) AV), mass average molecular weight (Mw), softening point (Tc), strength, various resistances, flexibility, compatibility, emulsification, and other physical properties can be appropriately controlled.

  The weight average molecular weight (Mw) of the copolymer resin (B) is preferably in the range of 1,000 to 500,000, and more preferably in the range of 2,000 to 300,000. Further, the acid value (AV) of the copolymer resin (B) is preferably in the range of 10 to 300, and more preferably in the range of 40 to 200. When the weight average molecular weight (Mw) and the acid value (AV) are within the above ranges, the viscosity of the tackifier resin aqueous dispersion is low and the emulsifiability is good, so that the particle diameter of the tackifier resin is 0.01 to 10 μm. It becomes easy to control in the range of.

  The aqueous tackifier resin dispersion of the present invention preferably contains the copolymer resin (B) in an amount of 0.5 to 50 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the tackifier resin (A). It is more preferable to include a part. When the copolymer resin (B) is within this range, the viscosity of the resulting tackifier resin aqueous dispersion is reduced, and the workability is significantly improved, and a stable aqueous dispersion can be obtained. Storage stability is improved. In addition, even when a water-based pressure-sensitive adhesive is contained in a base polymer described below, a stable water-based pressure-sensitive adhesive can be obtained without separation, thickening, or thinning when left over time. The pressure-sensitive adhesive sheet obtained after application and drying of the water-based pressure-sensitive adhesive exhibits good adhesiveness, and can improve curved surface adhesiveness and heat-resistant holding power.

<Liquid resin (C) having a number average molecular weight of 300 to 50,000>
Next, the liquid resin (C) having a number average molecular weight of 300 to 50,000 will be described.
In one embodiment of the aqueous tackifier resin dispersion of the present invention, the tackifier aqueous resin dispersion further has a number average molecular weight (hereinafter may be abbreviated as “Mn”) of 300 to 300 in addition to the above essential components. 50,000 liquid resin (C) (hereinafter, referred to as liquid resin (C)). The liquid resin is a resin that is liquid or paste at 25 ° C. However, the tackifying resin (A) and the copolymer resin (B) are not included.
The number average molecular weight (Mn) of the liquid resin (C) is 300 to 50,000, preferably 500 to 10,000. When the number average molecular weight (Mn) is in this range, the adsorbability to the tackifying resin (A) is increased, so that the dispersibility is improved, and the heat resistance can be maintained.
The liquid resin (C) is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the copolymer (A). When the liquid resin (C) is in this range, the dispersibility of the tackifier resin (A) is improved, and not only can the particle diameter be controlled with high accuracy, but also the tackifier resin aqueous dispersion, The storage stability of the aqueous pressure-sensitive adhesive containing the applied resin aqueous dispersion and the water resistance of the pressure-sensitive adhesive layer formed from the aqueous pressure-sensitive adhesive can be compatible.

Specific examples of such a liquid resin (C) include olefin polymers, cyclic olefins, polyols and liquid rosin esters, but from the viewpoint of compatibility, particularly unsaturated hydrocarbons having 4 to 5 carbon atoms. An olefin polymer, a cyclic olefin, or a liquid rosin ester obtained by polymerizing is preferred. Examples of the unsaturated hydrocarbon having 4 to 5 carbon atoms include 1-butene, isobutene, 2-butene, butadiene, 1-pentene, 2-pentene, isopentene, isoprene and the like. The polymerization may be performed by a known method, and radical polymerization, cationic polymerization, or the like can be employed.
As the liquid resin (C), a commercially available product can be used. As the olefin polymer, for example, NISSO-PB B-1000 (Mn = 1,200) NISSO-PB G-1000 (Mn = 1,400, Hydroxyl value: 68-78 mgKOH / g), NISSO-PB BI-2000 (Mn = 2,200), NISSO-PB GI-2000 (Mn = 1,500, hydroxyl value = 60-75 mgKOH / g) [More than Japan Soda Corporation];
LBR-302 (Mn = 5,500), LBR-361 (Mn = 5,500), L-SBR-820 (Mn = 8,500) [all manufactured by Kuraray Co.];
Nisseki polybutene LV-7 (Mn = 300), Nisseki polybutene LV-50 (Mn = 430), Nisseki polybutene LV-100 (Mn = 500), Nisseki polybutene HV-15 (Mn = 630), Nisseki Polybutene HV-35 (Mn = 750), Nisseki Polybutene HV-50 (Mn = 800) [all manufactured by JXTG Energy];
NOF polybutene 0N (Mn = 370), NOF polybutene 015N (Mn = 580), NOF polybutene 3N (Mn = 720), NOF polybutene 10N (Mn = 1,000) [manufactured by NOF CORPORATION];
RT2730 (Mn = 1,000) and RT2304 (Mn = 800) [all manufactured by HUNSTMAN].

Examples of the liquid rosin ester include superester L (Mn = 650, liquid rosin ester), superester A-18 (Mn = 700, liquid rosin ester), and KE-364C (Mn = 221, liquid modified rosin ester) [ Above, liquid rosin manufactured by Arakawa Chemical Industry Co., Ltd.];
Banbeam UV-22C (Mn = 3,800, rosin-modified epoxy acrylate) and Banbeam UV-500 (Mn = 4,200, rosin-modified epoxy acrylate) [the above is a liquid rosin manufactured by Harima Chemicals, Inc.].

  Examples of the cyclic olefin include PRIPOL2033 (Mn = 540, dimer diol) and PRIPOL1006 (Mn = 600, dimer acid) [all manufactured by CRODA Coatings & Polymers].

  Examples of the polyol include a polyether polyol, a polyester polyol, a polycarbonate polyol, a copolymer thereof, and other glycols.

<Surfactant (D)>
Next, the surfactant (D) will be described.
In one embodiment of the aqueous tackifier resin dispersion of the present invention, the aqueous tackifier resin dispersion may further contain a surfactant (D) in addition to the above essential components.
When the above-mentioned tackifier resin (A) is made into an aqueous dispersion, it is possible to contain a surfactant (D) from the viewpoint of emulsion stability.
The surfactant (D) is not particularly limited, and various known surfactants such as anionic, nonionic, cationic, and amphoteric can be used. Anionic surfactant or nonionic surfactant alone or It is preferable to contain them in combination. The content is 1 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the tackifying resin (A). When the surfactant (D) is contained within the above range, it is possible to ensure the storage stability of the aqueous dispersion without impairing the water resistance and wet heat resistance of the adhesive layer.

  Examples of the anionic surfactant include organic sulfonic acids, alkali metal salts of sulfuric acid esters, and ammonium salts. Specific examples thereof include alkyl aryl sulfonate, alkyl (or alkenyl) sulfate, and polyoxyethylene. Alkyl (or alkenyl) ether sulfates, polyoxyethylene alkyl aryl ether sulfates, alkyl sulfosuccinates, alkyl diaryl ether disulfonic acids, and derivatives thereof.

  As the nonionic surfactant, in addition to the above-mentioned compound (b2-4-1) having at least one hydroxyl group in the molecule, which is an ether type or ether ester type nonionic surfactant, fatty acid monoglyceride Ester nonionic surfactants such as fatty acid diglyceride, fatty acid triglyceride, fatty acid trimethylolpropane, fatty acid pentaerythritol, sorbitan fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, lauric acid diethanolamide, polyoxyethylene alkyl Examples include nitrogen-containing nonionic surfactants such as amine monostearate and polyoxyethylene stearamide. These can be used alone or in combination of two or more.

<Basic compound (E)>
Next, the basic compound (E) will be described.
In one embodiment of the aqueous tackifier resin dispersion of the present invention, the aqueous tackifier resin dispersion may further contain a basic compound (E) in addition to the above essential components.
The carboxyl groups in the tackifying resin (A) or the copolymer resin (B) are partially or entirely neutralized by the basic compound (E), and the fine particles are formed by the electric repulsion between the generated carboxyl anions. Agglomeration between them is prevented, and stability is imparted to the aqueous dispersion.

