Water dispersion composition, tackifier resin water dispersion composition, aqueous adhesive composition, and adhesive sheet

Abstract

This water dispersion composition comprises at least one resin (A) selected from the group consisting of a rosin resin (a1), a petroleum resin (a2), and a terpene resin (a3), and a copolymer (B) comprising a structural unit (b1) derived from a hydrophilic unsaturated monomer and a structural unit (b2) derived from a hydrophobic unsaturated monomer. The softening point of the resin (A) is 95°C or higher, and the acid value of the resin (A) is 100 mgKOH / g or less, the structural unit (b1) contains a structural unit derived from (meth)allylsulfonic acid or a salt thereof, the structural unit (b2) contains a structural unit derived from an aromatic vinyl compound, and the molar ratio ((b1) / (b2)) of the structural unit (b1) to the structural unit (b2) is 0.3-3.0.

Description

Water-dispersed composition, tackifying resin water-dispersed composition, water-based pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet

[0001] The present invention relates to a water-dispersed composition, a water-dispersed tackifying resin composition, a water-based pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet.

[0002] Resins such as rosin-based resins, petroleum resins, and terpene-based resins are widely used in various fields, such as tackifiers for adhesives such as hot melts and pressure-sensitive adhesives, modifiers for rubber and plastics, binder resins for road marking paints and inks, etc. These resins have traditionally been generally dissolved in organic solvents, but in recent years, in consideration of the environment, safety and hygiene, resource conservation, etc., aqueous dispersion compositions in which the resins are dispersed or emulsified in water are becoming mainstream.

[0003] Conventionally, such aqueous dispersion compositions have been proposed as tackifiers for aqueous pressure-sensitive adhesives, which are prepared by emulsifying resins in the presence of various anionic emulsifiers or nonionic emulsifiers (see Patent Documents 1 to 3).

[0004] JP 2010-106259 A JP 2012-140500 A JP 2007-186588 A

[0005] However, some conventional water-dispersed compositions generate a large amount of aggregates, and their emulsification properties are still insufficient. Furthermore, when conventional water-dispersed compositions are used as tackifiers for water-based pressure-sensitive adhesives, they may not be able to impart sufficient adhesive strength to the water-based pressure-sensitive adhesives.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel aqueous dispersion composition that has excellent emulsification properties and can impart high adhesive strength to an aqueous pressure-sensitive adhesive composition.

[0007] As a result of extensive research, the present inventors have found that the above object can be achieved by an aqueous dispersion composition containing a specific resin and a specific copolymer.

[0008] The present disclosure provides the following:

[0009] (Item 1) An aqueous dispersion composition comprising: at least one resin (A) selected from the group consisting of a rosin-based resin (a1), a petroleum resin (a2), and a terpene-based resin (a3); and a copolymer (B) comprising a structural unit (b1) derived from a hydrophilic unsaturated monomer and a structural unit (b2) derived from a hydrophobic unsaturated monomer; wherein the softening point of the resin (A) is 95°C or higher; the acid value of the resin (A) is 100 mgKOH / g or lower; the structural unit (b1) comprises a structural unit derived from (meth)allylsulfonic acid or a salt thereof; the structural unit (b2) comprises a structural unit derived from an aromatic vinyl compound; and the molar ratio of the structural unit (b1) to the structural unit (b2), ((b1) / (b2)), is 0.3 to 3.0.

[0010] (Item 2) The aqueous dispersion composition according to Item 1, wherein the rosin-based resin (a1) has a softening point of 130° C. or higher.

[0011] (Item 3) The water-dispersed composition according to Item 1 or 2, wherein the structural unit (b2) includes a structural unit derived from a hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms.

[0012] (Item 4) A tackifier resin aqueous dispersion composition comprising the aqueous dispersion composition according to any one of items 1 to 3.

[0013] (Item 5) An aqueous pressure-sensitive adhesive composition comprising the aqueous dispersion composition according to any one of items 1 to 3 and a base polymer.

[0014] (Item 6) The aqueous pressure-sensitive adhesive composition according to Item 5, wherein the base polymer comprises an acrylic polymer emulsion.

[0015] (Item 7) The aqueous pressure-sensitive adhesive composition according to claim 5, wherein the base polymer comprises a rubber latex.

[0016] (Item 8) A pressure-sensitive adhesive sheet comprising a substrate and a pressure-sensitive adhesive layer made of the aqueous pressure-sensitive adhesive composition according to any one of Items 5 to 7.

[0017] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated.

[0018] Throughout this disclosure, the range of values ​​for each physical property, content, etc. may be set as appropriate (e.g., by selecting from the values ​​described in each item below). Specifically, when the example of the value α is A3, A2, or A1 (where A3 > A2 > A1), the range of the value α may be, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and less than A2), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, and the like. In this disclosure, the term "to" is used to mean that the values ​​before and after it are included as both the lower and upper limits. The components and manufacturing methods of this disclosure will be described in detail below.

[0019] As long as the object of the present invention is achieved, there are no particular limitations on the components, conditions, values, etc.

[0020] The "γ ratio (A / B)" means a γ ratio calculated by the formula "A÷B." Examples of the γ ratio include a mass ratio and a molar ratio.

[0021] "Nonvolatile content" means the total mass of components other than organic solvents and water.

[0022] "(Meth)acrylic" means "acrylic and / or methacrylic". "(Meth)acrylate" means "acrylate and / or methacrylate". "(Meth)acryloyl" means "acryloyl and / or methacryloyl". "(Meth)allyl" means "allyl and / or methallyl".

[0023] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0024] [Water-Dispersed Composition] The present disclosure relates to a water-dispersed composition comprising at least one resin (A) (hereinafter also referred to as component (A)) selected from the group consisting of a rosin-based resin (a1) (hereinafter also referred to as component (a1)), a petroleum resin (a2) (hereinafter also referred to as component (a2)), and a terpene-based resin (a3) ​​(hereinafter also referred to as component (a3)), and a copolymer (B) (hereinafter also referred to as component (B)) containing a structural unit (b1) derived from a hydrophilic unsaturated monomer and a structural unit (b2) derived from a hydrophobic unsaturated monomer.

[0025] <Resin (A)> The component (A) is at least one resin selected from the group consisting of components (a1), (a2), and (a3), and is not particularly limited as long as it has a softening point of 95°C or higher and an acid value of 100 mgKOH / g or lower, and various known resins can be used. One type of component (A) may be used alone, or two or more types may be used in combination.

[0026] <Rosin-Based Resin (a1)> The component (a1) is not particularly limited as long as it is a rosin-based resin, and various known resins can be used. As the component (a1), one type may be used alone, or two or more types may be used in combination.

[0027] Examples of the component (a1) include rosin esters, rosin phenolic resins, and rosin polyols.

[0028] (Rosin Esters) Examples of the rosin esters include reaction products of natural rosin, purified rosin (hereinafter, natural rosin and purified rosin are collectively referred to as unmodified rosin), hydrogenated rosin, disproportionated rosin, polymerized rosin, and α,β-unsaturated carboxylic acid-modified rosin (hereinafter, these are collectively referred to as rosins) with alcohol. In the present disclosure, reaction products of unmodified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and α,β-unsaturated carboxylic acid-modified rosin with alcohol are referred to as unmodified rosin ester, hydrogenated rosin ester, disproportionated rosin ester, polymerized rosin ester, and α,β-unsaturated carboxylic acid-modified rosin ester, respectively.

[0029] Examples of the natural rosin include Pinus massoniana, Slash pine, Yunnan pine, Merkusii pine, Caribbean pine, Tropical pine, Kesiya pine, Loblolly pine, Pinus taeda, Great King pine, Camphor pine, Resinosa pine, White pine, and Aleppo pine. Examples of suitable rosins include natural rosins (gum rosin, tall oil rosin, wood rosin) derived from, for example, Saccharomyces cerevisiae.

[0030] The purified rosin can be obtained using various known methods. Specifically, the purified rosin can be obtained using various known purification methods, such as distillation, extraction, recrystallization, and adsorption. Examples of distillation methods include distilling the natural rosin at a temperature of approximately 200 to 300°C under a reduced pressure of approximately 0.01 to 3 kPa. Examples of extraction methods include dissolving the natural rosin in an alkaline aqueous solution, extracting the insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer. Examples of recrystallization methods include dissolving the natural rosin in an organic solvent as a good solvent, distilling off the solvent to obtain a concentrated solution, and then adding an organic solvent as a poor solvent. Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, chlorinated hydrocarbon solvents such as chloroform, lower alcohols, ketones such as acetone, and acetate esters such as ethyl acetate. Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane. The adsorption method may involve contacting the natural rosin in a molten state or in a solution state obtained by dissolving the natural rosin in an organic solvent with a porous adsorbent, such as activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and microporous clay.

[0031] In one embodiment, the purified rosin may be obtained by further subjecting the obtained purified rosin to the disproportionation and hydrogenation procedures described below, either alone or in combination of two or more thereof.

[0032] The disproportionated rosin can be obtained by various known means. Specifically, the disproportionated rosin can be obtained, for example, by heating the unmodified rosin in the presence of a disproportionation catalyst (disproportionation). Examples of the disproportionation catalyst that can be used include supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; and iodides such as iodine and iron iodide. In one embodiment, the amount of catalyst used is typically about 0.01 to 5 parts by mass, and preferably about 0.01 to 1 part by mass, per 100 parts by mass of the unmodified rosin. In one embodiment, the reaction temperature is about 100 to 300°C, and preferably about 150 to 290°C.

[0033] In one embodiment, the disproportionated rosin may be obtained by further subjecting the obtained disproportionated rosin to the purification, disproportionation, and hydrogenation described below, either alone or in combination of two or more thereof.

[0034] The hydrogenated rosin can be obtained using various known means. Specifically, the hydrogenated rosin can be obtained, for example, by hydrogenating the unmodified rosin using known hydrogenation conditions. Examples of hydrogenation conditions include heating the unmodified rosin to about 100 to 300°C under a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst. In one embodiment, the hydrogen pressure is preferably about 5 to 20 MPa. In one embodiment, the reaction temperature is preferably about 150 to 300°C. Various known hydrogenation catalysts can be used, such as supported catalysts and metal powders. Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon. Examples of metal powders include nickel and platinum. In one embodiment, the metal powder is preferably a palladium-, rhodium-, ruthenium-, or platinum-based catalyst. In one embodiment, by using these as the metal powder, the hydrogenation rate of the unmodified rosin is increased and the hydrogenation time is shortened. In one embodiment, the amount of the hydrogenation catalyst used is typically about 0.01 to 5 parts by mass, and preferably about 0.01 to 2 parts by mass, per 100 parts by mass of the unmodified rosin.

[0035] In one embodiment, the hydrogenation may be carried out, if necessary, with the unmodified rosin dissolved in a solvent. The solvent used is not particularly limited. In one embodiment, the solvent is preferably a solvent that is inert to the reaction and easily dissolves the raw materials and products. Specifically, the solvent may be, for example, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, or the like, either alone or in combination. In one embodiment, the amount of solvent used is typically such that the nonvolatile content is 10% by mass or more, preferably such that the nonvolatile content is about 10 to 70% by mass, based on the unmodified rosin.

[0036] In one embodiment, the hydrogenated rosin may be obtained by further subjecting the obtained hydrogenated rosin to the purification, hydrogenation, and disproportionation procedures, either alone or in combination of two or more thereof.

[0037] In one embodiment, for the purpose of improving color tone, purified rosin, hydrogenated rosin, and disproportionated rosin may be further subjected to a dehydrogenation treatment. The dehydrogenation treatment is not particularly limited. In one embodiment, the dehydrogenation treatment is carried out in a sealed container with purified rosin, hydrogenated rosin, or disproportionated rosin in the presence of a dehydrogenation catalyst at an initial hydrogen pressure of less than 10 kg / cm, preferably less than 5 kg / cm, and at a reaction temperature of approximately 100 to 300°C, preferably in the range of a lower limit of 200°C and an upper limit of 280°C. In one embodiment, the dehydrogenation catalyst is preferably a palladium-based, rhodium-based, or platinum-based catalyst, and is typically used supported on a carrier such as silica or carbon. In one embodiment, the amount of the catalyst used is typically 0.01 to 5% by mass, preferably a lower limit of 0.05% by mass and an upper limit of 3% by mass, based on the purified rosin, hydrogenated rosin, or disproportionated rosin.

[0038] The polymerized rosin can be obtained by various known methods. Specifically, the polymerized rosin can be obtained, for example, by reacting the unmodified rosin as a raw material in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, or titanium tetrachloride at a reaction temperature of about 40 to 160° C. for about 1 to 5 hours.

[0039] Specific examples of the polymerized rosin include gum-based polymerized rosin using gum rosin as a raw material (for example, trade name "Polymerized Rosin B-140" manufactured by Shinzhou (Wuping) Hayashi Chemical Co., Ltd.), tall oil-based polymerized rosin using tall oil rosin (for example, trade name "Silvatack 140" manufactured by Arizona Chemical Co.), and wood-based polymerized rosin using wood rosin (for example, trade name "Dymalex" manufactured by Eastman Chemical Co.).

[0040] In one embodiment, the polymerized rosin may be obtained by subjecting the obtained polymerized rosin to various treatments, such as the purification, hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification such as acrylate, maleinization, and fumaric acid modification, which will be described later. The various treatments may be performed alone or in combination of two or more.

[0041] The α,β-unsaturated carboxylic acid modified rosin is obtained by subjecting the unmodified rosin to an addition reaction with an α,β-unsaturated carboxylic acid.

[0042] The α,β-unsaturated carboxylic acid is not particularly limited, and various known α,β-unsaturated carboxylic acids can be used. Specific examples of the α,β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, maleic acid half ester, fumaric acid half ester, and itaconic acid half ester. In one embodiment, the α,β-unsaturated carboxylic acid is preferably acrylic acid, maleic acid, maleic anhydride, or fumaric acid. In one embodiment, the amount of the α,β-unsaturated carboxylic acid used is typically about 1 to 20 parts by mass, and preferably about 1 to 3 parts by mass, per 100 parts by mass of the unmodified rosin, in order to achieve excellent flowability in a melt and excellent moldability.

[0043] The α,β-unsaturated carboxylic acid-modified rosin can be obtained using various known means. Specifically, the α,β-unsaturated carboxylic acid-modified rosin can be obtained, for example, by adding the α,β-unsaturated carboxylic acid to the unmodified rosin melted under heating, and reacting the mixture at a temperature of about 180 to 240°C for about 1 to 9 hours. In one embodiment, the reaction may be carried out while blowing an inert gas such as nitrogen into a sealed reaction system. In one embodiment, the reaction may use a known catalyst, such as a Lewis acid such as zinc chloride, iron chloride, or tin chloride, or a Brønsted acid such as paratoluenesulfonic acid or methanesulfonic acid. In one embodiment, the amount of the catalyst used is typically about 0.01 to 10% by mass relative to the unmodified rosin.