The basic compound (E) may be used to neutralize the tackifier resin (A) or the copolymer resin (B) in advance to prepare an aqueous dispersion of the tackifier resin, or the tackifier resin (A) And the copolymer resin (B) may be blended when they are mixed, or both may be used in combination.
Although it does not specifically limit as a basic compound (E), An inorganic salt, ammonia, an organic base, etc. are mentioned. Among the organic bases, an organic amine compound having a boiling point of 300 ° C. or less is preferable from the viewpoint of water resistance and wet heat resistance of the coating film. When the boiling point is 300 ° C. or lower, the resin film can be easily removed by drying, and the coating film has good water / moisture / heat resistance, and good adhesion and adhesion to a substrate.
Specific examples of the organic amine compound include triethylamine, tributylamine, N, N-dimethylethanolamine, aminoethanol, N-methyl-N, N-diethanolamine, N, N-dimethylbenzylamine, isopropylamine, iminobispropylamine , Ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, dibutylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N -Ethylmorpholine, diazabicycloundecene and the like.

  Of these organic amine compounds, tertiary amines (e1), which have good scattering properties and do not easily remain in the coating film and are non-reactive with the copolymer resin (B), are particularly preferred, and are commercially available. Particularly preferred are triethylamine, tributylamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, diazabicycloundecene and the like. Basic compounds other than the tertiary amine (e1) are referred to as basic substances (e2).

  The content of the basic compound (E) may be 0.5 to 20.0 times equivalent to the total amount of carboxyl groups contained in the tackifier resin (A) and the copolymer resin (B). Preferably, 1.0 to 10.0 equivalents are more preferable. When the content of the basic compound (E) is in the above range, the drying time at the time of forming the coating film is short, and the stability of the aqueous dispersion can be improved.

<Other compounds (F)>
Next, the other compound (F) will be described.
In one embodiment of the aqueous tackifier resin dispersion of the present invention, the tackifier aqueous resin dispersion may further contain, in addition to the above essential components, other compounds (F) as long as the problem can be solved.
Other compounds (F) include the above tackifier resin (A), copolymer resin (B), liquid resin (C), surfactant (D), surfactant (D), basic compound (E), It is a compound other than the base polymer (P) and has a function of improving the stability and physical properties of the material by adding a small amount of a component. For example, curing agents, thickeners, plasticizers, preservatives, rust inhibitors, freeze-thaw stabilizers, pigments, colorants, fillers, wetting agents, antioxidants, flame retardants, storage stabilizers, ultraviolet absorption Agents, thixotropy-imparting agents, dispersion stabilizers, fluidity-imparting agents, film-forming auxiliaries, humectants, pH adjusters, leveling agents, hydrolysis inhibitors, defoamers and the like.
The other compound (F) can be further added to an aqueous pressure-sensitive adhesive described later.

<Tackifying resin aqueous dispersion>
Next, the tackifier resin aqueous dispersion will be described.
As described above, the tackifier resin aqueous dispersion of the present invention comprises a copolymer resin (B) and, if necessary, a surfactant (D), a surfactant (D), a basic compound (E) and other components. It is obtained by emulsifying the tackifier resin (A) while allowing the compound (F) to coexist.
Further, the tackifier resin aqueous dispersion preferably does not contain an organic solvent, even if it is contained due to residual organic solvent derived from raw materials, the content is preferably 1,000 ppm or less, more preferably 500 ppm or less. It is preferably at most 100 ppm.
The emulsification method is not particularly limited, and any of known emulsification methods, such as a high-pressure emulsification method, an inverse emulsification method, an ultrasonic emulsification method, and a solvent emulsification method, may be employed. In consideration of environmental issues in addition to the reduction of the amount of the solvent, it is preferable to employ a solventless inversion emulsification method that does not use an organic solvent. In the case of the solventless inversion emulsification method, the tackifier resin (A) is melted at a softening point or higher using various emulsifiers such as various mixers, colloid mills, high-pressure emulsifiers, and high-pressure discharge emulsifiers. Under pressure or pressure, the copolymer resin (B) and, if necessary, a surfactant (D), a surfactant (D), a basic compound (E) and another compound (F) are premixed. By adding water and inverting the phase, an aqueous dispersion can be obtained.

  The non-volatile content of the aqueous dispersion of tackifier resin thus obtained is not particularly limited, but is usually adjusted appropriately and used so as to be about 20 to 70%. The average particle diameter of the obtained aqueous dispersion of tackifying resin is usually about 0.1 to 2 μm, and most of the particles are uniformly dispersed as particles of 1 μm or less. The aqueous dispersion has a white or milky white appearance, a pH value of about 5 to 11, and a viscosity of usually about 10 to 2,000 mPa · s.

<Aqueous adhesive>
The aqueous pressure-sensitive adhesive of the present invention contains the base polymer (P) and the above-mentioned aqueous dispersion of the tackifying resin.

<<< base polymer (P) >>
The base polymer (P) used in the present invention has a glass transition temperature (Tg) of −70 to 0 ° C., exhibits a tack (adhesion) at 25 ° C., and is mainly made of a resin aqueous solution used as a main component of an aqueous adhesive. It is a dispersion. The base polymer (P) is preferably at least one selected from the group consisting of an aqueous acrylic dispersion, an aqueous rubber dispersion, and an aqueous synthetic resin dispersion. One base polymer may be used alone, or two or more base polymers may be used in combination.
As the acrylic aqueous dispersion, those generally used for various acrylic pressure-sensitive adhesives and the like can be used. For example, an aqueous dispersion manufactured by polymerizing (meth) acrylic acid ester can be used. Can be.
As the rubber-based aqueous dispersion, various known ones used for an aqueous pressure-sensitive adhesive can be used. For example, natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex and the like can be mentioned.
Further, the synthetic resin-based aqueous dispersion is a synthetic resin-based emulsion excluding the acrylic aqueous dispersion, and various known ones used for water-based pressure-sensitive adhesives can be used. Examples thereof include synthetic resin-based aqueous dispersions such as vinyl acetate-based aqueous dispersion, ethylene-vinyl acetate copolymer-based aqueous dispersion, and urethane-based aqueous dispersion.

  The acrylic aqueous dispersion is synthesized according to a standard method using 0.001 to 20 parts by mass of a polymerization initiator based on 100 parts by mass of the total amount of the monomer mixture. For example, azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride and 2,2′-azobis (2-amidinopropane) dihydrochloride, and persulfates such as potassium persulfate and ammonium persulfate; Peroxides such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide can be used. Also, a redox initiator composed of a combination of a persulfate and sodium bisulfite or a combination of a peroxide and sodium ascorbate can be used. Usually, a predetermined amount of these polymerization initiators may be added at each stage of the emulsion polymerization so that the polymerization reaction is carried out.

  In the aqueous pressure-sensitive adhesive of the present invention, the combination ratio of the base polymer (P) and the tackifier resin aqueous dispersion is not particularly limited, but the effect of modification by the tackifier resin aqueous dispersion can be sufficiently exhibited, and An appropriate use range that does not cause a decrease in heat resistance, tackiness, and the like due to excessive use is, based on 100 parts by mass (in terms of nonvolatile components) of the base polymer (P), usually 1 to 100 parts by mass of the tackifier resin aqueous dispersion. Parts (in terms of nonvolatile content).

  It is preferable that the viscosity of the aqueous pressure-sensitive adhesive of the present invention is appropriately adjusted according to the use form. The water-based pressure-sensitive adhesive of the present invention may additionally use water, if necessary, to adjust the viscosity. Further, the viscosity can be reduced by heating the aqueous pressure-sensitive adhesive without using additional moisture.

When forming a pressure-sensitive adhesive layer using the aqueous pressure-sensitive adhesive of the present invention, the thickness of the pressure-sensitive adhesive layer is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the film thickness is in the above range, a sufficient adhesive strength can be obtained.
Accordingly, from the viewpoint of coating film formation, the viscosity of the aqueous pressure-sensitive adhesive is preferably in the range of 500 to 10,000 mPa · s when measured with a B-type viscometer at 25 ° C. More preferably, the range is 8,000 mPa · s. When the viscosity is 10,000 mPa · s or less, a thin film having a thickness of 0.5 to 100 μm can be easily formed on the substrate by coating, and it is also easy to enhance the tacky physical properties such as tack, adhesive strength and holding power. It is. On the other hand, when the viscosity is 500 mPa · s or more, it is easy to control the thickness of the pressure-sensitive adhesive layer formed from the aqueous pressure-sensitive adhesive. In the present embodiment, the thickness, viscosity, or nonvolatile content of the pressure-sensitive adhesive layer is set according to the use of the laminate.

  The viscous pressure-sensitive adhesive of the present invention may further contain the above-mentioned other compound (F) in addition to the above-mentioned essential components as long as the problem can be solved.

<Adhesive sheet>
Next, the pressure-sensitive adhesive sheet will be described.
The pressure-sensitive adhesive sheet (also referred to as a pressure-sensitive adhesive film) of the present application is obtained by forming a pressure-sensitive adhesive layer composed of the above-described water-based pressure-sensitive adhesive on a substrate described later, and a sheet-shaped substrate having a surface subjected to a release treatment (also referred to as a release liner). ) May be stacked.
When manufacturing the pressure-sensitive adhesive sheet, in an appropriate manner according to a conventional method, after applying an aqueous pressure-sensitive adhesive to a substrate described below, water is removed by a method such as heating, and a pressure-sensitive adhesive layer is formed on the substrate. Can be formed. For example, there is a method in which an aqueous pressure-sensitive adhesive is applied to a release-treated surface of a release liner, dried, and a base material is attached to the release liner.

  The method for applying the aqueous pressure-sensitive adhesive is not particularly limited. For example, various known methods such as a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, kiss coater, lip coater, comma coater, blade coater, knife coater, reverse coater, spin coater, dip coater, etc. Can be applied. Further, the form of thin film coating or thick film coating can be selected without any particular limitation according to the application.

  The basic lamination structure of the pressure-sensitive adhesive sheet is a single-sided pressure-sensitive adhesive sheet such as a substrate / pressure-sensitive adhesive layer / release liner, or a double-sided pressure-sensitive adhesive sheet such as a release liner / pressure-sensitive adhesive layer / substrate / pressure-sensitive adhesive layer / release liner. . The laminate thus laminated on the release liner is called an adhesive sheet. During use, the release liner is peeled off, and the pressure-sensitive adhesive layer is adhered to the adherend. The water-based pressure-sensitive adhesive is not only an adhesive layer having the adhesive property at the moment when the pressure-sensitive adhesive layer touches the adherend at the time of application, but also an adhesive other than the adhesive (hereinafter simply referred to as an adhesive). On the other hand, it is necessary to have a cohesive force for maintaining the adhered state while maintaining the adhered state without completely solidifying even during the adherence and having a tack and moderate hardness. The cohesion greatly depends on the molecular weight and the crosslink density. The laminate thus laminated in the configuration of the base material / adhesive layer / adherend is referred to as an adhesive laminate.

  The pressure-sensitive adhesive sheet using the water-based pressure-sensitive adhesive of the present invention is used for a wide range of applications such as various known pressure-sensitive adhesive products (labels, seals, tapes, stickers, etc.). One of the materials forms a pressure-sensitive adhesive layer in which a base material of the pressure-sensitive adhesive sheet and a substrate (hereinafter referred to as an adherend) to which the other of the substrates are bonded are bonded. The water-based pressure-sensitive adhesive of the present invention is generally used for building materials used for bonding materials such as concrete, cement mortar, various metals, leather, glass, PVC sheets, decorative paper, plywood panels, gypsum boards, ceilings, etc. It is used for automotive interior parts such as materials, decorative parts, door rims, seats, instrument panels, dash silencers, center consoles, pillar trims, rear parcels, etc., and wire coating materials such as binding tape for wires. Among these, it is particularly preferable to use those used for a poorly adherent substrate.

Non-adhesive substrates include foam substrates having pores such as polyolefin foams, soft polyethers, soft polyesters, rigid polyethers, rigid polyester polyurethane foams, and vinyl chloride foams;
Polyethylene, polypropylene, poly-1-butene, polyisobutylene, ethylene-propylene copolymer, propylene-1-butene copolymer or block copolymer, ethylene-propylene-diene terpolymer, polymethylpentene, cyclo Olefin-based resin base materials such as a copolymer of pentadiene and ethylene and / or propylene;
Plastic resin substrates such as PET (polyethylene phthalate resin), PBT (polybutylene terephthalate resin), PVC (vinyl chloride resin), nylon, PC (polycarbonate resin), polyarylate resin, and PPS (polyphenylene sulfide resin). Can be The tackifier resin aqueous dispersion contained in the aqueous pressure-sensitive adhesive of the present invention exhibits excellent adhesion to a poorly adherent substrate.

  As described above, examples of the release liner include those obtained by subjecting the surface of a sheet-like substrate such as cellophane, various plastic sheets, paper, and metal foil to a release treatment. Further, as the sheet-shaped substrate, a single-layered substrate or a multi-layered substrate formed by laminating a plurality of substrates can be used.

  Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.

<Synthesis of copolymer (X)>
(Synthesis example 1)
The following monomers and polymerization initiators were charged at the following ratios into a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a nitrogen inlet tube.

[Polymerization tank]
1-decene (b1) 58.66 parts Di-t-butyl peroxide (polymerization initiator) 0.084 parts
[Drip device]
Maleic anhydride (b2-1) 41.34 parts

  After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 150 ° C. while stirring under a nitrogen atmosphere, and 12.3 parts of the above maleic anhydride was added every 2 minutes from the dropping device, and di-t- was added. 0.252 parts of butyl peroxide (polymerization initiator) were added three times, 0.084 parts every 20 minutes. After completion of the addition, the temperature was maintained at 180 ° C., and the reaction was continued. Further, after 1 hour and 3 hours, 0.169 g of t-butyl peroxide was post-added, respectively, and reacted for 3 hours. Thereafter, while maintaining the reaction temperature at 200 ° C., unreacted monomers were removed under a reduced pressure of 5 torr (1666.6 Pa) for 4 hours to terminate the reaction. The contents were taken out while hot and cooled and solidified. The weight average molecular weight (Mw) and the acid value (AV) of the obtained copolymer (X) were determined. Table 1 shows the results.

(Synthesis Examples 2 to 11)
Copolymer (X) was synthesized in the same manner as in Synthesis Example 1 except that the materials and the formulations shown in Table 1 were changed. In the example using the compound (b2-2), the compound (b2-2) was charged into a dropping device and synthesized. Among these, the copolymers obtained in Synthesis Examples 1 to 6 and 8 to 11 are copolymers (X), and the copolymers obtained in Synthesis Example 7 are not copolymers (X). It is a copolymer. The appearance of the obtained copolymer, the weight average molecular weight (Mw) of the copolymer, and the acid value (AV) of the copolymer were determined in accordance with the method described later, and the results are shown in Table 1. The numerical values of the compounds used as monomers described in Table 1 represent the amount charged to the polymerization tank and the amount (parts) charged to the dropping device.

(Synthesis Example 12)
The following monomers and polymerization initiators were charged at the following ratios into a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a nitrogen inlet tube.