[0044] In one embodiment, the α,β-unsaturated carboxylic acid-modified rosin may be obtained by further subjecting the obtained α,β-unsaturated carboxylic acid-modified rosin to various treatments such as the purification, hydrogenation, disproportionation, etc. The various treatments may be performed alone or in combination of two or more.

[0045] The alcohol is not particularly limited, and various known alcohols can be used. Examples of the alcohol include trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as pentaerythritol, diglycerin, and di(trimethylolpropane); pentahydric alcohols such as triglycerin; and hexahydric alcohols such as dipentaerythritol. The alcohol may be a glycidyl ether or glycidol that reacts with a carboxylic acid to form an ester. The alcohol may be used alone or in combination of two or more.

[0046] In one embodiment, the alcohol is preferably a trihydric to hexahydric alcohol, and more preferably glycerin, pentaerythritol, diglycerin, or dipentaerythritol.

[0047] The rosin esters can be obtained by various known methods. Specifically, the rosin esters can be obtained, for example, by reacting the rosins with the alcohols at a temperature of about 150 to 300°C for about 1 to 24 hours. The amounts of the rosins and alcohols used are not particularly limited. In one embodiment, the amounts of the rosins and alcohols used are typically determined so that the OH group of the alcohol / COOH group of the rosins (equivalent ratio) is about 0.8 to 8, preferably about 1.1 to 1.3.

[0048] In one embodiment, the esterification reaction in the method for producing rosin esters may be carried out in the presence of a catalyst to shorten the reaction time. Examples of the catalyst include acid catalysts such as paratoluenesulfonic acid, acetic acid, methanesulfonic acid, hypophosphorous acid, and sulfuric acid; metal hydroxides such as calcium hydroxide and magnesium hydroxide; metal oxides such as calcium oxide and magnesium oxide; and metal salts such as iron chloride and calcium formate. A single catalyst may be used, or two or more catalysts may be used in combination. Furthermore, water is produced as a result of the esterification reaction. Therefore, the reaction can be carried out while removing the produced water from the system. In one embodiment, considering the color tone of the resulting rosin esters, the reaction is preferably carried out in an inert gas stream. In one embodiment, the reaction may be carried out under pressure, if necessary.

[0049] In one embodiment, the method for producing rosin esters may involve reacting the rosins and alcohols in an organic solvent that is non-reactive with the rosins and alcohols. Examples of such organic solvents include hexane, cyclohexane, toluene, and xylene. When an organic solvent is used, the organic solvent or unreacted raw materials can be removed by vacuum distillation, if necessary.

[0050] In one embodiment, in the method for producing rosin esters, the obtained rosin esters may be further subjected to various treatments such as the purification, hydrogenation, disproportionation, and modification with an α,β-unsaturated carboxylic acid. The various treatments may be performed alone or in combination of two or more.

[0051] In one embodiment, the method for producing the polymerized rosin ester or the α,β-unsaturated carboxylic acid-modified rosin ester may further include reacting the polymerized rosin or the α,β-unsaturated carboxylic acid-modified rosin and the alcohol with unmodified rosin.

[0052] In one embodiment, the method for producing the hydrogenated rosin ester, the disproportionated rosin ester, the polymerized rosin ester, and the α,β-unsaturated carboxylic acid-modified rosin ester may be a method in which a reaction product of the unmodified rosin and the alcohol is subjected to hydrogenation, disproportionation, polymerization, and modification with an α,β-unsaturated carboxylic acid, respectively.

[0053] In the rosin esters, the content of components having a weight-average molecular weight of 300 or less contained in the rosin esters is, for example, 5.0 mass%, 4.9 mass%, 4.8 mass%, 4.7 mass%, 4.6 mass%, 4.5 mass%, 4.4 mass%, 4.3 mass%, 4.2 mass%, 4.1 mass%, 4.0 mass%, 3.9 mass%, 3.8 mass%, 3.7 mass%, 3.6 mass%, 3.5 mass%, 3.4 mass%, 3.3 mass%, 3.2 mass%, 3.1 mass%, 3.0 mass%, 2.9 mass%, Examples of the rosin esters include 2.8 mass%, 2.7 mass%, 2.6 mass%, 2.5 mass%, 2.4 mass%, 2.3 mass%, 2.2 mass%, 2.1 mass%, 2.0 mass%, 1.9 mass%, 1.8 mass%, 1.7 mass%, 1.6 mass%, 1.5 mass%, 1.4 mass%, 1.3 mass%, 1.2 mass%, 1.1 mass%, 1.0 mass%, 0.9 mass%, 0.8 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.4 mass%, 0.3 mass%, 0.2 mass%, 0.1 mass%, 0 mass%, etc. In one embodiment, the content of the component having a weight-average molecular weight of 300 or less contained in the rosin esters is preferably 5.0 mass% or less, more preferably 4.1 mass% or less, and even more preferably 1.5 mass% or less, from the viewpoint of being able to impart higher adhesive strength to the aqueous pressure-sensitive adhesive composition.

[0054] In the present disclosure, the content of components having a weight-average molecular weight of 300 or less contained in rosin esters is determined from the ratio of peak areas of polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC), i.e., by dividing the sum of the peak areas of components having a molecular weight of 300 or less as determined by GPC analysis by the sum of the areas of all peaks of the rosin esters.

[0055] There are no particular limitations on the method for removing components contained in the rosin esters that have a weight-average molecular weight of 300 or less. Specific examples of methods for removing components contained in the rosin esters that have a weight-average molecular weight of 300 or less include reduced pressure distillation, molecular distillation, steam distillation, and solvent extraction.

[0056] The reduced pressure distillation method is, for example, a method in which treatment is continued under conditions of a temperature of about 220 to 300°C and a pressure of about 0.01 to 3 kPa until the content of components having a molecular weight of 300 or less becomes 5.0 mass% or less.

[0057] The steam distillation method typically includes a method in which steam heated and pressurized to 0.1 to 1 MPa is continuously blown into the mixture at a temperature of about 220 to 300°C under normal pressure until the content of components having a molecular weight of 300 or less becomes 5.0% by mass or less.

[0058] The solvent extraction method may, for example, be a method in which the rosin esters are crushed and extracted with a solvent that dissolves only components having a molecular weight of 300 or less. Examples of the solvent that can be used include aliphatic hydrocarbons such as hexane and heptane, and alcohols such as methanol and ethanol.

[0059] (Rosin Phenolic Resin) The rosin phenolic resin is obtained by reacting the unmodified rosin with a phenol.

[0060] The phenols are not particularly limited, and various known phenols can be used. The phenols may be used alone or in combination of two or more.

[0061] Examples of the phenols include phenol, naphthols, alkylphenols, and arylphenols.

[0062] Examples of the alkylphenols include o-cresol, o-normal butylphenol, o-isobutylphenol, o-tertiary butylphenol, o-pentylphenol, o-(cyclohexyl)phenol, o-octylphenol, o-nonylphenol, m-cresol, m-normal butylphenol, m-isobutylphenol, m-tertiary butylphenol, m-pentylphenol, m-(cyclohexyl)phenol, m-octylphenol, m-nonylphenol, p-cresol, p-normal butylphenol, p-isobutylphenol, p-tertiary butylphenol, p-pentylphenol, p-(cyclohexyl)phenol, p-octylphenol, and p-nonylphenol.

[0063] The phenols are not particularly limited, and various known phenols can be used. Specific examples include alkylphenols such as cresol, butylphenol, octylphenol, and nonylphenol, phenol, bisphenols, and naphthols. These may be used alone or in combination of two or more.

[0064] The method for producing the rosin phenolic resin is not particularly limited. Specifically, the method for producing the rosin phenolic resin may include, for example, a method in which the unmodified rosin and a phenol are heated and reacted, if necessary, in the presence of an acid catalyst. In one embodiment, the reaction temperature is typically about 180 to 350°C. In one embodiment, the reaction time is typically about 6 to 18 hours. In one embodiment, the amount of phenol used in the method for producing the rosin phenolic resin is typically about 0.8 to 1.5 moles per mole of the unmodified rosin.

[0065] The acid catalyst is not particularly limited. Specific examples of the acid catalyst include inorganic acid catalysts such as sulfuric acid, hydrogen chloride, and boron trifluoride, and organic acid catalysts such as paratoluenesulfonic acid and methanesulfonic acid. In one embodiment, the amount of the acid catalyst used is about 0.01 to 1.0 part by mass per 100 parts by mass of the unmodified rosin.

[0066] In one embodiment, the rosin phenolic resin may be an ester obtained by further reacting the resin obtained by the above reaction with an alcohol. The alcohol used in this case is not particularly limited, and examples thereof include those mentioned above in connection with the disclosure of rosin esters.

[0067] In one embodiment, the component (a1) preferably includes at least one selected from the group consisting of rosin esters and rosin phenolic resins from the viewpoint of providing excellent emulsification properties for the water-dispersed composition and imparting high adhesive strength to the water-based pressure-sensitive adhesive composition; from the same viewpoint, it more preferably includes at least one selected from the group consisting of polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters, and rosin phenolic resins; and from the same viewpoint, it is even more preferably includes at least one selected from the group consisting of polymerized rosin esters and rosin phenolic resins.

[0068] In one embodiment, component (a1) may optionally contain various known additives as long as the object of the present disclosure is achieved. Examples of additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers. The above additives may be used alone or in combination of two or more.

[0069] Examples of the antioxidant include phenol sulfides, thiophosphites, phosphorus compounds, hindered phenols, and xanthones.

[0070] <Petroleum Resin (a2)> The component (a2) is not particularly limited as long as it is a petroleum resin, and various known resins can be used. As the component (a2), one type may be used alone, or two or more types may be used in combination.

[0071] Examples of the component (a2) include various known petroleum resins, such as aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, alicyclic-aromatic petroleum resins, pure monomer resins, and hydrogenated products thereof (hereinafter, these hydrogenated products are referred to as hydrogenated petroleum resins).

[0072] Examples of the aliphatic petroleum resin include C5 petroleum resins obtained from C5 petroleum fractions of naphtha. Examples of C5 petroleum fractions include conjugated diolefinic unsaturated hydrocarbons having 4 to 6 carbon atoms, such as isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, and methylcyclopentadiene; monoolefinic unsaturated hydrocarbons having 4 to 6 carbon atoms, such as butene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, and cyclopentene; aliphatic saturated hydrocarbons, such as cyclopentane, 2-methylpentane, 3-methylpentane, and n-hexane; and mixtures thereof.

[0073] Examples of the alicyclic petroleum resin include dicyclopentadiene petroleum resins obtained from cyclopentadiene petroleum fractions of naphtha. Examples of the cyclopentadiene petroleum fraction include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, and their dimers, trimers, co-dimers, and mixtures thereof. Examples of the dimer include dicyclopentadiene.

[0074] Examples of the aromatic petroleum resin include C9 petroleum resins obtained from C9 petroleum fractions of naphtha, copolymers obtained by polymerizing the C9 petroleum resins alone or in combination, etc. Examples of the C9 petroleum fraction include aromatic compounds having 8 carbon atoms such as styrene, aromatic compounds having 9 carbon atoms such as α-methylstyrene, β-methylstyrene, vinyltoluene, and indene, aromatic compounds having 10 carbon atoms such as 2-isopropenyltoluene, 4-isopropenyltoluene, 1-methylindene, 2-methylindene, and 3-methylindene, aromatic compounds having 11 carbon atoms such as 2,3-dimethylindene and 2,5-dimethylindene, and mixtures thereof.

[0075] Examples of the aliphatic / aromatic petroleum resin include C5 / C9 copolymer petroleum resins obtained from the C5 petroleum fraction and C9 petroleum fraction.

[0076] Examples of the alicyclic / aromatic petroleum resins include cyclopentadiene / C9 copolymer petroleum resins obtained from the cyclopentadiene petroleum fraction and C9 petroleum fraction. Specific examples of the cyclopentadiene / C9 copolymer petroleum resins include dicyclopentadiene / styrene copolymer petroleum resins and dicyclopentadiene / C9 copolymer petroleum resins.

[0077] Examples of the pure monomer resin include resins obtained by polymerizing polymerizable monomers (styrene, vinyltoluene, α-methylstyrene, isopropenyltoluene, indene) obtained by refining the C9 petroleum fraction, by cationic polymerization, radical polymerization, or the like.

[0078] The hydrogenated petroleum resin can be obtained by various known means. Specifically, the hydrogenated petroleum resin can be obtained, for example, by hydrogenating the various petroleum resins (aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, alicyclic-aromatic petroleum resins, and pure monomer resins) under known hydrogenation conditions.

[0079] The hydrogenation conditions are not particularly limited, and various known hydrogenation methods can be used. Specifically, examples of hydrogenation conditions include heating the various petroleum resins (aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, alicyclic-aromatic petroleum resins, and pure monomer resins) in the presence of a hydrogenation catalyst at a hydrogen partial pressure of about 0.2 to 30 MPa and a temperature of about 200 to 350°C. Examples of hydrogenation catalysts include metals such as nickel, palladium, cobalt, ruthenium, platinum, and rhodium, as well as oxides of these metals. In one embodiment, the amount of hydrogenation catalyst used is preferably about 0.01 to 10 parts by mass per 100 parts by mass of the raw material resin.

[0080] In one embodiment, the hydrogenation may be carried out by melting the various petroleum resins (aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, alicyclic-aromatic petroleum resins, pure monomer resins) or dissolving them in a solvent. The solvent for dissolving the petroleum resin is not particularly limited, as long as it is inert to the reaction and easily dissolves the raw materials and products. Specific examples of the solvent include cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, and dioxane. In one embodiment, one of the solvents may be used alone, or two or more may be used in combination. In one embodiment, the amount of the solvent used is typically 10% by mass or more of the nonvolatile content relative to the petroleum resin, preferably about 10 to 70% by mass of the nonvolatile content.

[0081] The above hydrogenation conditions are explained for the case where a batch reaction system is used as the reaction system, but a flow reaction system (fixed bed system, fluidized bed system, etc.) can also be used as the reaction system.

[0082] In one embodiment, the component (a2) preferably contains at least one selected from the group consisting of aliphatic petroleum resins, aromatic petroleum resins, aliphatic / aromatic petroleum resins, and hydrogenated petroleum resins, from the viewpoint of providing excellent emulsification properties for the water-dispersed composition and imparting high adhesive strength to the water-based pressure-sensitive adhesive / adhesive composition; from the same viewpoint, it more preferably contains at least one selected from the group consisting of aliphatic petroleum resins, aromatic petroleum resins, and aliphatic / aromatic petroleum resins; and from the same viewpoint, it is even more preferably contains at least one selected from the group consisting of C5 petroleum resins, C9 petroleum resins, and C5 / C9 copolymer petroleum resins.