[Polymerization tank]
Butyl acrylate (b2-2) 40.00 parts Acrylic acid (b2-1) 19.41 parts Di-tert-butyl peroxide (polymerization initiator) 0.5 parts Isopropyl alcohol (organic solvent) 10.5 parts
[Drip device]
Butyl acrylate (b2-2) 40.59 parts Di-t-butyl peroxide (polymerization initiator) 0.4 parts Isopropyl alcohol (organic solvent) 4.5 parts

  After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 80 ° C. while stirring under a nitrogen atmosphere to start polymerization. A mixture containing the compound, the polymerization initiator and the organic solvent was added dropwise over 2 hours from a dropping device at the reflux temperature. With further stirring, 0.05 parts of the polymerization initiator was added twice every 1 hour after the completion of dropping, and the mixture was aged for 6 hours, and the reaction was continued. Thereafter, 18.33 parts of isopropyl alcohol was added and the mixture was cooled to 25 ° C. to obtain a copolymer solution other than the copolymer (X). This solution was colorless and transparent, had a nonvolatile content concentration (NV) of 75.1%, a solution viscosity (Vis) of 8,500 mPa · s (25 ° C.), and had a copolymer having an acid value (AV) of 206 mg KOH / g, The weight average molecular weight (Mw) was 19,800.

(Synthesis Example 13)
The materials described in Table 1 were charged with 22.67 parts of acrylic acid (b2-1), 19.41 parts of butyl acrylate (b2-2), an organic solvent and a polymerization initiator in a polymerization tank, and lauroxypolyethylene methacrylate was charged. Glycol (b2-2), 21.58 parts of acrylic acid (b2-1), an organic solvent and a polymerization initiator were charged into a dropping device, and a copolymer other than the copolymer (X) was prepared in the same manner as in Synthesis Example 12. Was synthesized. The solution appearance, non-volatile content (NV), solution viscosity (Vis), copolymer acid value (AV), and weight average molecular weight (Mw) of the obtained copolymer solution were determined by the methods described below. And the results are shown in Table 1. The numerical values of the compounds used as monomers described in Table 1 represent the amount charged to the polymerization tank and the amount (parts) charged to the dropping device.

<Synthesis of copolymer resin (B)>
(Synthesis Example 51)
The following materials were charged in the following ratios into a reaction tank and a dropping device of a reaction device equipped with a reaction tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube.

[Reaction tank]
36.64 parts of the copolymer (X) obtained in Synthesis Example 1 63.36 parts of triethylene glycol monomethyl ether (b3-1-1)
[Drip device]
33.3 parts of triethylamine (e1)

  After replacing the air in the reaction tank with nitrogen gas, the mixture was melted in a nitrogen stream with stirring, and a dehydration reaction was performed at a reaction temperature of 100 ° C. for 4 hours. Thereafter, the temperature was lowered to 80 ° C., and 20 parts of triethylamine (e1) was dropped from the dropping apparatus over 0.5 hours, and the reaction was continued for another hour after the completion of the dropping. Thereafter, 8.3 parts of triethylamine (e1) was added, and the mixture was cooled to 25 ° C. to obtain an amine solution of the copolymer resin (B). The solution appearance, nonvolatile content (NV), solution viscosity (Vis), and mass average molecular weight (Mw) of the obtained copolymer resin (B) were determined. Table 2 shows the results.

(Synthesis examples 52 to 80)
A copolymer resin (B) was synthesized in the same manner as in Synthesis Example 51, except that the materials and formulations shown in Table 2 were changed. The copolymer (X), the compound (b3), and the compound (b2-4) were charged in a reaction vessel, and the basic compound (E) was charged in a dropping device to synthesize. Among these, the copolymer resins obtained in Synthesis Examples 51 to 54, 57 to 69 and 71 to 80 are the copolymer resins (B), and the copolymers obtained in Synthesis Examples 55, 56 and 70 The resin is a copolymer resin (for a comparative example) other than the copolymer resin (B).
The solution appearance, non-volatile content (NV), solution viscosity (Vis), and mass average molecular weight (Mw) of the obtained copolymer resin were determined according to the methods described below. The results are shown in Table 2. In addition, the numerical value described in Table 2 is the total amount (part) of the charged amount to the reaction tank and the charged amount to the dropping device, and a blank column indicates that it is not used.

<Production of tackifier resin aqueous dispersion>
(Production Example 1)
The following tackifier resin (A), copolymer resin (B), Ion-exchanged water and, if necessary, a surfactant (D), a surfactant (D), and a basic compound (E) were charged at the following ratios.

[Stirred tank]
D-160 (A) 100 parts Copolymer resin (B) obtained in Synthesis Example 51 20 parts
[Drip device 1]
20 parts of triethylamine (e1)
[Drip device 2]
80 parts of ion exchange water

After replacing the air in the stirring tank with nitrogen gas, the temperature was raised to 180 ° C. in a nitrogen stream with stirring, and the mixture was heated and melted for 1 hour. Thereafter, the reaction temperature was cooled to 120 ° C., and then triethylamine (e1) was dropped from the dropping device 1 in 0.5 hours. Further, the system was vigorously stirred while maintaining the system at 100 ° C., and ion-exchanged water was dropped from the dropping device 2 over 2 hours, and the phase was inverted to obtain an aqueous dispersion. Further, 10 parts of ion-exchanged water was added, the mixture was cooled to 25 ° C., and filtered with a 180-mesh furnace cloth to obtain a tackifier resin aqueous dispersion having a nonvolatile content of 50%. At this time, filterability, pot stainability, storage stability, and mechanical stability as productivity were evaluated according to the methods described below, and the results are shown in Table 3.
The nonvolatile content (NV), solution viscosity (Vis), average particle size (Dm), and hydrogen ion index (pH) of the obtained tackifier resin aqueous dispersion were determined in accordance with the method described later. It was shown to.

(Production Examples 2 to 80)
Except that the types and amounts of the tackifying resin (A), the copolymer resin (B) and other materials were changed according to Table 3 as needed, the same procedures as in Production Example 1 were carried out, and Production Examples 2 to 2, respectively. 75 aqueous tackifier resin dispersions were prepared. The liquid resin (C) was placed in a stirring tank, the basic compound (E) was placed in a dropping device 1, and ion-exchanged water and, if necessary, a surfactant (D) were placed in a dropping device 2. . The other compound (F) was added and mixed after cooling to 25 ° C.
In Production Examples 76 to 80, the copolymer (X) (Production Examples 76 to 78), the liquid resin (C) (Production Example 79), and the surfactant were used without using the copolymer resin (B). (D) (Production Example 80) was used.
The numerical values shown in Table 3 represent "parts" unless otherwise specified, and blank columns indicate that they are not used.
Among these, the aqueous dispersions obtained in Production Examples 1-4, 7-15, 18-29, 32-37, 42-57, 59-63 and 66-75 are the tackifier resin aqueous dispersions of the present invention. The aqueous dispersions obtained in Production Examples 5, 6, 16, 17, 30, 31, 38 to 41, 58, 64, 65, 73, and 76 to 80 are the tackifier resin aqueous dispersions of the present invention. There is no aqueous dispersion. The nonvolatile concentration (NV), solution viscosity (Vis), average particle size (Dm), hydrogen ion exponent (pH), and organic solvent content of the obtained aqueous dispersion were determined according to the methods described below. It was shown to. In addition, the ion-exchanged water shown in Table 3 represents the total value (part) of the amount charged into the dropping device 2 and the amount for adjusting the nonvolatile content concentration. In addition, in Production Examples 64 and 65, in addition to the above, a part of ion-exchanged water charged into the stirring tank was changed to toluene as an organic solvent.

<Synthesis of base polymer (P)>
(Synthesis Example 101)
The following ethylenically unsaturated monomers, a chain transfer agent, a surfactant, and ion-exchanged water were charged into the stirring tank of a stirring apparatus equipped with a stirring tank, a stirrer, and a thermometer at the following ratios.

[Stirred tank]
2-ethylhexyl acrylate 81.94 parts Methyl methacrylate 10.18 parts 2-hydroxyethyl methacrylate 3.31 parts 4.58 parts acrylic acid 0.02 parts Octyl thioglycolate (chain transfer agent) 0.02 parts Reactive surface activity Agent 5.0 parts Ion exchange water 30.5 parts

  An aqueous dispersion of the monomer was obtained while stirring the inside of the stirring tank. Next, an aqueous dispersion of the following monomer and a polymerization initiator were respectively added to a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a reaction tank and a dropping device of a polymerization reaction device equipped with a nitrogen inlet tube, respectively. It was charged at the ratio of

[Polymerization tank]
36.17 parts of ion exchange water
[Drip device]
Aqueous dispersion of the above monomer 0.05 part 3% potassium persulfate aqueous solution (polymerization initiator) 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere, and 0.1% of a 3% aqueous solution of potassium persulfate was added as a nonvolatile component.
Five minutes later, the aqueous dispersion of the monomer and a 3% aqueous solution of potassium persulfate were dropped from the dropping device over 3 hours.
While maintaining the reaction temperature at 80 ° C., with further stirring, a 3% aqueous solution of potassium persulfate was added dropwise at an interval of 1.0 part every 0.5 hour after the completion of the dropwise addition, and then the mixture was aged for 2 hours to continue the reaction. did. Thereafter, the mixture was cooled to 25 ° C. and adjusted to pH = 7.5 with aqueous ammonia to obtain a base polymer (aqueous acrylic resin dispersion) having a nonvolatile content of 60%. The nonvolatile content (NV), the solution viscosity (Vis), and the average particle size (Dm) of the obtained base polymer were determined according to the methods described later, and the results are shown in Table 4.

(Synthesis examples 102 and 103)
A base polymer (aqueous dispersion of an acrylic resin) was synthesized in the same manner as in Synthesis Example 101, except that the materials and the blending amounts described in Table 4 were changed. The nonvolatile content (NV), the solution viscosity (Vis), and the average particle size (Dm) of the obtained base polymer were determined according to the methods described later, and the results are shown in Table 4.

《Solution appearance》
The appearance of the copolymer (X) obtained in Synthesis Examples 1 to 13 and the appearance of the copolymer (B) solution obtained in Synthesis Examples 51 to 80 were visually observed at 25 ° C. respectively. did. It is good if it is not extremely dark.

<< Non-volatile content (NV) >>
The copolymer (B) solution obtained in Synthesis Examples 51 to 80, the aqueous dispersion of the base polymer obtained in Synthesis Examples 12, 13, 101 to 103, and the tackifier resin obtained in Production Examples 1 to 75 About 1 g of each of the aqueous dispersions was weighed in a metal container, dried in a 150 ° C. oven for 20 minutes, the residue was weighed, and the residual ratio was calculated to obtain a nonvolatile content (solid content) (unit: %).

<< Solution viscosity (Vis) >>
Copolymer (B) solution obtained in Synthesis Examples 12, 13, 51 to 80, aqueous dispersion of base polymer obtained in Synthesis Examples 101 to 103, and tackifier resin obtained in Production Examples 1 to 75 Each aqueous dispersion was measured at 25 ° C. with a B-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.) under the conditions of rotor Nos. 2 to 4, rotation speed of 0.5 to 100 rpm, rotation for 1 minute, and solution or The aqueous dispersion viscosity (mPa · s) was used.

《Average molecular weight》
For the copolymer (X) obtained in Synthesis Examples 1 to 13 and the copolymer (B) obtained in Synthesis Examples 51 to 80, measurement of the number average molecular weight (Mn) and the mass average molecular weight (Mw) GPC (gel permeation chromatography) manufactured by Showa Denko KK was used. The determination of the number average molecular weight (Mn) and the mass average molecular weight (Mw) was based on the converted value of polystyrene as a standard substance.
Apparatus name: Showa Denko GPC (gel permeation chromatography) "Shodex GPC System-21"
Column: Tosoh GMHXL: 4, Tosoh HXL-H: 1 connected in series.
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Column temperature: 40 ° C

<< acid value (AV) >>
About the copolymer (X) obtained in Synthesis Examples 1 to 13, about 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was used. Was added and dissolved. To this, phenolphthalein TS was added as an indicator, and after holding for 30 seconds, titration was performed with a 0.1N alcoholic potassium hydroxide solution until the solution turned red.
The acid value was determined by the following equation. The acid value was a value in the dry state of the resin (unit: mgKOH / g).
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (nonvolatile concentration / 100)
Here, S: sampled amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution

<< Average particle size (Dm) >>
The average particle diameter obtained from the aqueous dispersion of the base polymer obtained in Synthesis Examples 101 to 103, and the aqueous dispersion of the tackifying resin obtained in Production Examples 1 to 75 uses Nikkiso's “Microtrack”. And measured. As the average particle size, a value of 50% of the cumulative percentage was applied.

<< Hydrogen ion index (pH) >>
The pH of the aqueous dispersion of the base polymer obtained in Synthesis Examples 101 to 103 and the aqueous dispersion of the tackifier resin obtained in Production Examples 1 to 80 were F-52S manufactured by HORIBA, electrode: Model 6377-10D. Measured.

<< Evaluation of filterability >>
The aqueous tackifier resin dispersions obtained in Production Examples 1 to 80 were filtered through a 180-mesh furnace cloth and evaluated in three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: prompt filtration, no residue at all. Good.
Δ: A little time is required for filtration, and a small amount of residue that does not affect the concentration of nonvolatile components remains. Available for practical use.
X: Filtration time is long and the residue is considerably large. The nonvolatile content concentration has decreased. Not practical.

《Evaluation of pot stain》
After the production of the aqueous dispersion of tackifying resin obtained in Production Examples 1 to 80, the state of adhesion of solids to the tank wall of the stirring tank and the washability with water were evaluated in three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: No adhesion at all, and good cleaning performance Δ: Some adhesion of solid matter, but good cleaning performance Available for practical use.
X: Solid adhered much and could not be removed by washing. Not practical.

<< Evaluation of storage stability >>
The aqueous dispersion of tackifier resin obtained in Production Examples 1 to 80 was collected in a 225 ml mayonnaise bottle, stored for 1 month at 25 ° C. with a lid, and then the dispersoid and liquid layer of the aqueous dispersion ( The state of separation of the dispersion medium) was evaluated in three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
○: The aqueous dispersion does not separate when stored for one month. Good.
Δ: Separated after storage for 2 weeks or longer, but returned to a uniform aqueous dispersion by shaking. Available for practical use.
X: Separation after storage for less than 2 weeks, or does not return to a uniform aqueous dispersion even if shaken. Not practical.

《Evaluation of mechanical stability》
5 g of water was added to and diluted with 50 g of the aqueous tackifier resin dispersion obtained in Production Examples 1 to 80, and the mixture was passed through a 300-mesh wire net, and 50 g of the mixture was used as a test sample. Using a Malon mechanical stability tester [manufactured by Tester Sangyo Co., Ltd.], a mechanical load was applied for 10 minutes at a temperature of 25 ° C., a load of 15 kg, and a rotation speed of 1,000 rpm, and the formed aggregates were reduced to 300 mesh. , And the dry mass of the agglomerate with respect to the initial dry mass of the aqueous dispersion was calculated, and the mechanical stability was evaluated in three stages based on the formation ratio (%) of the agglomerate. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: The generation rate of aggregates is less than 0.1%. Good.
Δ: The generation rate of aggregates is in the range of 0.1 to 1.0%. Available for practical use.
X: The generation rate of aggregates exceeds 1.0%. Not practical.
Here, the generation rate of the aggregate was calculated by the following method.
Aggregate generation ratio (%) = 100 × (mass of aggregate) / (initial mass of test sample)

<< Evaluation of solvent content >>
The aqueous dispersion of the tackifying resin obtained in Production Examples 1 to 80 was diluted with water to 1% by mass as necessary using gas chromatography ["Gas Chromatograph GC-8A" manufactured by Shimadzu Corporation]. The resulting product was directly charged into the apparatus, and the content of the organic solvent was determined and evaluated in three steps. In the case of "○" or "△" evaluation, there is no problem in actual use. The detection limit was 100 ppm.
Carrier gas: nitrogen
Column packing material (GL Science)
: PEG-HT (5%)-Uniport HP (60/80 mesh)
Column size: diameter 3mm x 3m,
Sample injection temperature (injection temperature): 180 ° C
Column temperature: 80 ° C
Internal standard substance: n-butanol]
：: The content of the organic solvent is less than 100 ppm (below the detection limit). Good.
Δ: The content of the organic solvent is in the range of 100 to 1,000 ppm. Available for practical use.
×: The content of the organic solvent exceeds 1,000 ppm. Not practical.