[0083] In one embodiment, component (a2) may optionally contain various known additives as long as the object of the present disclosure is achieved. Examples of additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers. The above additives may be used alone or in combination of two or more.

[0084] Examples of the antioxidant include phenol sulfides, thiophosphites, phosphorus compounds, hindered phenols, and xanthones.

[0085] <Terpene Resin (a3)> The component (a3) ​​is not particularly limited as long as it is a terpene resin, and various known resins can be used. The component (a3) ​​may be used alone or in combination of two or more.

[0086] Examples of the component (a3) ​​include resins obtained by copolymerizing known terpenes and phenols. In one embodiment, the component (a3) ​​may be hydrogenated.

[0087] In one embodiment, component (a3) ​​may optionally contain various known additives as long as the object of the present disclosure is achieved. Examples of additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers. The above additives may be used alone or in combination of two or more.

[0088] Examples of the antioxidant include phenol sulfides, thiophosphites, phosphorus compounds, hindered phenols, and xanthones.

[0089] In one embodiment, the component (A) preferably includes at least one selected from the group consisting of the component (a1) and the component (a2) from the viewpoint of providing excellent emulsification properties for the water-dispersed composition and imparting high adhesive strength to the water-based pressure-sensitive adhesive composition; from the same viewpoint, it more preferably includes at least one selected from the group consisting of rosin esters, rosin phenolic resins, aliphatic petroleum resins, aromatic petroleum resins, and aliphatic-aromatic petroleum resins; and from the same viewpoint, it is even more preferably includes at least one selected from the group consisting of polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters, rosin phenolic resins, C5 petroleum resins, C9 petroleum resins, and C5 / C9 copolymer petroleum resins.

[0090] (Physical Properties of Resin (A)) Examples of the softening point of the (A) component include 190°C, 185°C, 180°C, 175°C, 170°C, 165°C, 160°C, 155°C, 150°C, 145°C, 140°C, 135°C, 130°C, 125°C, 120°C, 115°C, 110°C, 105°C, 100°C, and 95°C. In one embodiment, the softening point of the (A) component is preferably 95°C or higher, more preferably 95 to 190°C, even more preferably 130°C or higher, even more preferably 130 to 190°C, still more preferably 140 to 190°C, and particularly preferably 160 to 190°C, from the viewpoint of being able to impart high adhesive strength to the aqueous pressure-sensitive adhesive composition. In the present disclosure, the softening point is a value measured by the ring and ball method (JIS K5902).

[0091] If the softening point of the component (A) is less than 95°C, the aqueous dispersion composition tends to be unable to impart sufficient adhesive strength to the aqueous pressure-sensitive adhesive composition.

[0092] Furthermore, the higher the softening point of the component (A) in the aqueous dispersion composition, the greater the adhesive strength that can be imparted to the aqueous pressure-sensitive adhesive composition.

[0093] In the present disclosure, when the component (A) contains two or more resins, the softening point of the component (A) is a value calculated by summing the values ​​obtained by multiplying the softening point of each resin by the mass ratio of each resin (the content ratio of each resin relative to the total amount of the component (A)).

[0094] The acid value of the component (A) is, for example, 100 mgKOH / g, 95 mgKOH / g, 90 mgKOH / g, 85 mgKOH / g, 80 mgKOH / g, 75 mgKOH / g, 70 mgKOH / g, 65 mgKOH / g, 60 mgKOH / g, 55 mgKOH / g, 50 mgKOH / g, 45 mgKOH / g, 40 mgKOH / g, 35 mgKOH / g, 30 mgKOH / g, 25 mgKOH / g, 20 mgKOH / g, 19 mgKOH / g,

[0033] In one embodiment, the acid value of the component (A) is preferably 100 mgKOH / g or less, more preferably 50 mgKOH / g or less, even more preferably 20 mgKOH / g or less, and even more preferably 15 mgKOH / g or less, from the viewpoint of excellent emulsification properties of the water-dispersed composition and imparting high adhesive strength to the water-based pressure-sensitive adhesive composition. In the present disclosure, the acid value is a value measured according to JIS K0070.

[0095] If the acid value of the component (A) exceeds 100 mgKOH / g, the emulsifiability of the aqueous dispersion composition tends to decrease, and the aqueous pressure-sensitive adhesive composition tends not to be able to impart sufficient adhesive strength.

[0096] In the present disclosure, when the component (A) contains two or more types of resins, the acid value of the component (A) is a value calculated by summing the values ​​obtained by multiplying the acid value of each resin by the mass ratio of each resin (the content ratio of each resin to the total amount of the component (A)).

[0097] In one embodiment, component (A) may optionally contain various known additives as long as the object of the present disclosure is achieved. Examples of additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers. The above additives may be used alone or in combination of two or more.

[0098] Examples of the antioxidant include phenol sulfides, thiophosphites, phosphorus compounds, hindered phenols, and xanthones.

[0099] The content of the additive is not particularly limited. Examples of the content of the additive per 100 parts by mass of the component (A) include 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, and 0.1 parts by mass. In one embodiment, the content of the additive is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A).

[0100] <Copolymer (B)> The component (B) is a copolymer containing a structural unit (b1) (hereinafter also referred to as structural unit (b1)) derived from a hydrophilic unsaturated monomer and a structural unit (b2) (hereinafter also referred to as structural unit (b2)) derived from a hydrophobic unsaturated monomer, and the structural unit (b1) contains a structural unit derived from (meth)allylsulfonic acid or a salt thereof, and the structural unit (b2) contains a structural unit derived from an aromatic vinyl compound, and various known structural units can be used without any particular limitation. The component (B) may be used alone or in combination of two or more types.

[0101] In one embodiment, the component (B) may be a salt obtained by neutralizing the copolymer with a base. The salt is not particularly limited. Examples of the salt include alkali metal salts such as sodium salts and potassium salts, ammonium salts, and amine salts such as methylamine and ethanolamine.

[0102] <Structural Unit (b1) Derived from Hydrophilic Unsaturated Monomer> The structural unit (b1) is a structural unit contained in a polymer chain when a polymer is produced using a hydrophilic unsaturated monomer (b1′) (hereinafter also referred to as component (b1′)). One type of component (b1′) may be used alone, or two or more types may be used in combination.

[0103] The component (b1') is not particularly limited, and various known compounds can be used, as long as they have one polymerizable carbon-carbon double bond in the molecule, at least one hydrophilic functional group in the molecule, and a solubility of 7 g or more in 100 g of water at 20° C. Examples of the hydrophilic functional group include a hydroxyl group, a carboxyl group (including salts thereof), a sulfonic acid group (including salts thereof), a phosphate group (including salts thereof), a quaternary amino group, and a polyoxyalkylene group.

[0104] In the present disclosure, the "polymerizable carbon-carbon double bond" includes, for example, a (meth)acryloyl group, a 1-propenyl group (hereinafter also referred to as an allyl group), a 2-methyl-1-propenyl group (hereinafter also referred to as a methallyl group), an isopropenyl group, a vinyl group, and the like.

[0105] The component (b1') contains (meth)allylsulfonic acid or a salt thereof. Since the component (b1') contains (meth)allylsulfonic acid or a salt thereof, the component (B) can sufficiently emulsify the component (A) in water, and therefore the aqueous dispersion composition has excellent emulsifiability and can impart sufficient adhesive strength to the aqueous pressure-sensitive adhesive composition.

[0106] Examples of the salts of (meth)allylsulfonic acid include alkali metal salts of (meth)allylsulfonic acid (sodium salt, potassium salt), amine salts of (meth)allylsulfonic acid, and ammonium salts of (meth)allylsulfonic acid.

[0107] In one embodiment, component (b1') may optionally contain an unsaturated compound other than the (meth)allylsulfonic acid or a salt thereof, as long as the object of the present disclosure is achieved. Examples of such unsaturated compounds include anionic unsaturated compounds, hydroxyl group-containing (meth)acrylates having 5 to 9 carbon atoms, hydroxyalkyl vinyl ethers having 4 to 7 carbon atoms, hydroxyl group-containing allyl ethers having 4 to 6 carbon atoms, quaternary amino group-containing unsaturated compounds, polyoxyalkylene group-containing unsaturated compounds, and acrylonitrile.

[0108] The anionic unsaturated compound is not particularly limited as long as it has one polymerizable carbon-carbon double bond in the molecule and at least one anionic functional group in the molecule, and various known compounds can be used.

[0109] Examples of the anionic unsaturated compound include a carboxyl group-containing unsaturated compound, a sulfonic acid group-containing unsaturated compound other than (meth)allylsulfonic acid, a phosphoric acid group-containing unsaturated compound, and salts thereof. The anionic unsaturated compound may be used alone or in combination of two or more.

[0110] Examples of the salts of the anionic unsaturated compounds include alkali metal salts such as sodium salts and potassium salts, ammonium salts, and amine salts such as methylamine and ethanolamine.

[0111] Examples of the carboxyl group-containing unsaturated compound and salts thereof include α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; α,β-unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and citraconic anhydride; and salts thereof.

[0112] Examples of the sulfonic acid group-containing unsaturated compound and salts thereof include styrenesulfonic acid, vinylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamido-tert-butylsulfonic acid, sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, and salts thereof.

[0113] Examples of the phosphate group-containing unsaturated compound and salts thereof include mono[2-hydroxyethyl(meth)acrylate] acid phosphate, mono[2-hydroxypropyl(meth)acrylate] acid phosphate, mono[3-hydroxypropyl(meth)acrylate] acid phosphate, mono[3-chloro-2-hydroxypropyl(meth)acrylate] acid phosphate, (meth)allyl alcohol acid phosphate and mono[2-hydroxyethyl(meth)acrylate] acid phosphite, bis((meth)acryloxyethyl)phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, monomethyl-2-(meth)acryloyloxyethyl phosphate, 3-(meth)acryloxy-2-hydroxypropanephosphoric acid, and salts thereof.

[0114] In one embodiment, from the viewpoint of excellent emulsification properties of the water-dispersed composition, the anionic unsaturated compound is preferably at least one selected from the group consisting of the carboxyl group-containing unsaturated compounds, the sulfonic acid group-containing unsaturated compounds, and salts thereof, more preferably at least one selected from the group consisting of the carboxyl group-containing unsaturated compounds and salts thereof, even more preferably at least one selected from the group consisting of itaconic acid, (meth)acrylic acid, styrenesulfonic acid, and salts thereof, and even more preferably at least one selected from the group consisting of itaconic acid, (meth)acrylic acid, and salts thereof.

[0115] The hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms is not particularly limited, and various known compounds can be used, as long as it has one (meth)acryloyl group and one hydroxyl group in the molecule and contains 5 to 9 carbon atoms in the molecule. One type of the hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms may be used alone, or two or more types may be used in combination.

[0116] Examples of the hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms include hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 1-hydroxy-2-methylethyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2 ... ethylpropyl (meth)acrylate, 1-hydroxy-1-methylpropyl (meth)acrylate, 3-hydroxy-1-methylpropyl (meth)acrylate, 1-ethyl-2-hydroxyethyl (meth)acrylate, 1-hydroxy-2-methylpropyl (meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, 3-hydroxy-2-methylpropyl (meth)acrylate, 1,1-dimethyl-2-hydroxyethyl (meth)acrylate, hydroxypentyl (meth)acrylate, and the like.

[0117] In one embodiment, the hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms is preferably a hydroxyl group-containing (meth)acrylate having 5 to 7 carbon atoms, from the viewpoint of excellent emulsification properties of the water-dispersed composition, and more preferably at least one selected from the group consisting of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0118] The hydroxyalkyl vinyl ether having 4 to 7 carbon atoms is not particularly limited, and various known compounds can be used, as long as it has one vinyl group and one hydroxyl group in the molecule and has 4 to 7 carbon atoms in the molecule. The hydroxyalkyl vinyl ether having 4 to 7 carbon atoms may be used alone or in combination of two or more.

[0119] Examples of the hydroxyalkyl vinyl ether having 4 to 7 carbon atoms include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, and 4-hydroxycyclopentyl vinyl ether.

[0120] The hydroxyl group-containing allyl ether having 4 to 6 carbon atoms is not particularly limited, and various known compounds can be used, as long as it has one allyl group and at least one hydroxyl group in the molecule and has 4 to 6 carbon atoms in the molecule. The hydroxyl group-containing allyl ether having 4 to 6 carbon atoms may be used alone or in combination of two or more.

[0121] Examples of the hydroxyl group-containing allyl ether include 3-allyloxy-1,2-propanediol and glycerol α-monoallyl ether.

[0122] The quaternary amino group-containing unsaturated compound is not particularly limited, and various known compounds can be used, as long as they are quaternized by reacting a tertiary amino group-containing unsaturated compound described below with a quaternizing agent. The quaternary amino group-containing unsaturated compound may be used alone or in combination of two or more.

[0123] The tertiary amino group-containing unsaturated compound is not particularly limited as long as it is a compound having one polymerizable carbon-carbon double bond and one tertiary amino group in the molecule, and various known compounds can be used.

[0124] Examples of the tertiary amino group-containing unsaturated compound include N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminomethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminomethyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminomethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate. amide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, 3-diethylamino-2-hydroxypropyl(meth)acrylate, 3-(N',N'-dimethylamino-N-methylamino)-2-hydroxypropyl(meth)acrylate, 3-dimethylamino-2-hydroxypropyl(meth)acrylamide, 3-diethylamino-2-hydroxypropyl(meth)acrylamide, 3-allyloxy-2-hydroxypropyldimethylamine, vinylbenzyldimethylamine, and 4-(vinylbenzyl)morpholine.

[0125] The quaternizing agent is not particularly limited. Examples of the quaternizing agent include oxides, organic halides, dimethyl sulfate, diethyl sulfate, etc. Examples of the oxides include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide; styrene oxide, etc. Examples of the organic halides include methyl halides, ethyl halides, benzyl halides, epihalohydrin, glycidyl trimethyl ammonium halide, and 3-chloro-2-hydroxyammonium halide. The quaternizing agents may be used alone or in combination of two or more.

[0126] The polyoxyalkylene group-containing unsaturated compound is not particularly limited, and any known compound can be used as long as it has one polymerizable carbon-carbon double bond and at least one polyoxyalkylene group in the molecule. One type of the polyoxyalkylene group-containing unsaturated compound may be used alone, or two or more types may be used in combination.