  Abbreviations of the materials used in each synthesis example and each production example are shown below. Numerical values represent parts, and blank columns mean no compounding.

<Table 1>
-Compound (b1)
1D: 1-decene, OD: 1-octadecene, L124: 1-dodecene / 1-tetradecene = 56/44 (mass ratio) [Idemitsu Kosan Co., Ltd. “Linearylene 124”], St: styrene, EHVE: 2-ethylhexyl vinyl ether , FVS: phenylvinyl sulfide Compound (b2-2)
BA: butyl acrylate, PLE: lauroxy polyethylene glycol methacrylate (EO = 30 mol) [“PLE-1300” manufactured by NOF Corporation]
-Compound (b2-1)
MAH: maleic anhydride, CAH: citraconic anhydride, FA: fumaric acid, AA: acrylic acid-organic solvent IPA: isopropyl alcohol-polymerization initiator DBO: di-tert-butyl peroxide

<Table 2>
・ Copolymer (X)
Synthesis Examples: Compounds obtained in each of the synthesis examples described in Table 1 (Synthesis Examples 1 to 11), 130MA: maleic acid-modified polybutadiene [“Ricon 130MA20” manufactured by CRAY VALLEY, Mw = 3,000, AV = 120 mgKOH / g ]
-Compound (b3-1-1)
TEGM: triethylene glycol monomethyl ether (EO = 3 mol, M = 164.2]), N1020: polyoxyethylene 2-ethylhexyl ether [“Newcol 1020” manufactured by Nippon Emulsifier Co., Ltd., EO = 20 mol, Mn = 997.3]
-Compound (b3-1-2)
MEOA: methoxytriethylene glycol amine (EO = 3 mol, M = 207.3), M1000: methoxypolyoxyethylene tripropoxyamine [“Jeffamine M-1000” manufactured by HUNTSMAN, EO = 19 mol, M = 1,000]
-Compound (b3-1-3)
EX171: Lauryl alcohol polyoxyethylene glycidyl ether [Nagae ChemteX Co., Ltd. “Denacol EX-171”, EO = 15 mol, Mn = 903]
-Compound (b3-2)
TPOM: tripropylene glycol methyl ether (PO = 3 mol, Mn = 206.3), M600: methoxy polypropylene glycol amine [“Jeffamine M-600” manufactured by HUNTSMAN, PO = 9 mol, M = 997.8], PTG: Polytetramethylene ether glycol [“PTG-1000” manufactured by Hodogaya Chemical Co., TO = 14 mol, M = 1,000]
-Compound (b4)
LAOH: lauryl alcohol, LAAM: laurylamine • catalyst PTNS: sodium paratoluenesulfonate • basic compound (e1)
TEA: triethylamine, DBU: diazabicycloundecene Basic compound (e2)
EA: 2-aminoethanol

<Table 3>
・ Tackifying resin (A)
D160: Polymerized rosin ester [Pencel D-160, manufactured by Arakawa Chemical Industries, softening point = 160 ° C], KT3: Polymerized rosin ester [Hariester KT-3, manufactured by Harima Chemicals, softening point = 180 ° C], KR140: hydrogenated rosin ester [Pine Crystal KR-140, manufactured by Arakawa Chemical Industries, softening point = 140 ° C], FTR: petroleum-based resin [FTR-6125, manufactured by Mitsui Chemicals, softening point = 125 ° C], T160: Terpene / phenol resin [Yshara Chemical Co., Ltd. “YS Polystar T160”, softening point = 160 ° C.]
-Tackifier resin not tackifier resin (A) E-H: Rosin ester [Arakawa Chemical Industries "Ester gum H", softening point = 68 ° C]
・ Copolymer resin (B)
Synthesis Examples: Compounds obtained in each of the synthesis examples shown in Table 2 (Synthesis Examples 1, 12, 13, 51 to 80)
・ Liquid resin (C)
HV100: Polybutene [Nisseki polybutene HV-100, manufactured by JXTG Energy, Mn = 980], P1025: Dimer acid [Pripol1025, Mn = 560.9, manufactured by CRODA], P2010: Polyester polyol [Kuraray manufactured] Kuraray polyol P-2010 ", Mn = 2,000], UV22C: rosin-modified epoxy acrylate [" Banbeam UV-22C "manufactured by Harima Chemicals, Mn = 3,800]
・ Surfactant (D) (anion)
LAEOA: Polyoxyethylene lauryl ether ammonium sulfate (EO addition mole number: 20), SR20: Polyoxyethylene-1- (allyloxymethyl) alkyl ether glycerin sulfonate ammonium (EO addition mole number: 20) [ADEKASOAP manufactured by ADEKA CORPORATION SR20 "]
・ Surfactant (D) (nonionic)
STEO: polyoxyethylene stearyl ether (number of moles of EO added: 50)
-Basic compound (e1)
TEA: triethylamine, DMBA: N, N-dimethylbenzylamine Basic compound (e2)
EA: 2-aminoethanol • Water W: Ion exchange water • Organic solvent TOL: Toluene • Other compound (F)
KM73A: Silicone antifoaming agent [Shin-Etsu Silicone KM-73A manufactured by Shin-Etsu Chemical Co., Ltd.]

<Table 4>
Ethylenically unsaturated monomer BA: butyl acrylate, 2EHA: 2-ethylhexyl acrylate, MMA: methyl methacrylate, MA: methyl acrylate, HEMA: 2-hydroxyethyl methacrylate, AA: acrylic acid, DAAM: Diacetone acrylamide ・ Chain transfer agent SGO Octyl thioglycolate ・ Surfactant KH10: Reactive surfactant [[Aqualon KH-10 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.]
・ Polymerization initiator KPS: 3% potassium persulfate aqueous solution ・ Water W: Ion exchange water

  In addition, the mass described in the column of the polymerization initiator in Table 1 is the total of the mass added in the polymerization tank, the total of the mass added three times during the dropwise addition, and the post-addition is the total of the mass added twice after the completion of the dropwise addition. Means In addition, the mass described in the column of the polymerization initiator in Table 4 means the sum of the mass charged in the dropping tank and the mass added twice after the completion of the dropping.

<Aqueous adhesive>
Using the tackifier resin aqueous dispersions obtained in the above Production Examples, aqueous pressure-sensitive adhesives were respectively prepared by the following methods.
(Example 1)
In a stirring tank of a stirrer equipped with a stirrer, stirrer, and thermometer, the following base polymer, tackifier resin aqueous dispersion and other compound (F) {crosslinking agent, viscosity modifier, defoamer, and preservative} were respectively added. The following ratios were used.

[Stirred tank]
100 parts of base polymer (P) of Synthesis Example 101 10 parts of aqueous dispersion of tackifying resin of Production Example 1 10 parts 5% aqueous solution of adipic acid dihydrazide (crosslinking agent) 1.0 part Adecanol UH-420 (viscosity modifier) 0.4 Part SN deformer 154 (antifoaming agent) 0.1 part,
Deltop 100N (preservative) 0.01 parts

  Using a homomixer (“LZB46-HM-3” manufactured by Chuo Rika Co., Ltd.) as a stirrer, the mixture was stirred for 0.5 hour at a rotation speed of 2,000 rpm. Next, while stirring, Acrysol ASE-60 (viscosity modifier), ammonia water and ion-exchanged water were added to adjust, and the non-volatile content (NV) was about 50% and the solution viscosity (Vis) was about 8,000 mPa · s. The pH was adjusted to about 8.2 to obtain an aqueous pressure-sensitive adhesive. The non-volatile content (NV), solution viscosity (Vis) and hydrogen ion index (pH) of the obtained water-based pressure-sensitive adhesive were determined according to the above-mentioned methods. The results are shown in Table 5.