[0127] Examples of the polyoxyalkylene group-containing unsaturated compound include polyalkylene glycol mono(meth)acrylate, polyalkylene glycol monovinyl ether, and reactive emulsifiers.

[0128] Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxyisopropylene group, a polyoxybutylene group, and block products thereof.

[0129] Examples of the polyalkylene glycol mono(meth)acrylate include polymethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0130] Examples of the polyalkylene glycol monovinyl ether include polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and polypropylene glycol monovinyl ether.

[0131] The reactive emulsifier is not particularly limited, and various known ones can be used. Examples of the reactive emulsifier include a compound having one polymerizable carbon-carbon double bond in the molecule, at least one hydrophobic group in the molecule, and at least one polyoxyalkylene group having about 2 to 100 repeating units in the molecule. The reactive emulsifiers may be used alone or in combination of two or more.

[0132] Examples of the hydrophobic group include an alkyl group and an aromatic group.

[0133] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cycloalkyl group, and a substituent formed by combining these groups.

[0134] In the present disclosure, a "branched alkyl group" refers to a group that does not have a cyclic structure, in which at least one hydrogen atom of a linear alkyl group is replaced with an alkyl group.

[0135] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a fused ring cycloalkyl group, etc. A cycloalkyl group in which at least one hydrogen atom of the cycloalkyl group is substituted with an alkyl group is also considered to be a cycloalkyl group.

[0136] In this disclosure, "monocyclic ring" refers to a ring structure formed by a covalent carbon bond and having no internal bridges. "Fused ring" refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one edge (fused) with another ring). "Bridged ring" refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0137] The aromatic groups (aryl groups, arylene groups) may be substituted or unsubstituted. Examples of the substituents on the aromatic groups include linear alkyl groups, branched alkyl groups, cycloalkyl groups, thioalkyl groups, thioaryl groups, and carbonylaryl groups. Examples of the aryl groups include monocyclic aryl groups and fused ring aryl groups. Examples of the monocyclic aryl groups include phenyl groups, tolyl groups, and mesityl groups. Examples of the fused ring aryl groups include naphthyl groups. Examples of the arylene groups include monocyclic arylene groups and fused ring arylene groups. Examples of the monocyclic arylene groups include phenylene groups and tolylene groups. Examples of the fused ring arylene groups include naphthylene groups.

[0138] Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxyisopropylene group, a polyoxybutylene group, and block products thereof.

[0139] Examples of the reactive emulsifier include polyoxyethylene alkyl ethers having at least one polymerizable carbon-carbon double bond, one hydrophobic group, and one polyoxyalkylene group having about 2 to 100 repeating units in the molecule (hereinafter, these substituents are also collectively referred to as specific functional groups), polyoxyethylene phenyl ethers having at least one specific functional group in the molecule, polyoxyethylene alkyl phenyl ethers having at least one specific functional group in the molecule, and sulfosuccinate salts thereof, sulfate salts thereof, phosphate salts thereof, aliphatic carboxylate salts thereof, and aromatic carboxylate salts thereof.

[0140] Examples of the reactive emulsifier include those described in JP-A-63-23725, JP-A-63-240931, JP-A-62-104802, JP-A-4-50204, JP-A-4-53802, JP-A-4-256429, JP-A-9-324394, JP-A-2003-293288, and JP-A-2010-242280.

[0141] In one embodiment, from the viewpoint of environmental protection, the reactive emulsifier is preferably not one containing nonylphenol ethoxylate, for example, a reactive emulsifier having a polyoxyethylene nonylphenyl ether structure.

[0142] In one embodiment, the component (b1') is, from the viewpoint of excellent emulsification properties of the water-dispersed composition, preferably the anionic unsaturated compound and the hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms. It includes at least one selected from the group consisting of, more preferably, the carboxyl group-containing unsaturated compound and its salt, the sulfonic acid group-containing unsaturated compound and its salt, and the hydroxyl group-containing (meth)acrylate having 5 to 7 carbon atoms. It includes at least one selected from the group consisting of, more preferably, the carboxyl group-containing unsaturated compound and its salt, and the hydroxyl group-containing (meth)acrylate having 5 to 7 carbon atoms. It includes at least one selected from the group consisting of, more preferably, itaconic acid, (meth)acrylic acid, styrene sulfonic acid and salts thereof, and hydroxypropyl (meth)acrylate. It includes at least one selected from the group consisting of, more preferably, itaconic acid, (meth)acrylic acid and salts thereof, and hydroxypropyl (meth)acrylate.

[0143] <Structural Unit (b2) Derived from Hydrophobic Unsaturated Monomer> The structural unit (b2) is a structural unit contained in a polymer chain when a polymer is produced using a hydrophobic unsaturated monomer (b2') (hereinafter also referred to as component (b2')). One type of component (b2') may be used alone, or two or more types may be used in combination.

[0144] The component (b2') is not particularly limited, and various known compounds can be used, as long as they have one polymerizable carbon-carbon double bond in the molecule, at least one hydrophobic functional group in the molecule, and a solubility of 0 to 6.0 g in 100 g of water at 20° C. Examples of the hydrophobic functional group include the hydrophobic groups described above in connection with the disclosure of the reactive emulsifier.

[0145] The component (b2') contains an aromatic vinyl compound. Since the component (B) contains an aromatic vinyl compound, the component (A) can be sufficiently emulsified in water, and therefore the aqueous dispersion composition has excellent emulsification properties.

[0146] The aromatic vinyl compound is not particularly limited as long as it has one vinyl group and at least one aromatic group in the molecule, and various known compounds can be used. The aromatic group may have a substituent or may not have a substituent. Examples of the aromatic group include the aromatic groups described above in relation to the disclosure of the reactive emulsifier. The aromatic vinyl compound may be used alone or in combination of two or more.

[0147] Examples of the aromatic vinyl compound include styrenes such as styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, and hydroxystyrene; vinyltoluenes such as vinyltoluene and chlorovinyltoluene; allyltoluenes such as allylbenzene, p-allyltoluene, and o-allyltoluene; vinylnaphthalene; and vinylanthracene.

[0148] In one embodiment, the aromatic vinyl compound is preferably a styrene, more preferably at least one selected from the group consisting of styrene and α-methylstyrene, in terms of excellent emulsification properties of the water-dispersed composition.

[0149] In one embodiment, component (b2') may optionally contain an unsaturated compound other than the aromatic vinyl compound, as long as the object of the present disclosure is achieved. Examples of such unsaturated compounds include alkyl (meth)acrylates, vinyl carboxylic acid esters, unsaturated dicarboxylic acid alkyl esters, α-olefins, alkyl vinyl ethers, and methacrylonitrile.

[0150] Examples of the alkyl (meth)acrylate include (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 20 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, tertiary butyl, normal octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, octadecenyl, docosyl, cyclopentyl, and cyclohexyl groups. One type of alkyl (meth)acrylate may be used alone, or two or more types may be used in combination.

[0151] In one embodiment, the alkyl (meth)acrylate is preferably a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, from the viewpoint of excellent emulsification properties of the water-dispersed composition, and more preferably at least one selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0152] Examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl laurate, etc. The vinyl carboxylate may be used alone or in combination of two or more.

[0153] Examples of the unsaturated dicarboxylic acid alkyl ester include monoalkyl esters and dialkyl esters of the above-mentioned α,β-unsaturated dicarboxylic acids. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, octadecenyl, docosyl, cyclopentyl, and cyclohexyl. The above unsaturated dicarboxylic acid alkyl esters may be used alone or in combination of two or more.

[0154] Examples of the α-olefin include α-olefins having an alkyl group with 6 to 22 carbon atoms. Examples of the α-olefin include 2,4,4-trimethylpentene-1, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-tetracosene, 1-triacontene, cyclohexene, methylcyclohexene, vinylcyclohexane, 4-vinylcyclohexene, cyclopentene, and methylcyclopentene. One type of the α-olefin may be used alone, or two or more types may be used in combination.

[0155] Examples of the alkyl vinyl ether include alkyl vinyl ethers in which the number of carbon atoms in the alkyl group is 1 to 22. The alkyl vinyl ethers may be used alone or in combination of two or more.

[0156] In one embodiment, the component (b2') preferably contains the alkyl (meth)acrylate, more preferably contains a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, from the viewpoint of excellent emulsification properties of the water-dispersed composition, and even more preferably contains at least one selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0157] (Structural Unit (b3) Derived from Other Unsaturated Monomers) In one embodiment, the component (B) may optionally include a structural unit (b3) derived from another unsaturated monomer (hereinafter also referred to as structural unit (b3)), as long as the object of the present disclosure is achieved.

[0158] The structural unit (b3) is a structural unit contained in a polymer chain when a polymer is produced using another unsaturated monomer (b3') (hereinafter also referred to as the component (b3')). The component (b3') may be used alone or in combination of two or more types.

[0159] The component (b3') is not particularly limited as long as it is a compound other than the components (b1') and (b2') that has at least one polymerizable carbon-carbon double bond in the molecule, and various known compounds can be used.

[0160] Examples of the component (b3') include chain transfer unsaturated compounds, the above-mentioned tertiary amino group-containing unsaturated compounds, and crosslinkable unsaturated compounds.

[0161] The chain transfer unsaturated compound is not particularly limited, and various known compounds can be used as long as they have one polymerizable carbon-carbon double bond and one chain transfer functional group in the molecule. Note that the chain transfer unsaturated compound does not include (meth)allylsulfonic acid or a salt thereof.

[0162] Examples of the chain transfer unsaturated compound include N-substituted acrylamide, α-methylstyrene dimer, 2,4-diphenyl-4-methyl-1-pentene, etc. Examples of the N-substituted acrylamide include dimethyl(meth)acrylamide, isopropyl(meth)acrylamide, methylol(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine, etc.

[0163] The crosslinkable unsaturated compound is not particularly limited as long as it is a compound having at least two polymerizable carbon-carbon double bonds in the molecule, and various known compounds can be used.

[0164] Examples of the crosslinkable unsaturated compound include divinylbenzene, trivinylbenzene, divinyl sulfone, hexanediol di(meth)acrylate, 1,9-nonanediol diacrylate, dicyclopentanyl di(meth)acrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,3,5-tri(meth)acryloylhexahydro-1,3,5-triazine, ethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, hexaethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene ... Examples of the copolymer include acrylate, diacrylamide dimethyl ether, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-propylenebis(meth)acrylamide, N,N'-butylenebis(meth)acrylamide, N-[tris(3-(meth)acrylamidopropoxymethyl)methyl](meth)acrylamide, N,N-bis(2-(meth)acrylamidoethyl)(meth)acrylamide, N,N-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bis(meth)acrylamide, N,N-1,2-ethanediylbis{N-[2-((meth)acryloylamino)ethyl](meth)acrylamide}, and conjugated dienes.

[0165] Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear conjugated pentadiene, substituted and side-chain conjugated hexadiene, etc. One type of the conjugated diene may be used alone, or two or more types may be used in combination.

[0166] In one embodiment, it is not preferable for component (B) to contain a structural unit derived from (meth)acrylamide. If (meth)acrylamide is contained in the raw materials when producing component (B), the production of component (B) tends to be difficult due to the low reactivity of (meth)acrylamide with the aromatic vinyl compound. Furthermore, if component (B) contains a structural unit derived from (meth)acrylamide, component (B) tends to be unable to sufficiently emulsify component (A) in water.

[0167] (Content of Each Structural Unit) In the component (B), the molar ratio of the structural unit (b1) to the structural unit (b2) ((b1) / (b2)) is, for example, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, or 0.3. In one embodiment, the molar ratio of the structural unit (b1) to the structural unit (b2) ((b1) / (b2)) is preferably 0.3 to 3.0, and more preferably 0.5 to 2.5, in view of excellent emulsifiability of the water-dispersed composition.

[0168] In the (B) component, when the molar ratio ((b1) / (b2)) exceeds 3.0, or when the molar ratio ((b1) / (b2)) is less than 0.3, the emulsifiability of the water-dispersed composition tends to decrease.

[0169] In the component (B), the content of the structural unit (b1) is not particularly limited. Examples of the content of the structural unit (b1) in the component (B), relative to 100% by mass of the component (B), include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 20% by mass. In one embodiment, the content of the structural unit (b1) in the component (B), relative to 100% by mass of the component (B), is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, even more preferably 30 to 75% by mass, and even more preferably 30 to 70% by mass.

[0170] The content of the structural unit (b1) in the component (B) is, for example, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, etc., relative to 100 mol% of the component (B). In one embodiment, the content of the structural unit (b1) in the component (B) is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 75 mol%, and even more preferably 30 to 70 mol%, relative to 100 mol% of the component (B).

[0171] Within the component (B), there are no particular limitations on the amount of structural units derived from (meth)allylsulfonic acid or salts thereof (hereinafter, also referred to as structural units (b1-1)). The content of the structural unit (b1-1) in component (B) is, for example, 20% by mass, 19% by mass, 18% by mass, 17% by mass, 16% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 3% by mass, based on 100% by mass of component (B). , 2% by mass, 1% by mass, 0.9% by mass, 0.8% by mass, 0.7% by mass, 0.6% by mass, 0.5% by mass, 0.3% by mass, 0.2% by mass, 0.1% by mass, 0.09% by mass %, 0.08% by mass, 0.07% by mass, 0.06% by mass, 0.05% by mass, 0.04% by mass, 0.03% by mass, 0.02% by mass, 0.01% by mass, and the like. In one embodiment, the amount of the structural unit (b1-1) in the component (B), relative to 100% by mass of the component (B), is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0172] The amount of the structural unit (b1-1) in the component (B), relative to 100% by mass of the component (B), for example, may be 15 mol%, 14 mol%, 13 mol%, 12 mol%, 11 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.8 mol%, 0.7 mol%, 0.6 mol%, 0.5 mol%, 0.3 mol%, 0.2 mol%, 0.1 mol%, 0.09 mol%, 0.08 mol%, 0.07 mol%, 0.06 mol%, 0.05 mol%, 0.04 mol%, 0.03 mol%, 0.02 mol%, or 0.01 mol%. In one embodiment, the amount of the structural unit (b1-1) in the component (B), relative to 100 mol% of the component (B), is preferably 0.01 to 15 mol%, more preferably 0.05 to 10 mol%, and even more preferably 0.05 to 7 mol%.

[0173] In the component (B), there are no particular limitations on the content of the structural unit derived from the hydroxyl group-containing (meth)acrylate having 4 to 9 carbon atoms (hereinafter also referred to as structural unit (b1-2)). The content of the structural unit (b1-2) in the component (B) may be, for example, 25% by mass, 24% by mass, 23% by mass, 22% by mass, 21% by mass, 20% by mass, 19% by mass, 18% by mass, 17% by mass, 16% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, or 6% by mass, relative to 100% by mass of the component (B). , 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.8 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.3 mass%, 0.2 mass%, 0.1 mass%, 0.09 mass%, 0.08 mass%, 0.07 mass%, 0.06 mass%, 0.05 mass%, 0.04 mass%, 0.03 mass%, 0.02 mass%, 0.01 mass%, etc. In one embodiment, the content of the structural unit (b1-2) in the component (B) is preferably 0.01 to 25 mass%, and more preferably 0.05 to 20 mass%, relative to 100 mass% of the component (B).

[0174] The amount of the structural unit (b1-2) in the component (B), relative to 100 mol% of the component (B), for example, may be 20 mol%, 19 mol%, 18 mol%, 17 mol%, 16 mol%, 15 mol%, 14 mol%, 13 mol%, 12 mol%, 11 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.8 mol%, 0.7 mol%, 0.6 mol%, 0.5 mol%, 0.3 mol%, 0.2 mol%, 0.1 mol%, 0.09 mol%, 0.08 mol%, 0.07 mol%, 0.06 mol%, 0.05 mol%, 0.04 mol%, 0.03 mol%, 0.02 mol%, or 0.01 mol%. In one embodiment, the amount of the structural unit (b1-2) in the component (B), relative to 100 mol % of the component (B), is preferably 0.01 to 20 mol %, and more preferably 0.05 to 16 mol %.

[0175] In the component (B), the content of the structural unit (b2) is not particularly limited. Examples of the content of the structural unit (b2) in the component (B), relative to 100% by mass of the component (B), include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 20% by mass. In one embodiment, the content of the structural unit (b2) in the component (B), relative to 100% by mass of the component (B), is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass.

[0176] The content of the structural unit (b2) in the component (B) is, for example, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, etc., relative to 100 mol% of the component (B). In one embodiment, the content of the structural unit (b2) in the component (B) is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and even more preferably 30 to 65 mol%, relative to 100 mol% of the component (B).

[0177] In the component (B), the content of the structural unit derived from the aromatic vinyl compound (hereinafter also referred to as structural unit (b2-1)) is not particularly limited. Examples of the content of the structural unit (b2-1) in the component (B), relative to 100% by mass of the component (B), include 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 19% by mass, 18% by mass, 17% by mass, 16% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, and 1% by mass. In one embodiment, the amount of the structural unit (b2-1) in the component (B), relative to 100% by mass of the component (B), is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and even more preferably 5 to 30% by mass.

[0178] The content of the structural unit (b2-1) in the component (B) is, for example, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 19 mol%, 18 mol%, 17 mol%, 16 mol%, 15 mol%, 14 mol%, 13 mol%, 12 mol%, 11 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, etc., relative to 100 mol% of the component (B). In one embodiment, the content of the structural unit (b2-1) in the component (B) is preferably 1 to 70 mol%, more preferably 5 to 65 mol%, and even more preferably 5 to 30 mol%, relative to 100 mol% of the component (B).

[0179] In the component (B), the content of the structural unit (b3) is not particularly limited. Examples of the content of the structural unit (b3) in the component (B), relative to 100 mass% of the component (B), include 15 mass%, 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.8 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.3 mass%, 0.2 mass%, 0.1 mass%, 0.09 mass%, 0.08 mass%, 0.07 mass%, 0.06 mass%, 0.05 mass%, 0.04 mass%, 0.03 mass%, 0.02 mass%, 0.01 mass%, and 0 mass%, etc. In one embodiment, the amount of the structural unit (b3) in the component (B), relative to 100% by mass of the component (B), is preferably 0 to 15% by mass, more preferably 0.01 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0180] Examples of the content of the structural unit (b3) in the component (B), relative to 100 mol% of the component (B), include 15 mol%, 14 mol%, 13 mol%, 12 mol%, 11 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.8 mol%, 0.7 mol%, 0.6 mol%, 0.5 mol%, 0.3 mol%, 0.2 mol%, 0.1 mol%, 0.09 mol%, 0.08 mol%, 0.07 mol%, 0.06 mol%, 0.05 mol%, 0.04 mol%, 0.03 mol%, 0.02 mol%, 0.01 mol%, and 0 mol%. In one embodiment, the amount of the structural unit (b3) in the component (B), relative to 100 mol% of the component (B), is preferably 0 to 15 mol%, more preferably 0.01 to 15 mol%, and even more preferably 0.05 to 10 mol%.

[0181] (Physical Properties of Copolymer (B)) The physical properties of the component (B) are not particularly limited. Examples of the weight average molecular weight of the component (B) include 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, and 1,000. In one embodiment, the weight average molecular weight of the (B) component is preferably about 1,000 to 500,000, more preferably about 4,000 to 100,000, and even more preferably about 5,000 to 50,000, from the viewpoint of providing excellent emulsification properties of the water-dispersed composition and high adhesive strength to the water-based pressure-sensitive adhesive composition. In the present disclosure, the weight average molecular weight of the (B) component means a polyethylene oxide-equivalent value measured by gel permeation chromatography (GPC).

[0182] (Method for Producing Copolymer (B)) The method for producing copolymer (B) is not particularly limited, as long as it is a method (polymerization method) for polymerizing component (b1') and component (b2'), and optionally component (b3'), and various known methods can be used. Examples of the polymerization method include solution polymerization, emulsion polymerization, and suspension polymerization. The polymerization conditions for the polymerization method are not particularly limited. In one embodiment, the reaction temperature is typically about 80 to 180°C. In one embodiment, the reaction time is typically about 1 to 10 hours. In one embodiment, the polymerization method may use various reaction solvents, radical polymerization initiators, chain transfer agents, and surfactants as needed. In one embodiment, the carboxyl group, sulfonic acid group, and phosphate group contained in the structural unit (b1) in the resulting component (B) may be neutralized with a base as needed.

[0183] The reaction solvent is not particularly limited, and various known solvents can be used. Examples of the reaction solvent include alcohols such as ethyl alcohol and isopropyl alcohol; lower ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; organic solvents such as ethyl acetate, chloroform and dimethylformamide; water; and mixed solvents of such organic solvents with water. The reaction solvents may be used alone or in combination of two or more.

[0184] The radical polymerization initiator is not particularly limited, and various known initiators can be used. Examples of the radical polymerization initiator include inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate; organic peroxides such as t-butyl peroxybenzoate, dicumyl peroxide, and lauryl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate. One type of radical polymerization initiator may be used alone, or two or more types may be used in combination.

[0185] The chain transfer agent is not particularly limited, and various known agents can be used. Examples of the chain transfer agent include oil-soluble chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, cumene, bromotrichloromethane, 2-mercaptobenzothiazole, and 2-mercaptoethanol; and water-soluble chain transfer agents such as ethanethiol, propanethiol, thioglycolic acid, thiomalic acid, dimethyldithiocarbamic acid, isopropyl alcohol, and sodium hypophosphite. The chain transfer agents may be used alone or in combination of two or more.

[0186] The surfactant is not particularly limited, and various known surfactants can be used. Examples of the surfactant include the reactive emulsifiers, anionic surfactants that do not have a polymerizable carbon-carbon double bond in the molecule, and nonionic surfactants. The surfactants may be used alone or in combination of two or more.

[0187] Examples of the anionic surfactant include dialkyl sulfosuccinates, dialkyl sulfosuccinate ester salts, alkanesulfonates, α-olefinsulfonates, polyoxyethylene alkyl ether sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinate ester salts, polyoxyethylene styryl phenyl ether sulfosuccinates, polyoxyethylene styryl phenyl ether sulfosuccinate ester salts, naphthalenesulfonic acid formalin condensates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfates, and polyoxyethylene alkyl phenyl ether sulfate ester salts.

[0188] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, and polyoxyethylene sorbitan fatty acid ester.

[0189] (Surfactant (C)) In one embodiment, the aqueous dispersion composition may optionally contain a surfactant (C) (hereinafter also referred to as component (C)), as long as the object of the present disclosure is achieved.

[0190] By including the component (C), the water-dispersed composition can emulsify the component (A) more sufficiently in water, and therefore the water-dispersed composition has better emulsification properties.

[0191] The component (C) is not particularly limited as long as it is a surfactant, and various known surfactants can be used. The component (C) may be used alone or in combination of two or more types.

[0192] Examples of the component (C) include the reactive emulsifiers, and the anionic surfactants and nonionic surfactants described above in connection with the disclosure of the method for producing the copolymer (B).

[0193] Commercially available products of component (C) include, for example, "Neohitenol S-70" and "Neohitenol F-10" (both manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), "KAYAMER PM-1", "KAYAMER PM-2", and "KAYAMER Representative examples include "PM-21" (manufactured by Nippon Kayaku Co., Ltd.), "SE-10N", "NE-10", "NE-20", "NE-30", "ADEKA REASOAP SR-10", "ADEKA REASOAP SR-20", and "ADEKA REASOAP ER-20" (all manufactured by ADEKA Corporation), "New Frontier A229E", "New Frontier N117E", "New Frontier N250Z", "Aqualon RN-10", "Aqualon RN-20", "Aqualon RN-50", "Aqualon HS-10", "Aqualon KH-05", and "Aqualon KH-10" (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), "Eminol JS-2" (manufactured by Sanyo Chemical Industries, Ltd.), and "Latherm K-180" (manufactured by Kao Corporation).

[0194] In one embodiment, from the standpoint of environmental protection, the reactive emulsifier in component (C) preferably does not contain nonylphenol ethoxylate. Examples of such reactive emulsifiers include reactive emulsifiers having a polyoxyethylene nonylphenyl ether structure.

[0195] (Additives) In one embodiment, the aqueous dispersion composition may optionally contain various known additives as long as the object of the present disclosure is achieved. Examples of additives include crosslinkers, antifoaming agents, thickeners, fillers, UV absorbers, light stabilizers, antioxidants, water-resistant agents, film-forming aids, preservatives, and pH adjusters such as aqueous ammonia and sodium bicarbonate. The additives may be used alone or in combination of two or more.

[0196] Examples of the preservative include thiazoline-based preservatives and benzisothiazole-based preservatives.

[0197] (Content of Each Component) The content of the (B) component in the above-mentioned aqueous dispersion composition is not particularly limited. Examples of the content of the (B) component, in terms of nonvolatile content, per 100 parts by mass of the (A) component include 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, and 1 part by mass. In one embodiment, the content of the (B) component, in terms of nonvolatile content, per 100 parts by mass of the (A) component, is preferably about 1 to 20 parts by mass, more preferably about 2 to 10 parts by mass, in terms of nonvolatile content, in order to achieve excellent emulsification properties of the aqueous dispersion composition.

[0198] The content of the component (C) in the aqueous dispersion composition is not particularly limited. Examples of the content of the component (C), calculated as nonvolatile content, relative to 100 parts by mass of the component (A), include 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, and 0 parts by mass. In one embodiment, the content of the component (C), in terms of nonvolatile content, relative to 100 parts by mass of the component (A), is preferably about 0 to 20 parts by mass, more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.1 to 5 parts by mass, in terms of excellent emulsification properties of the water-dispersed composition.

[0199] The mass ratio of the (B) component to the (C) component ((B) component / (C) component) in the water-dispersed composition is not particularly limited. Examples of the mass ratio of the (B) component to the (C) component ((B) component / (C) component), calculated as nonvolatile content, include 100 / 0, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, and 34 / 66. In one embodiment, the mass ratio of the (B) component to the (C) component ((B) component / (C) component) in the water-dispersed composition, calculated as nonvolatile content, is preferably about 34 / 66 to 100 / 0, more preferably about 50 / 50 to 100 / 0, in terms of excellent emulsifiability of the water-dispersed composition.

[0200] (Physical Properties of Water-Dispersed Composition) The physical properties of the water-dispersed composition are not particularly limited. In one embodiment, the concentration of the water-dispersed composition is typically about 20 to 70% by mass in terms of solids content. In one embodiment, the volume average particle size of the water-dispersed composition is preferably about less than 0.7 μm in terms of storage stability. In one embodiment, the water-dispersed composition has a white to milky white appearance. In one embodiment, the viscosity of the water-dispersed composition is typically about 10 to 1,000 mPa s (temperature 25° C., concentration 50% by mass).

[0201] In one embodiment, the pH of the water-dispersed composition is typically about 2 to 10. In one embodiment, the pH of the water-dispersed composition may be adjusted by appropriately adding an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid; an alkanolamine such as monomethylamine, monoethanolamine, diethanolamine, or diisopropanolamine; an aliphatic amine such as ethylamine, n-butylamine, or triethylamine; an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide; or an alkaline earth metal hydroxide such as calcium hydroxide.

[0202] (Method for Producing Water-Dispersed Composition) The method for producing the water-dispersed composition is not particularly limited, and any known method can be used, as long as it is a method of emulsifying component (A) in the presence of component (B) and, if necessary, component (C) (hereinafter, components (B) and (C) are collectively referred to as "emulsifiers"). Examples of the emulsification method include high-pressure emulsification and phase inversion emulsification.

[0203] The high-pressure emulsification method is not particularly limited, and various known methods can be used. Examples of the high-pressure emulsification method include a method in which component (A) is melted, an emulsifier and water are premixed, the mixture is finely emulsified using a high-pressure emulsifier, and the solvent is removed as needed. In one embodiment, the method for melting the material to be emulsified may involve heating alone, dissolving the material in a solvent and then heating, or mixing a non-volatile substance such as a plasticizer and then heating, but heating alone is preferred. Examples of the solvent include organic solvents that can dissolve the material to be emulsified, such as toluene, xylene, methylcyclohexane, and ethyl acetate.

[0204] The phase inversion emulsification method is not particularly limited, and various known methods can be used. Examples of the phase inversion emulsification method include a method in which component (A) is heated and melted, and then an emulsifier and water are added with stirring to first form a W / O emulsion, and then the emulsion is phase inverted to an O / W emulsion by adding water or changing the temperature, etc.

[0205] [Tackifier resin aqueous dispersion composition] The present disclosure relates to a tackifier resin aqueous dispersion composition containing the above-mentioned aqueous dispersion composition. The above-mentioned aqueous dispersion composition can function as a tackifier when used in a pressure-sensitive adhesive (including the aqueous pressure-sensitive adhesive composition described below).

[0206] [Water-based pressure-sensitive adhesive / adhesive composition] The present disclosure relates to a water-based pressure-sensitive adhesive / adhesive composition comprising the above-mentioned water-dispersion composition (or the above-mentioned tackifier resin water-dispersion composition) and a base polymer. The above-mentioned water-based pressure-sensitive adhesive / adhesive composition can be used as a water-based pressure-sensitive adhesive / adhesive. In this disclosure, it is clear that the term "pressure-sensitive adhesive / adhesive" includes either or both of a pressure-sensitive adhesive and an adhesive.