(Examples 2 to 72, Comparative Examples 1 to 19)
Among the materials described in Table 5, a base polymer, an aqueous dispersion of a tackifier resin, a crosslinking agent, a viscosity modifier, an antifoaming agent and a preservative were blended according to the description in Table 5, and agitated and mixed. Obtained.
Each of the obtained water-based pressure-sensitive adhesives was applied to each substrate, dried and bonded, to prepare a pressure-sensitive adhesive sheet, which was evaluated by the following method. Table 6 shows the results. In Comparative Examples 6 and 18, the production and coating of the aqueous pressure-sensitive adhesive were not performed because the filterability of the tackifier resin aqueous dispersion was extremely poor.

<< Evaluation of storage stability >>
The aqueous pressure-sensitive adhesive obtained in each of the examples and comparative examples was collected in a 225 ml mayonnaise bottle in the same manner as described above, and stored for 1 month at 25 ° C. with the lid covered. The state of separation of the layer (dispersion medium) was evaluated in three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
○: The aqueous dispersion does not separate when stored for one month. Good.
Δ: Separated after storage for 2 weeks or longer, but returned to a uniform aqueous dispersion by shaking. Available for practical use.

X: Separation after storage for less than 2 weeks, or does not return to a uniform aqueous dispersion even if shaken. Not practical.

《Evaluation of mechanical stability》
In the same manner as described above, 50 g of the aqueous pressure-sensitive adhesive obtained in each of the examples and the comparative examples was collected, diluted with 5 g of water, and passed through a 300-mesh wire gauze. After applying a mechanical load for 10 minutes at a temperature of 25 ° C., a load of 15 kg, and a rotation speed of 1,000 rpm using a Maron mechanical stability tester [manufactured by Tester Sangyo Co., Ltd.], the formed aggregates were reduced to 300 mesh. , And the dry mass of the agglomerate with respect to the initial dry mass of the aqueous pressure-sensitive adhesive was calculated, and the mechanical stability was evaluated in three stages based on the formation ratio (%) of the agglutinate. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: The generation rate of aggregates is less than 0.1%. Good.
Δ: The generation rate of aggregates is in the range of 0.1 to 1.0%. Available for practical use.
X: The generation rate of aggregates exceeds 1.0%. Not practical.
Here, the generation rate of the aggregate was calculated by the following method.
Aggregate generation ratio (%) = 100 × (mass of aggregate) / (initial mass of test sample)

《Evaluation of coatability》
The obtained water-based pressure-sensitive adhesive is coated on a commercially available glassine paper (hereinafter also referred to as “glassine separator”) that has been subjected to a release treatment as a release liner so that the thickness of the pressure-sensitive adhesive layer after drying is 18 μm. Then, by drying with hot air at 100 ° C. for 2 minutes, an adhesive layer was formed. Then, a commercially available high-quality paper having a thickness of 60 μm was attached to the coated surface to produce an adhesive sheet composed of high-quality paper / adhesive layer / release liner. Then, the state of the pressure-sensitive adhesive layer surface (coated surface) after peeling off the release liner was visually observed and evaluated in three steps. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: No smoothing, foaming or streaking was observed on the coated surface, and the coated surface was smooth. Good.
Δ: Slight repelling or foaming is observed at the end of the coated surface. Available for practical use.
×: Repelling, foaming and streaking were observed on the entire coated surface. Bad.

《Evaluation of workability》
Each of the pressure-sensitive adhesive sheets prepared in the same manner as in <Evaluation of Coating Properties> was cured for 3 days in an environment of 23 ° C. and 50% relative humidity. Thereafter, the sheet was cut into a piece having a width of 100 mm and a length of 100 mm. Twenty pieces of the pieces were stacked and pressed out under the condition of 40 ° C.-60 kg / cm ² for 1 hour. Was evaluated in three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: No protrusion of the pressure-sensitive adhesive layer was observed. Good.
Δ: Extrusion of the pressure-sensitive adhesive layer of less than 0.3 mm was observed, but practically usable.
×: Extrusion of the pressure-sensitive adhesive layer of 0.3 mm or more is observed. Bad.

<< Measurement of peel strength >>
Each of the pressure-sensitive adhesive sheets prepared in the same manner as in the above <Evaluation of coating property> is cut into a width of 25 mm × length of 100 mm, the release liner is peeled off, and the exposed pressure-sensitive adhesive layer is a polyethylene (PE) plate having a thickness of 3 mm. Was adhered in an environment of 23 ° C. and a relative humidity of 50%, and a roll having a mass of 2 kg was reciprocated once to obtain a measurement sample. After leaving this measurement sample for 1 day in an environment of 23 ° C. and 50% relative humidity, a peeling rate of 300 mm / min. Was used in the same environment using a tensile tester (“Tensilon” manufactured by Orientec). The peel strength was measured under the condition of an angle of 180 ° (measurement of the peel strength one day after bonding).
Further, after the measurement sample was left in an environment of 60 ° C. and a relative humidity of 95% for 3 days, the peel strength was measured in the same manner (measurement of the peel strength after 3 days of wet heat aging). The peel strength was evaluated as adhesive strength in three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: Adhesive strength is 20.0 (mN / 25 mm) or more. Good.
Δ: Adhesion force is 15.0 (mN / 25 mm) or more and less than 20.0 (mN / 25 mm). Practical.
×: Adhesive strength is less than 15.0 (mN / 25 mm). Bad and impractical.

《Measurement of holding force》
Each of the pressure-sensitive adhesive sheets prepared in the same manner as in the above <Evaluation of Coating Properties> was cut into a width of 25 mm x a length of 100 mm, and the release liner was peeled off so that the bonded portion became 25 mm x 25 mm. The layer was adhered to a stainless steel (SUS) plate having a thickness of 3 mm in an environment of 23 ° C. and a relative humidity of 50%, and a roll having a mass of 2 kg was reciprocated once to obtain a measurement sample.
After leaving this measurement sample in a 40 ° C. environment for 20 minutes, a load of 1 kg was applied in a 40 ° C. environment and 70,000 seconds at 40 ° C. using a holding force tester [manufactured by Tester Sangyo Co., Ltd.] The measurement was performed, and the time required for the load to fall, or when the load did not fall, was measured for the length deviated from the time of the initial attachment, and evaluated in the following three stages. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: There is no load drop and the deviation is less than 0.5 mm. Good.
Δ: There is no load drop, but the deviation is 0.5 mm or more. Practical.
×: Dropped in less than 70,000 seconds. Bad and impractical.

<< Evaluation of curved surface adhesion >>
Each of the pressure-sensitive adhesive sheets prepared in the same manner as in the above <Evaluation of Coating Properties> was cut into a width of 20 mm × length of 22 mm, and the length direction of the sample was measured on a curved surface of a polyethylene (PE) resin cylinder having a diameter of 10 mm. It was adhered along the direction, pressed with a 2 kg rubber roller, and left for 24 hours in an atmosphere of 23 ° C. and 50%. Thereafter, the peeling state of the end portion in the length direction of the sample was visually observed, and evaluated in three steps based on the following criteria.
：: No peeling was observed, or a portion of the end of the sample less than 0.1 mm was peeled. Good Δ: The portion of 0.1 to 0.5 mm at the end of the sample was peeled off. Practical.
X: The part exceeding 0.5 mm at the end of the sample was peeled off. Bad and impractical.