[0207] Examples of the base polymer include acrylic polymer emulsion, rubber latex, synthetic resin emulsion, etc. The base polymer may be used alone or in combination of two or more.

[0208] In one embodiment, the aqueous pressure-sensitive adhesive composition may optionally contain additives such as a crosslinking agent, an antifoaming agent, a viscosity modifier, a filler, an antioxidant, a water-resistant agent, a film-forming aid, a preservative, a pH adjuster such as ammonia water or sodium bicarbonate, a leveling agent, a release adjuster, a plasticizer, a softener, a colorant (pigment, dye, etc.), a surfactant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.

[0209] In one embodiment, the aqueous pressure-sensitive adhesive composition may optionally contain a tackifier resin aqueous dispersion composition other than the aqueous dispersion composition, as long as the object of the present disclosure is achieved. In one embodiment, the concentration of the aqueous pressure-sensitive adhesive composition is usually about 40 to 70 mass %, preferably about 55 to 70 mass %, in terms of solids content.

[0210] The acrylic polymer emulsion can be any of various known emulsions used in aqueous pressure-sensitive adhesive compositions. For example, an acrylic polymer containing an alkyl (meth)acrylate as a monomer component can be used as the acrylic polymer emulsion. The acrylic polymer emulsion can be produced by any of various known emulsion polymerization methods, such as batch polymerization of the monomer components, sequential monomer addition polymerization, sequential emulsion monomer addition polymerization, or seed polymerization, in the presence of a polymerization initiator. The acrylic polymer emulsion can be used alone or in combination of two or more.

[0211] Examples of the alkyl(meth)acrylate include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, s-butyl(meth)acrylate, pentyl(meth)acrylate, isopentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, and isooctyl(meth)acrylate. Examples of alkyl (meth)acrylates include acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. These alkyl (meth)acrylates can be used alone or in combination of two or more.

[0212] In one embodiment, the monomer component in the acrylic polymer emulsion may further include another monomer copolymerizable with the alkyl(meth)acrylate, such as a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, a monomer having a nitrogen atom-containing ring, an alkoxysilyl group-containing monomer, or a polyfunctional monomer.

[0213] Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), and crotonic acid; and ethylenically unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and citraconic acid, and their anhydrides (maleic anhydride, itaconic anhydride, etc.).

[0214] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.

[0215] Examples of the amide group-containing monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

[0216] Examples of the amino group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate.

[0217] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether. Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile. Examples of the keto group-containing monomer include diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, and vinyl acetoacetate.

[0218] Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, and N-(meth)acryloylmorpholine.

[0219] Examples of the alkoxysilyl group-containing monomer include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane.

[0220] Examples of the polyfunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin di(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyl di(meth)acrylate, and hexyl di(meth)acrylate.

[0221] The content of the other monomer copolymerizable with alkyl(meth)acrylate in the monomer component is not particularly limited, and in one embodiment, the content of the other monomer is preferably about 40% by mass or less relative to 100% by mass of the monomer component.

[0222] The above-mentioned monomer components further include vinyl ester monomers such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.) and vinyl toluene; cycloalkyl(meth)acrylates such as cyclohexyl(meth)acrylate, cyclopentyl(meth)acrylate and isobornyl(meth)acrylate; aryl(meth)acrylates (e.g., phenyl(meth)acrylate), aryloxyalkyl(meth)acrylates (e.g., phenoxyethyl(meth)acrylate), arylalkyl(meth)acrylates, etc. The monomers may include aromatic ring-containing (meth)acrylates such as acrylates (e.g., benzyl (meth)acrylate); olefin-based monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; isocyanate group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether; and reactive emulsifiers. The content of these monomers is not particularly limited. In one embodiment, the content of these monomers is preferably about 10% by mass or less relative to 100% by mass of the above-mentioned monomer components.

[0223] Examples of the reactive emulsifier include the reactive emulsifiers described above in connection with the disclosure of the structural unit (b3) of the copolymer (B).

[0224] In one embodiment, from the viewpoint of environmental protection, the reactive emulsifier in the acrylic polymer emulsion is preferably not one containing nonylphenol ethoxylate, and examples of such reactive emulsifiers include reactive emulsifiers having a polyoxyethylene nonylphenyl ether structure.

[0225] The polymerization initiator is not particularly limited, and examples thereof include azo-based initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride; and 1,1-bis(t-hexylperoxy)-3,3,5-trimethylammonium bromide. Examples of the polymerization initiator include peroxide initiators such as ethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide; and persulfate initiators such as potassium persulfate and ammonium persulfate. These polymerization initiators may be used alone or in combination of two or more.

[0226] The weight average molecular weight (Mw) of the acrylic polymer in the acrylic polymer emulsion is not particularly limited. In one embodiment, the weight average molecular weight of the acrylic polymer is typically about 100,000 to 5,000,000. From the viewpoint of improving adhesive properties, it is preferably 1,500,000 or less, more preferably 1,000,000 or less. From the viewpoint of cohesion properties, it is preferably 200,000 or more, more preferably 300,000 or more. In the present disclosure, the weight average molecular weight refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0227] When the base polymer contains the acrylic polymer emulsion, the content of the water-dispersed composition in the water-based pressure-sensitive adhesive composition is not particularly limited. The content of the aqueous dispersion composition in the aqueous pressure-sensitive adhesive / tackifier composition, in terms of nonvolatile content, relative to 100 parts by mass of the acrylic polymer emulsion, for example, may be 40 parts by mass, 39 parts by mass, 38 parts by mass, 37 parts by mass, 36 parts by mass, 35 parts by mass, 34 parts by mass, 33 parts by mass, 32 parts by mass, 31 parts by mass, 30 parts by mass, 29 parts by mass, 28 parts by mass, 27 parts by mass, 26 parts by mass, 25 parts by mass, 24 parts by mass, 23 parts by mass, 22 parts by mass, 21 parts by mass, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, and the like. In one embodiment, when the base polymer contains the acrylic polymer emulsion, the content of the water-dispersed composition in the aqueous pressure-sensitive adhesive / tacky composition is preferably about 2 to 40 parts by mass, calculated as non-volatile content, relative to 100 parts by mass of the acrylic polymer emulsion, from the viewpoint that the effect of modification by the water-dispersed composition can be sufficiently exhibited and that excessive use does not cause a decrease in heat resistance holding power, tack, etc.

[0228] As the rubber latex, various known latexes used in aqueous pressure-sensitive adhesive compositions can be used. Examples of the rubber latex include natural rubber latex and synthetic rubber latex. In one embodiment, the natural rubber latex may be a modified natural rubber obtained by grafting natural rubber with a (meth)acrylic acid alkyl ester or the like. The rubber latexes may be used alone or in combination of two or more.

[0229] The synthetic rubber latex is an aqueous dispersion of a synthetic polymer, and examples of the synthetic polymer include polyisoprene, styrene-butadiene rubber (SBR), styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, reclaimed rubber, butyl rubber, polyisobutylene, styrene-butadiene-vinylpyridine rubber, polybutadiene, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber (NBR), and polychloroprene (CR).

[0230] When the base polymer contains the rubber latex, the content of the water-dispersed composition in the water-based pressure-sensitive adhesive composition is not particularly limited. Examples of the content of the water-dispersed composition in the water-based pressure-sensitive adhesive composition, calculated as non-volatile content, relative to 100 parts by mass of the rubber latex include 150 parts by mass, 145 parts by mass, 140 parts by mass, 135 parts by mass, 130 parts by mass, 125 parts by mass, 120 parts by mass, 115 parts by mass, 110 parts by mass, 105 parts by mass, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, and 10 parts by mass. In one embodiment, when the base polymer contains the rubber latex, the content of the water-dispersed composition in the aqueous pressure-sensitive adhesive / tacky composition is preferably about 10 to 150 parts by mass, calculated as non-volatile content, per 100 parts by mass of the rubber latex, from the viewpoint that the effect of modification by the water-dispersed composition can be sufficiently exhibited and that a decrease in heat resistance holding power, tackiness, etc. due to excessive use is not caused.

[0231] As the synthetic resin emulsion, various known emulsions used in aqueous pressure-sensitive adhesive compositions can be used. Examples of the synthetic resin emulsion include vinyl acetate emulsions, ethylene-vinyl acetate copolymer emulsions, and urethane emulsions. The synthetic resin emulsions may be used alone or in combination of two or more.

[0232] When the base polymer contains the synthetic resin emulsion, the content of the water-dispersed composition in the water-based pressure-sensitive adhesive composition is not particularly limited. The content of the aqueous dispersion composition in the aqueous pressure-sensitive adhesive / tackifier composition, in terms of nonvolatile content, relative to 100 parts by mass of the synthetic resin emulsion, can be, for example, 40 parts by mass, 39 parts by mass, 38 parts by mass, 37 parts by mass, 36 parts by mass, 35 parts by mass, 34 parts by mass, 33 parts by mass, 32 parts by mass, 31 parts by mass, 30 parts by mass, 29 parts by mass, 28 parts by mass, 27 parts by mass, 26 parts by mass, 25 parts by mass, 24 parts by mass, 23 parts by mass, 22 parts by mass, 21 parts by mass, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, and the like. In one embodiment, when the base polymer contains the synthetic resin emulsion, the content of the water-dispersed composition in the water-based pressure-sensitive adhesive / tacky composition is preferably about 2 to 40 parts by mass, calculated as non-volatile content, per 100 parts by mass of the synthetic resin emulsion, from the viewpoint that the effect of modification by the water-dispersed composition can be sufficiently exhibited and that excessive use does not cause a decrease in heat resistance holding power, tack, etc.

[0233]

[0033] In one embodiment, the base polymer in the aqueous pressure-sensitive adhesive / tackifier composition preferably includes at least one selected from the group consisting of an acrylic polymer emulsion and a rubber latex, since this provides the aqueous pressure-sensitive adhesive / tackifier composition with high emulsifiability and adhesive strength.

[0234]

[0044] In one embodiment, when the base polymer comprises the acrylic polymer emulsion, the component (A) in the aqueous dispersion composition preferably comprises the component (a1) from the viewpoint of high emulsifiability and adhesive strength of the aqueous pressure-sensitive adhesive / tackifier composition, and from the same viewpoint, it is more preferable that the component (A) comprises at least one selected from the group consisting of rosin esters and rosin phenolic resins, and from the same viewpoint, it is even more preferable that the component (A) comprises at least one selected from the group consisting of polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters, and rosin phenolic resins.

[0235] In one embodiment, when the base polymer contains the rubber latex, the component (A) in the water-dispersed composition preferably contains the component (a2) from the viewpoint of high emulsifiability and adhesive strength of the aqueous pressure-sensitive adhesive / tackifier composition; from the same viewpoint, it is more preferable that the component (A) contains at least one selected from the group consisting of aliphatic petroleum resins and aliphatic / aromatic petroleum resins; and from the same viewpoint, it is even more preferable that the component (A) contains at least one selected from the group consisting of C5 petroleum resins and C5 / C9 copolymer petroleum resins.

[0236] In one embodiment, the aqueous pressure-sensitive adhesive composition may optionally contain various known additives, as long as the object of the present disclosure is achieved. Examples of the additives include a crosslinking agent, an antifoaming agent, a viscosity modifier, a filler, a water-resistant agent, a film-forming aid, a preservative, a pH adjuster such as ammonia water or sodium bicarbonate, a leveling agent, a release adjuster, a plasticizer, a softener, a colorant (pigment, dye, etc.), a surfactant, an antistatic agent, an antioxidant, an ultraviolet absorber, an antioxidant, a light stabilizer, etc.

[0237] Examples of the preservative include thiazoline-based preservatives and benzisothiazole-based preservatives.

[0238] Examples of the crosslinking agent include an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent. The content of the crosslinking agent is not particularly limited. In one embodiment, the content of the crosslinking agent is preferably 20 parts by mass or less, and more preferably about 0.01 to 10 parts by mass, relative to 100 parts by mass of the base polymer.

[0239] Examples of the isocyanate crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate; and biuret, isocyanurate, allophanate, and adduct thereof, as well as complexes obtained by reacting two or more selected from the group consisting of biuret, isocyanurate, allophanate, and adduct.

[0240] Examples of the epoxy crosslinking agent include compounds having two or more epoxy groups in the molecule, such as bisphenol A epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N'-diamineglycidylaminomethyl)cyclohexane.

[0241] The method for producing the aqueous pressure-sensitive adhesive composition is not particularly limited. Examples of the method for producing the aqueous pressure-sensitive adhesive composition include a method (mixing method) in which the aqueous dispersion composition, the base polymer, and, if necessary, various additives are mixed together. The mixing method is not particularly limited, and various known methods can be used.

[0242] [Adhesive / Adhesive Sheet] The present disclosure relates to a pressure-sensitive adhesive sheet comprising a substrate and an adhesive layer made of the aqueous pressure-sensitive adhesive composition. In one embodiment, the pressure-sensitive adhesive sheet may be a substrate-attached adhesive sheet having the adhesive layer on one or both sides of a substrate, or may be a substrate-less adhesive sheet having the adhesive layer supported on a release liner (which may also be understood as a substrate having a release surface).

[0243] In the present disclosure, the concept of adhesive sheet may include those called adhesive tape, adhesive label, adhesive film, and the like.

[0244] Examples of the substrate include polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.) films, polyester (polyethylene terephthalate, etc.) films, vinyl chloride resin films, vinyl acetate resin films, polyimide resin films, polyamide resin films, fluorine-based resin films, and other plastic films such as cellophane; papers such as Japanese paper, kraft paper, glassine paper, fine paper, synthetic paper, and top-coated paper; fabrics such as woven fabrics and nonwoven fabrics made from fibrous materials such as natural fibers, semi-synthetic fibers, and synthetic fibers, either alone or in combination, such as cotton fiber, staple fiber, Manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and polyolefin fiber; rubber sheets made from natural rubber, butyl rubber, etc.; foam sheets made from foams such as polyurethane foam and polychloroprene rubber foam; metal foils such as aluminum foil and copper foil; and composites thereof. The film may be either unstretched or stretched (uniaxially or biaxially stretched). The substrate may have a single layer structure or a laminate structure.

[0245] In one embodiment, the base material may optionally contain various additives such as fillers (inorganic fillers, organic fillers, etc.), antioxidants, antioxidants, ultraviolet absorbers, lubricants, plasticizers, colorants (pigments, dyes, etc.), etc.