<< Evaluation of constant load peelability test >>
The obtained water-based pressure-sensitive adhesive was applied on the release surface of the glassine separator so that the thickness after drying became 60 μm, and dried with hot air at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Subsequently, a polyester nonwoven fabric layer of a skin material having a thickness of 10 mm and having a three-layer structure of a skin layer (fabric) / urethane foam layer / polyester nonwoven fabric layer is bonded to each other. To obtain a pressure-sensitive adhesive sheet composed of a skin material / pressure-sensitive adhesive layer / release liner.
Each of the obtained pressure-sensitive adhesive sheets is cut into a width of 25 mm × length of 100 mm, the release liner is peeled off, and the exposed pressure-sensitive adhesive layer is 25 mm wide × 80 mm long at a polypropylene plate (hereinafter also referred to as “PP plate”) 23 ° C. The sample was adhered in an environment with a relative humidity of 50%, and reciprocated on a roll having a mass of 2 kg once to obtain a measurement sample.
The obtained measurement sample was allowed to stand for 24 hours in an environment of 23 ° C. and a relative humidity of 50%, and then for 1 hour in an environment of 80 ° C., and then the PP plate was placed so that the attachment surface was on the lower side. It was kept horizontal, a 100 g weight was hung on the end of the pressure-sensitive adhesive sheet where it was not stuck, left for 1 hour, and the length of the part peeled off from the PP plate was measured. When all the pieces were peeled off from the PP plate within one hour, the time up to that point was measured and evaluated in three steps based on the following criteria. The test was performed in an environment at 80 ° C. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: no fall, displacement less than 20 mm. Good and practically no problem.
Δ: Dropped in 50 minutes or more. Practical.
X: Dropped in less than 50 minutes. Bad and impractical.
<< Evaluation of substrate adhesion >>
Above, << Evaluation of constant load peelability test >>
The release liner was peeled off from each of the pressure-sensitive adhesive sheets prepared in the same manner as described above, and the exposed pressure-sensitive adhesive layer was rubbed with a finger, and whether or not the pressure-sensitive adhesive layer dropped off from the skin material as the base material was evaluated in three steps based on the following criteria. In the case of "○" or "△" evaluation, there is no problem in actual use.
：: Does not fall off from the substrate even after rubbing more than 15 times. Good and practically no problem.
Δ: Drops off from the substrate after 5 to 15 reciprocations. Practical.
×: The adhesive falls off in less than 5 reciprocations. Bad and impractical.

The materials used in the examples and comparative examples are shown below. In Tables 5 and 6, blanks indicate no formulation, and "-" indicates uncoated.
・ Base polymer (P)
Synthesis Examples: Acrylic aqueous dispersions (Synthesis Examples 101 to 103) obtained in each of the synthesis examples shown in Table 4, LA50: chloroprene latex [“LA-50” manufactured by Denka, NV = 50%], GFL280: chloroprene Latex [Tosoh “Skyprene Latex GFL-280”, NV = 52%]
-Tackifying resin aqueous dispersion Production example: Tackifying resin aqueous dispersion obtained in each production example shown in Table 3 (Production Examples 1 to 75)
・ Crosslinking agent (F)
ADH: 5% aqueous solution of adipic dihydrazide ・ Viscosity modifier (F)
UH420: “ADEKANOL UH-420” manufactured by Adeka, NV = 30%, ASE60: “Acrysol ASE-60” manufactured by Dow Chemical, NV = 28%
・ Antifoaming agent (F)
SN154: "SN Deformer 154" manufactured by San Nopco
・ Preservative (F)
100N: "Deltop 100N" manufactured by Osaka Gas Chemical Company
・ Water W: Ion exchange water

As described above, in Examples 1 to 18, 21 to 39, 41 to 53, 57 to 60, 62, 63 and 68 to 75, the aqueous adhesives of the present invention exhibited storage stability, mechanical stability, and coating stability. In all of the workability, workability, peel strength, holding power, curved surface adhesiveness, constant load peeling and substrate adhesion, the “△” evaluation (practicable level) is 3 or less out of 10 items, and the others are All were evaluated as "O" (good level), which means that they were excellent.
In Examples 19, 20, 40, 54 to 56, 61, and 64 to 67, the “△” evaluation (practicable level) of each evaluation was 4 to 10 out of 10 items, and the “X” evaluation ( Since there is no defect level, it can be used without any practical problems.
On the other hand, in Comparative Examples 1 to 19, any one of storage stability, mechanical stability, coatability, workability, peel strength, holding power, curved surface adhesiveness, constant load peeling, and substrate adhesion was used. It turns out that it is extremely inferior.

  The aqueous dispersion of the tackifier resin according to the present invention has excellent filterability even if the tackifier resin is contained at a high concentration without using an organic solvent, and has good potability, mechanical stability and storage stability. Since it can have an aqueous dispersion of a tackifying resin having a high softening point and has good compatibility with a base polymer, the aqueous adhesive containing the aqueous dispersion of the tackifier resin has excellent storage stability. Since it provides mechanical stability, coatability, workability, adhesiveness, curved surface adhesiveness, wet heat resistance, constant load peelability, substrate adhesion, etc., in the construction field (eg, exterior, interior, equipment, etc.) It can also be used in various industrial fields other than optical fields such as electric equipment (for example, home appliances, kitchen equipment, air conditioning, etc.), transport equipment (for example, ships and automobiles), furniture, and miscellaneous goods. is there.

Claims (13)

It contains a tackifying resin (A) having a softening point of 100 to 180 ° C. and a copolymer resin (B). 0.5 to 50 parts by mass, a content of an organic solvent is 1000 ppm or less, and the following (1) and (2) are satisfied.
(1) The copolymer resin (B) is obtained by modifying the copolymer (X) with a compound (b3) having an alkylene oxide unit.
(2) The copolymer (X) is, as a monomer constituting the copolymer, at least one compound (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide, and diolefin. And a dibasic acid having an unsaturated group or its anhydride (b2-1).   The tackifier resin aqueous dispersion according to claim 1, wherein the compound (b3) having an alkylene oxide unit is a compound having an ethylene oxide unit.   The tackifier resin aqueous dispersion according to claim 1, wherein the dibasic acid having an unsaturated group or an anhydride thereof (b2-1) is maleic anhydride.   The tackifier resin aqueous dispersion according to any one of claims 1 to 3, wherein the copolymer resin (B) has a mass average molecular weight of 1,000 to 500,000.   The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the tackifying resin (A) is at least one resin selected from the group consisting of a rosin-based resin, a terpene-based resin, and a petroleum-based resin. An aqueous resin dispersion.   Further, it comprises a liquid resin (C) having a number average molecular weight of 300 to 50,000 (excluding the case of a tackifying resin (A) and a copolymer resin (B)). Item 6. The tackifier resin aqueous dispersion according to any one of Items 1 to 5.   The tackifier resin aqueous dispersion according to any one of claims 1 to 6, further comprising a surfactant (D).   The tackifier resin aqueous dispersion according to claim 7, wherein the surfactant (D) contains at least one of an anionic surfactant and a nonionic surfactant.   The tackifier resin aqueous dispersion according to any one of claims 1 to 8, further comprising a basic compound (E).   The tackifier resin aqueous dispersion according to claim 9, wherein the basic compound (E) is a tertiary amine.   An aqueous pressure-sensitive adhesive comprising: a base polymer (P); and the aqueous dispersion of a tackifier resin according to claim 1.   An adhesive sheet comprising a substrate (G) and an adhesive layer formed from the aqueous adhesive according to claim 11.   Copolymerization of at least one compound (b1) selected from the group consisting of α-olefin, styrene, vinyl ether, vinyl sulfide and diolefin with a dibasic acid having an unsaturated group or an anhydride thereof (b2-1) A second step of obtaining a copolymer resin (B) by modifying the copolymer (X) with a compound (b3) having an alkylene oxide unit to obtain a copolymer (X); A method for producing a tackifier resin aqueous dispersion, comprising: a third step of mixing the tackifier resin (A) having a temperature of 100 to 180 ° C and the copolymer resin (B).