[0246] In one embodiment, the surface of the substrate (particularly the surface on the polymer layer side) may be subjected to an appropriate known or conventional surface treatment, for example, a physical treatment such as a corona discharge treatment or a plasma treatment, or a chemical treatment such as a primer treatment or a backside treatment.

[0247] The pressure-sensitive adhesive sheet can be produced by a known method. For example, the pressure-sensitive adhesive sheet can be produced by first coating one or both surfaces of a substrate with the aqueous pressure-sensitive adhesive composition to form a coating layer made of the aqueous pressure-sensitive adhesive composition, and then heating or drying the coating layer to form a pressure-sensitive adhesive layer made of the aqueous pressure-sensitive adhesive composition. Known methods can be used for the coating method. Examples of the coating method include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method. The conditions for heating or drying the coating layer can be appropriately set depending on the thickness of the pressure-sensitive adhesive layer, etc. In one embodiment, the heating or drying temperature of the coating layer is typically about 10 to 120°C. In one embodiment, the heating or drying time of the coating layer is typically about 0.1 to 10 hours. The thickness of the pressure-sensitive adhesive layer (thickness after drying) varies depending on the application. In one embodiment, the thickness of the adhesive layer (thickness after drying) is preferably about 5 to 200 μm.

[0248] The present disclosure provides the following: (Item A1) An aqueous dispersion composition comprising: at least one resin (A) selected from the group consisting of a rosin-based resin (a1), a petroleum resin (a2), and a terpene-based resin (a3); and a copolymer (B) comprising a structural unit (b1) derived from a hydrophilic unsaturated monomer and a structural unit (b2) derived from a hydrophobic unsaturated monomer, wherein the softening point of the resin (A) is 95°C or higher, the acid value of the resin (A) is 100 mgKOH / g or lower, the structural unit (b1) comprises a structural unit derived from (meth)allylsulfonic acid or a salt thereof, the structural unit (b2) comprises a structural unit derived from an aromatic vinyl compound, and the molar ratio of the structural unit (b1) to the structural unit (b2) ((b1) / (b2)) is 0.3 to 3.0. (Item A2) The water-dispersed composition according to any one of the preceding items, wherein the rosin-based resin (a1) comprises at least one selected from the group consisting of rosin esters and rosin phenolic resins. (Item A3) The water-dispersed composition according to any one of the preceding items, wherein the rosin-based resin (a1) comprises at least one selected from the group consisting of polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters, and rosin phenolic resins. (Item A4) The water-dispersed composition according to any one of the preceding items, wherein the rosin-based resin (a1) comprises at least one selected from the group consisting of polymerized rosin esters and rosin phenolic resins. (Item A5) The water-dispersed composition according to any one of the preceding items, wherein the petroleum resin (a2) comprises at least one selected from the group consisting of aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, and hydrogenated petroleum resins. (Item A6) The water-dispersed composition according to any one of the preceding items, wherein the petroleum resin (a2) comprises at least one selected from the group consisting of C5 petroleum resins, C9 petroleum resins, and C5 / C9 copolymer petroleum resins. (Item A7) The water-dispersed composition according to any one of the preceding items, wherein the resin (A) comprises at least one selected from the group consisting of rosin esters, rosin phenolic resins, aliphatic petroleum resins, aromatic petroleum resins, and aliphatic-aromatic petroleum resins.(Item A8) The water-dispersed composition according to any one of the above items, wherein the resin (A) comprises at least one selected from the group consisting of polymerized rosin ester, α,β-unsaturated carboxylic acid-modified rosin ester, rosin phenolic resin, C5 petroleum resin, C9 petroleum resin, and C5 / C9 copolymer petroleum resin. (Item A9) The water-dispersed composition according to any one of the above items, wherein the resin (A) comprises at least one selected from the group consisting of polymerized rosin ester, rosin phenolic resin, C9 petroleum resin, and C5 / C9 copolymer petroleum resin. (Item A10) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has a softening point of 95 to 190°C. (Item A11) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has a softening point of 130°C or higher. (Item A12) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has a softening point of 130 to 190°C. (Item A13) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has a softening point of 140 to 190°C. (Item A14) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has a softening point of 160 to 190°C. (Item A15) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has an acid value of 50 mgKOH / g or less. (Item A16) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has an acid value of 20 mgKOH / g or less. (Item A17) The water-dispersed composition according to any one of the above items, wherein the rosin-based resin (a1) has an acid value of 15 mgKOH / g or less. (Item A18) The water-dispersed composition according to any one of the preceding items, wherein the structural unit (b1) comprises at least one selected from the group consisting of structural units derived from an anionic unsaturated compound or a salt thereof, and structural units derived from a hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms. (Item A19) The water-dispersed composition according to any one of the preceding items, wherein the structural unit (b1) comprises at least one selected from the group consisting of structural units derived from a carboxyl group-containing unsaturated compound or a salt thereof, and structural units derived from a hydroxyl group-containing (meth)acrylate having 5 to 7 carbon atoms.(Item A20) The water-dispersed composition according to any one of the above items, wherein the structural unit (b1) comprises at least one selected from the group consisting of a structural unit derived from itaconic acid or a salt thereof, a structural unit derived from (meth)acrylic acid or a salt thereof, and a structural unit derived from hydroxypropyl (meth)acrylate. (Item A21) The water-dispersed composition according to any one of the above items, wherein the structural unit (b1) comprises a structural unit derived from a hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms. (Item A22) The water-dispersed composition according to any one of the above items, wherein the structural unit (b1) comprises a structural unit derived from a hydroxyl group-containing (meth)acrylate having 5 to 7 carbon atoms. (Item A23) The water-dispersed composition according to any one of the above items, wherein the structural unit (b1) comprises a structural unit derived from hydroxypropyl (meth)acrylate. (Item A24) The water-dispersed composition according to any one of the above items, wherein the structural unit (b1) does not comprise a structural unit derived from a reactive emulsifier having a polyoxyethylene nonylphenyl ether structure. (Item A25) The water-dispersed composition according to any one of the preceding items, wherein the structural unit (b2) includes a structural unit derived from an alkyl (meth)acrylate. (Item A26) The water-dispersed composition according to any one of the preceding items, wherein the structural unit (b2) includes a structural unit derived from a (meth)acrylic acid alkyl ester in which the alkyl group has 1 to 8 carbon atoms. (Item A27) The water-dispersed composition according to any one of the preceding items, wherein the structural unit (b2) includes at least one selected from the group consisting of a structural unit derived from methyl (meth)acrylate, a structural unit derived from n-butyl (meth)acrylate, a structural unit derived from 2-ethylhexyl (meth)acrylate, and a structural unit derived from cyclohexyl (meth)acrylate. (Item A28) The water-dispersed composition according to any one of the preceding items, wherein the copolymer (B) does not include a structural unit derived from (meth)acrylamide. (Item A29) The water-dispersed composition according to any one of the preceding items, wherein the molar ratio of the structural unit (b1) to the structural unit (b2) ((b1) / (b2)) is 0.5 to 2.5. (Item A30) The water-dispersed composition according to any one of the preceding items, wherein the content of the structural unit (b1) in the component (B) is 30 to 70 mass%, relative to 100 mass% of the component (B).(Item A31) The water-dispersed composition according to any one of the preceding items, wherein the content of the structural unit (b1) in the component (B) is 30 to 70 mol %, relative to 100 mol % of the component (B). (Item A32) The water-dispersed composition according to any one of the preceding items, wherein the content of the structural unit (b2) in the component (B) is 30 to 70 mol %, relative to 100 mol % of the component (B). (Item A33) The water-dispersed composition according to any one of the preceding items, wherein the content of the structural unit (b2) in the component (B) is 30 to 65 mol %, relative to 100 mol % of the component (B). (Item A34) The water-dispersed composition according to any one of the preceding items, further comprising a surfactant (C). (Item A35) The water-dispersed composition according to any one of the preceding items, wherein the content of the component (B) in the water-dispersed composition, calculated as nonvolatile content, is 1 to 20 parts by mass relative to 100 parts by mass of the component (A). (Item A36) The water-dispersed composition according to any one of the above items, wherein the content of the component (C) in the water-dispersed composition is 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A) in terms of non-volatile content. (Item A37) A water-dispersed tackifier resin composition comprising the water-dispersed composition according to any one of the above items. (Item A38) A water-based pressure-sensitive adhesive composition comprising the water-dispersed composition according to any one of the above items and a base polymer. (Item A39) The water-based pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises an acrylic polymer emulsion. (Item A40) The water-based pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises an acrylic polymer emulsion, and wherein the resin (A) in the water-dispersed composition comprises a rosin resin (a1). (Item A41) The water-based pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises an acrylic polymer emulsion, and wherein the resin (A) in the water-dispersed composition comprises at least one selected from the group consisting of rosin esters and rosin phenolic resins. (Item A42) The aqueous pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises an acrylic polymer emulsion, and the resin (A) in the aqueous dispersion composition comprises at least one selected from the group consisting of polymerized rosin ester, α,β-unsaturated carboxylic acid-modified rosin ester, and rosin phenolic resin.(Item A43) The aqueous pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises a rubber latex. (Item A44) The aqueous pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises a rubber latex, and the resin (A) in the aqueous dispersion composition comprises a petroleum resin (a2). (Item A45) The aqueous pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises a rubber latex, and the resin (A) in the aqueous dispersion composition comprises at least one selected from the group consisting of an aliphatic petroleum resin and an aliphatic / aromatic petroleum resin. (Item A46) The aqueous pressure-sensitive adhesive composition according to any one of the above items, wherein the base polymer comprises a rubber latex, and the resin (A) in the aqueous dispersion composition comprises at least one selected from the group consisting of a C5 petroleum resin and a C5 / C9 copolymer petroleum resin. (Item A47) A pressure-sensitive adhesive sheet comprising a substrate and an adhesive layer composed of the aqueous pressure-sensitive adhesive composition according to any one of the above items.

[0249] The aqueous dispersion composition provided by the present disclosure has excellent emulsification properties because the generation of aggregates, etc. is suppressed. Furthermore, the aqueous dispersion composition provided by the present disclosure can impart high adhesive strength to an aqueous pressure-sensitive adhesive composition.

[0250] The present invention will be described in detail below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only by the claims. In the examples, "parts" and "%" are by mass unless otherwise specified.

[0251] <Production of Base Polymer> Production Example 1 A reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was charged with an aqueous solution consisting of 43.4 parts of water and 0.92 parts of polyoxyethylene alkyl ether sulfate ester ammonium salt (anionic emulsifier: trade name "Hitenol LA-16", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) under a nitrogen gas stream, and the temperature was raised to 70°C. Next, a mixture consisting of 90 parts of butyl acrylate, 7 parts of 2-ethylhexyl acrylate, and 3 parts of acrylic acid, and 1 / 10 of an aqueous initiator solution consisting of 0.24 parts of potassium persulfate (polymerization initiator), 0.11 parts of sodium bicarbonate (pH adjuster), and 8.83 parts of water were added to the reaction vessel, and a prepolymerization reaction was carried out at 70°C for 30 minutes under a nitrogen gas stream. Next, the mixture and the remaining 9 / 10 of the aqueous initiator solution were added to the reaction vessel over 2 hours to carry out emulsion polymerization, and then the mixture was maintained at 70°C for 1 hour to complete the polymerization reaction. The acrylic polymer emulsion thus obtained was cooled to room temperature and then filtered through a 100 mesh wire screen to obtain an acrylic polymer emulsion with a solids concentration of 47.8%.

[0252] <Production of Rosin Resin (a1)> Production Example 2 A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube and a steam inlet tube was charged with 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140°C) and melted at 220°C. Next, 11 parts of pentaerythritol was charged, and the mixture was heated to 250°C and reacted at that temperature for 2 hours. The mixture was further heated to 280°C and reacted at that temperature for 9 hours to complete the esterification. This was followed by a 2-hour treatment under reduced pressure to obtain polymerized rosin ester (a1-1) (hereinafter referred to as component (a1-1)). The component (a1-1) had a softening point of 160°C and an acid value of 12 mgKOH / g.

[0253] Production Example 3: 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140°C) was charged into a reaction vessel similar to that used in Production Example 2 and melted at 220°C. Next, 12 parts of pentaerythritol was charged, and the mixture was heated to 250°C and allowed to react at that temperature for 2 hours. The mixture was then heated to 280°C and allowed to react at that temperature for 14 hours. This was followed by a 3-hour treatment under reduced pressure to obtain polymerized rosin ester (a1-2) (hereinafter referred to as component (a1-2)). Component (a1-2) had a softening point of 180°C and an acid value of 9 mgKOH / g.

[0254] Production Example 4: 50 parts of gum rosin (acid value 160 mgKOH / g, softening point 70°C) and 100 parts of phenol were charged into a reaction vessel similar to that used in Production Example 2, and the mixture was heated to 100°C. 2.1 parts of 96% sulfuric acid was added and reacted for 3 hours under a nitrogen gas stream. 3.0 parts of slaked lime were then added, and the mixture was heated to 280°C under a reduced pressure of 10 kPa and reacted at that temperature for 4 hours. Water and other elements were then removed to obtain rosin phenolic resin (a1-3) (hereinafter referred to as component (a1-3)). Component (a1-3) had a softening point of 150°C and an acid value of 50 mgKOH / g.

[0255] Production Example 5: 50 parts of gum rosin (acid value 160 mgKOH / g, softening point 70°C) and 9.3 parts of glycerin were charged into a reaction vessel similar to that used in Production Example 2, heated to 250°C under a nitrogen stream, and esterified at that temperature for 8 hours to obtain a rosin ester with a softening point of 84°C and an acid value of 6. The rosin ester was then heated to 160°C, and 8.2 parts of maleic anhydride was added. The mixture was then heated and maintained at 210°C for 2 hours to obtain an α,β-unsaturated carboxylic acid-modified rosin ester (a1'-1) (hereinafter referred to as component (a1'-1)). Component (a1'-1) had a softening point of 100°C and an acid value of 180 mgKOH / g.

[0256] (Acid Value) The acid values ​​of the components (a1-1) to (a1-3), the component (a2-1) described below, the component (a1'-1) and the component (a2'-1) described below were measured in accordance with JIS K 0070.

[0257] (Softening Point) The softening points of the components (a1-1) to (a1-3), the component (a2-1) described below, the component (a1'-1) and the component (a2'-1) described below were measured in accordance with JIS K 5902.

[0258] <Production of Copolymer (B)> Production Example 6 A four-neck flask equipped with a nitrogen gas inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 2 parts of butyl acrylate, 23 parts of styrene, 4.5 parts of α-methylstyrene, 5 parts of itaconic acid, 40.5 parts of methacrylic acid, 10 parts of sodium allylsulfonate, 15 parts of 2-hydroxypropyl acrylate, 270 parts of ion-exchanged water, 1 part (non-volatile content equivalent) of a polyoxyethylene alkyl ether emulsifier (trade name "Hitenol LA-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)), and 4 parts of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent. The mixture was heated to 65°C, 4 parts of ammonium persulfate (APS) was added as a polymerization initiator, and the mixture was heated to 90°C and maintained for 120 minutes. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further maintained at that temperature for 1 hour. Thereafter, 45 parts of a 48% aqueous solution of sodium hydroxide and a predetermined amount of ion-exchanged water were added to the reaction system, which was then thoroughly stirred and cooled to room temperature, yielding an aqueous solution of copolymer (B-1) (hereinafter referred to as component (B-1)) with a solids content of 25.0%.

[0259] Production Example 7 Into a reaction vessel similar to that of Production Example 11, 12.8 parts of methyl methacrylate, 27.0 parts of styrene, 27.0 parts of α-methylstyrene, 33.1 parts of methacrylic acid, 0.1 parts of sodium allylsulfonate, 333 parts of ion-exchanged water, and 1.7 parts of n-dodecyl mercaptan as a chain transfer agent were charged, and the temperature was raised to 65 ° C., and 4 parts of ammonium persulfate (APS) was added as a polymerization initiator, and the temperature was raised to 90 ° C. and maintained for 120 minutes. Next, 1 part of ammonium persulfate was added to the reaction system, and the temperature was maintained for another 1 hour. Thereafter, 35 parts of a 48% aqueous sodium hydroxide solution and a predetermined amount of ion-exchanged water were added to the reaction system, followed by thorough stirring and cooling to room temperature. In this way, an aqueous solution of copolymer (B-2) (hereinafter referred to as component (B-2)) with a solids content of 25.0% was obtained.

[0260] Production Example 8: A four-neck flask equipped with a nitrogen gas inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 23 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, 10 parts of styrene, 1 part of itaconic acid, 52 parts of methacrylic acid, 1 part of sodium allylsulfonate, 1 part of 2-hydroxypropyl acrylate, 0.3 parts (based on non-volatile content) of a polyoxyethylene alkyl ether emulsifier (trade name "Hitenol LA-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)), and 10 parts of ion-exchanged water to prepare an aqueous monomer solution. Next, 5 parts of 2,4-diphenyl-4-methyl-1-pentene, 3.5 parts of ammonium persulfate, and 72 parts of ion-exchanged water were added to the aqueous monomer solution. The reaction system was then heated to 90°C and maintained at that temperature for 2 hours to carry out a radical polymerization reaction. Next, 1 part of ammonium persulfate was added to the reaction system, and the temperature was maintained for an additional 1 hour. Thereafter, 53 parts of a 48% aqueous solution of sodium hydroxide and a predetermined amount of ion-exchanged water were added to the reaction system, which was then thoroughly stirred and cooled to room temperature, yielding an aqueous solution of copolymer (B-3) (hereinafter referred to as component (B-3)) with a solids content of 25.0%.

[0261] Production Example 10 Into a reaction vessel similar to that of Production Example 11, 10 parts of butyl acrylate, 50 parts of styrene, 15 parts of α-methylstyrene, 2 parts of itaconic acid, 10 parts of methacrylic acid, 3 parts of sodium allylsulfonate, 3 parts of 2-hydroxypropyl acrylate, 270 parts of ion-exchanged water, 1 part (non-volatile content equivalent) of a polyoxyethylene alkyl ether-based emulsifier (trade name "Hitenol LA-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)), and 4 parts of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent were charged, and the mixture was heated to 65°C, and 4 parts of ammonium persulfate (APS) was added as a polymerization initiator, and the mixture was heated to 90°C and maintained for 120 minutes. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further maintained at that temperature for 1 hour. Thereafter, 12 parts of a 48% aqueous sodium hydroxide solution and a predetermined amount of ion-exchanged water were added to the reaction system, followed by thorough stirring and cooling to room temperature. In this way, an aqueous solution of copolymer (B'-1) (hereinafter referred to as component (B'-1)) with a solid content of 25.0% was obtained.

[0262] Into a reaction vessel similar to that of Production Example 11, 2 parts of butyl acrylate, 15 parts of styrene, 4.5 parts of α-methylstyrene, 5 parts of itaconic acid, 48.5 parts of methacrylic acid, 10 parts of sodium allylsulfonate, 15 parts of 2-hydroxypropyl acrylate, 270 parts of ion-exchanged water, 1 part (non-volatile content equivalent) of a polyoxyethylene alkyl ether-based emulsifier (trade name "Hitenol LA-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)), and 4 parts of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent were charged, and the mixture was heated to 65°C, and 4 parts of ammonium persulfate (APS) was added as a polymerization initiator, and the mixture was heated to 90°C and maintained for 120 minutes. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further kept at the same temperature for 1 hour. Thereafter, 21 parts of 48% aqueous sodium hydroxide solution and a predetermined amount of ion-exchanged water were added to the reaction system, followed by thorough stirring and cooling to room temperature. In this way, an aqueous solution of copolymer (B'-2) (hereinafter referred to as component (B'-2)) with a solid content of 25.0% was obtained.

[0263] Production Example 12 A reaction vessel similar to that of Production Example 11 was charged with 2.5 parts of butyl acrylate, 24 parts of styrene, 6 parts of α-methylstyrene, 7.5 parts of itaconic acid, 43 parts of methacrylic acid, 17 parts of 2-hydroxypropyl acrylate, 270 parts of ion-exchanged water, 1 part (based on non-volatile content) of a polyoxyethylene alkyl ether emulsifier (trade name "Hitenol LA-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)), and 4 parts of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent. The mixture was heated to 65°C, and 4 parts of ammonium persulfate (APS) was added as a polymerization initiator, and the mixture was heated to 90°C and maintained at that temperature for 120 minutes. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further maintained at that temperature for 1 hour. Thereafter, 50 parts of a 48% aqueous sodium hydroxide solution and a predetermined amount of ion-exchanged water were added to the reaction system, followed by thorough stirring and cooling to room temperature. In this way, an aqueous solution of copolymer (B'-3) (hereinafter referred to as component (B'-3)) with a solid content of 25.0% was obtained.

[0264] Production Example 13: Into a reaction vessel similar to that of Production Example 11, 24.5 parts of butyl acrylate, 5 parts of methyl methacrylate, 5 parts of itaconic acid, 40.5 parts of methacrylic acid, 10 parts of sodium allylsulfonate, 15 parts of 2-hydroxypropyl acrylate, 270 parts of ion-exchanged water, 1 part (non-volatile content equivalent) of a polyoxyethylene alkyl ether-based emulsifier (trade name "Hitenol LA-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)), and 4 parts of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent were charged, and the mixture was heated to 65°C, and 4 parts of ammonium persulfate (APS) was added as a polymerization initiator, and the mixture was heated to 90°C and maintained for 120 minutes. Next, 1 part of ammonium persulfate was added to the reaction system, and the mixture was further maintained at that temperature for 1 hour. Thereafter, 45 parts of a 48% aqueous sodium hydroxide solution and a predetermined amount of ion-exchanged water were added to the reaction system, followed by thorough stirring and cooling to room temperature. In this way, an aqueous solution of copolymer (B'-4) (hereinafter referred to as component (B'-4)) with a solid content of 25.0% was obtained.

[0265] [Preparation of Water-Dispersed Composition] Example 1 100 parts of component (a1-1) from Preparation Example 2 was dissolved in 80 parts of methylcyclohexane at 80°C over 3 hours, and then 5 parts of component (B-1) (based on non-volatile content) and 140 parts of water were added and stirred for 1 hour. Subsequently, the mixture was subjected to high-pressure emulsification at a pressure of 30 MPa using a high-pressure emulsifier (manufactured by Manton Gaulin) to obtain an emulsion. Subsequently, the emulsion was subjected to high-pressure emulsification at 70°C and 2.93 × 10 －２ The mixture was subjected to reduced pressure distillation under a condition of 100 MPa for 6 hours to obtain a water-dispersed composition with a solid content of 50%.

[0266] Examples 2 and 3 The same procedure as in Example 1 was carried out except that the component (a1-1) in Example 1 was changed to components (a1-2) and (a1-3), to obtain water-dispersed compositions with a solids concentration of 50%.

[0267] Example 4 The same procedure as in Example 1 was carried out, except that the component (a1-1) in Example 1 was changed to a commercially available C9 petroleum resin (softening point 140°C, acid value less than 1 mgKOH / g) (a2-1) (hereinafter referred to as component (a2-1)), to obtain a water-dispersed composition with a solids concentration of 50%.

[0268] Examples 5 and 6 The same procedure as in Example 1 was carried out except that the component (B-1) in Example 1 was changed to components (B-2) and (B-3), to obtain aqueous dispersion compositions with a solids concentration of 50%.

[0269] Example 7 The same procedure as in Example 1 was carried out, except that 100 parts of the component (a1-1) was changed to 60 parts of the component (a1-1) and 40 parts of the component (a1'-1), to obtain a water-dispersed composition with a solids concentration of 50%.

[0270] Example 8 The same procedure as in Example 1 was carried out, except that 100 parts of the component (a1-1) in Example 1 was changed to 50 parts of the component (a2-1) and 50 parts of a commercially available C5 / C9 copolymer petroleum resin (softening point 85°C, acid value less than 1 mgKOH / g) (a2'-1) (hereinafter referred to as component (a2'-1)), and the component (B-1) was changed to component (B-2), to obtain a water-dispersible composition with a solids concentration of 50%.

[0271] Comparative Example 1 The same procedure as in Example 1 was carried out, except that in Example 1, the component (a1-1) was changed to the component (a2'-1) and the component (B-1) was changed to the component (B-2), to obtain a water-dispersed composition with a solids concentration of 50%.

[0272] Comparative Example 2 The same procedure as in Example 1 was carried out, except that the component (a1-1) in Example 1 was changed to the component (a1'-1), to obtain a water-dispersed composition with a solids concentration of 50%.

[0273] Comparative Examples 3 to 6 The same procedure as in Example 1 was carried out except that the component (B-1) in Example 1 was changed to components (B'-1) to (B'-4), to obtain aqueous dispersion compositions with a solids concentration of 50%.

[0274] Comparative Example 7 The same procedure as in Example 1 was carried out, except that 100 parts of the component (a1-1) was changed to 30 parts of the component (a1-1) and 70 parts of the component (a1'-1), to obtain a water-dispersed composition with a solids concentration of 50%.

[0275] (Evaluation of aggregates)

[0276] The aqueous dispersion compositions of each Example and Comparative Example were filtered through a 150-mesh wire screen, and the mass % of the resulting residue relative to the resin (A) was weighed. The mass % of the residue was evaluated according to the following criteria. The results are shown in Table 1. The smaller the mass % of the residue, the more the generation of aggregates in the aqueous dispersion composition is suppressed, and the better its emulsifiability. ○: Less than 0.05 mass % △: 0.05 mass % or more but less than 0.1 mass % ×: 0.1 mass % or more

[0277] [Production of Water-Based Pressure-Sensitive Adhesive Composition] A water-based pressure-sensitive adhesive composition was obtained by mixing 90 parts (non-volatile content equivalent) of the acrylic polymer emulsion synthesized in Production Example 1 and 10 parts (non-volatile content equivalent) of the water-dispersed composition of Example 1. For each of the water-dispersed compositions of Examples 2 to 8 and Comparative Examples 1 to 7, a water-based pressure-sensitive adhesive composition was produced in the same manner.

[0278] [Preparation of Sample Tape] Using a dice-type applicator (manufactured by Taiyu Kizai Co., Ltd.), the aqueous pressure-sensitive adhesive composition was applied to a polyester film (trade name "S-100", manufactured by Mitsubishi Chemical Corporation, thickness: 38 μm) to a thickness of about 50 μm, and then dried in a circulating air dryer at 105° C. for 5 minutes to prepare a sample tape.

[0279] (Evaluation of Constant Load Peel) The above sample tape was cut into a width of 25 mm, and was adhered to an adherend (polyethylene plate (PE)) by rolling a 2 kg roller back and forth twice, and left to stand for 1 day. Next, a load of 200 g was applied to the end of the tape, and it was fixed so as to achieve 90° peeling, and the peel distance (mm) per hour was measured at 23°C. The peel distance was evaluated according to the following criteria. The results are shown in Table 1. The shorter the peel distance, the better the adhesive strength of the aqueous pressure-sensitive adhesive composition. ◎: Peel distance per hour is less than 20 mm ○: Peel distance per hour is 20 mm or more and less than 40 mm △: Peel distance per hour is 40 mm or more and less than 60 mm ×: Peel distance per hour is 60 mm or more

[0280] The annotations in Table 1 are as follows: (1) The molar ratio ((b1) / (b2)) of the structural unit (b1) to the structural unit (b2) in the component (B). (2) A large amount of aggregates was generated in the water-dispersed composition, so constant-load peel test could not be evaluated.

Claims

1. An aqueous dispersion composition comprising: at least one resin (A) selected from the group consisting of a rosin-based resin (a1), a petroleum resin (a2), and a terpene-based resin (a3); and a copolymer (B) comprising a structural unit (b1) derived from a hydrophilic unsaturated monomer and a structural unit (b2) derived from a hydrophobic unsaturated monomer; wherein the softening point of the resin (A) is 95°C or higher; the acid value of the resin (A) is 100 mgKOH / g or lower; the structural unit (b1) comprises a structural unit derived from (meth)allylsulfonic acid or a salt thereof; the structural unit (b2) comprises a structural unit derived from an aromatic vinyl compound; and the molar ratio of the structural unit (b1) to the structural unit (b2), ((b1) / (b2)), is 0.3 to 3.

0.

2. The aqueous dispersion composition according to claim 1, wherein the rosin-based resin (a1) has a softening point of 130°C or higher.

3. The water-dispersed composition according to claim 1, wherein the structural unit (b1) includes a structural unit derived from a hydroxyl group-containing (meth)acrylate having 5 to 9 carbon atoms.

4. A tackifying resin water-dispersed composition comprising the water-dispersed composition according to any one of claims 1 to 3.

5. A water-based pressure-sensitive adhesive composition comprising the water dispersion composition of claim 1 and a base polymer.

6. The aqueous pressure-sensitive adhesive composition according to claim 5, wherein the base polymer comprises an acrylic polymer emulsion.

7. The aqueous pressure-sensitive adhesive composition according to claim 5, wherein the base polymer comprises a rubber latex.

8. A pressure-sensitive adhesive sheet comprising a substrate and a pressure-sensitive adhesive layer made of the aqueous pressure-sensitive adhesive composition according to any one of claims 5 to 7.

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