JP2020152903A - Tackifier resin emulsion, aqueous tackifier adhesive composition, and tackifier adhesive sheet - Google Patents

Abstract

To provide a tackifier resin emulsion giving an aqueous tackifier adhesive composition excellent in curved surface adhesiveness while retaining adhesivity and retentivity of a tackifier adhesive layer to various substrates, and excellent in compatibility to a base polymer.SOLUTION: A tackifier resin emulsion includes: a rosin-based emulsion (A) having a softening point of 120-180°C; a petroleum resin (B) in which the ratio (S'NMR/SNMR) of a peak area value (S'NMR) of 6.3-7.6 ppm to a total area value (SNMR) in a 1H-NMR spectrum is 0-4.0%; and an emulsifier (C).SELECTED DRAWING: None

Description

The present invention relates to a tackifier resin emulsion, a water-based adhesive / adhesive composition, and an adhesive / adhesive sheet.

Generally, polyolefin resins such as polyethylene and polypropylene used for the exterior of food packaging and electronic and electrical products do not have functional groups and are non-polar, so they have poor affinity with polar molecules and adherence to adhesives. It is very weak and easy to peel off. Therefore, a method of applying a primer to the adhesive surface to modify the adhesive surface is generally used, but an adhesive / adhesive having sufficient adhesive strength to a polyolefin-based resin, particularly curved adhesiveness, without using a primer. Is strongly sought after.

Further, in recent years, in consideration of the safety of the environment and the human body, there has been a demand for water-based adhesives / adhesives having a low content of volatile organic solvents and the like and having a reduced environmental load. However, when trying to change the organic solvent-based adhesive / adhesive to an aqueous-based adhesive, there is a problem that the curved surface adhesiveness to the polyolefin-based resin becomes insufficient. Further, in addition to curved surface adhesiveness, water-based adhesives / adhesives are also required to have adhesive strength to various substrates and holding strength of the adhesive / adhesive layer.

As a water-based adhesive / adhesive having improved curved surface adhesiveness to a polyolefin resin, for example, Patent Document 1 describes adhesion from an acrylic copolymer, a rosin-based tackifier resin, and a C5 / C9 copolymer-based petroleum resin. Emulsion-type pressure-sensitive adhesives containing an imparting resin emulsion have been proposed.

Japanese Unexamined Patent Publication No. 2008-239871

However, the emulsion type pressure-sensitive adhesive of Patent Document 1 does not have sufficient curved surface adhesiveness to the polyolefin resin, and there is room for improvement. Further, since the tackifier resin emulsion has insufficient compatibility with the acrylic copolymer as the base polymer, there is a problem that the transparency of the emulsion type pressure-sensitive adhesive containing the emulsion is low.

The present invention provides a water-based adhesive / adhesive composition having excellent curved surface adhesiveness to a polyolefin-based resin while retaining the adhesive force to various substrates and the holding force of the adhesive / adhesive layer, and to a base polymer. An object of the present invention is to provide a tackifier resin emulsion having excellent compatibility.

As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by a tackifier resin emulsion in which a rosin-based resin having a specific softening point and a specific petroleum resin are used in combination. That is, the present invention relates to the following tackifier resin emulsions, water-based adhesive / adhesive compositions, and adhesive / adhesive sheets.

1. 1. Rosin resin (A) with a softening point of 120 to 180 ° C,
Total peak area values in ¹ H-NMR spectrum 'ratio of _(NMR (S peak area values of 6.3~7.6ppm for _{(S NMR) S)' NMR} / S NMR) is from 0 to 4.0% Petroleum resin (B),
as well as,
A tackifier resin emulsion containing the emulsifier (C).

2. 2. Item 2. The tackifier resin emulsion according to Item 1, wherein the component (A) is a polymerized rosin ester and / or a rosin phenol resin.

3. 3. Item 2. The tackifier resin according to Item 1 or 2, wherein the component (B) is at least one petroleum resin selected from the group consisting of an aliphatic petroleum resin, an alicyclic petroleum resin, and a hydrogenated petroleum resin. Emulsion.

4. The tackifier resin emulsion according to any one of Items 1 to 3 above, wherein the component (B) has a weight average molecular weight of 500 to 4,000.

5. Item 2. The item 1 to 4 above, wherein the mass ratio ((A) / (B)) of the component (A) to the component (B) is 60/40 to 99/1 in terms of solid content. Adhesive-imparting resin emulsion.

6. A water-based adhesive / adhesive composition containing the tackifier resin emulsion according to any one of the above items 1 to 5 and a base polymer.

7. Item 6. The water-based adhesive / adhesive composition according to Item 6, wherein the base polymer is an acrylic polymer emulsion.

8. A viscous / adhesive sheet containing a viscous / adhesive layer and a base material comprising the water-based adhesive / adhesive composition according to item 6 or 7 above.

The adhesive-imparting resin emulsion of the present invention provides a water-based adhesive / adhesive composition having excellent curved adhesiveness to a polyolefin-based resin while retaining adhesive strength to various substrates and holding power of an adhesive / adhesive layer. obtain. Further, since the tackifier resin emulsion of the present invention has excellent compatibility with the base polymer (hereinafter, also referred to as compatibility) in the water-based adhesive / adhesive composition, the water-based adhesive / adhesive composition containing the emulsion is transparent. It has high properties and is suitable as a sticky / adhesive for applications requiring transparency and design, for example, a sticky / adhesive for a transparent label used in a cosmetic container or a shampoo container.

[Adhesive-imparting resin emulsion]
The tackifier resin emulsion of the present invention comprises a rosin-based resin (A) having a softening point of 120 to 180 ° C. (hereinafter referred to as component (A)), and 6.3 with respect to the total peak area value (S _NMR ) of ¹ H-NMR spectrum. peak area of ~7.6ppm (S _'NMR) ratio _{(S' NMR} / S _NMR) is from 0 to 4.0% petroleum resin (B) (hereinafter, (B) as component) and the emulsifier (C ) (Hereinafter referred to as component (C)).

<Rosin resin (A)>
As for the physical properties of the component (A), the softening point is 120 to 180 ° C. When the softening point of the component (A) is less than 120 ° C., the curved surface adhesiveness is insufficient and the holding power is lowered. When the softening point of the component (A) exceeds 180 ° C., the compatibility is lowered and the curved surface adhesiveness is insufficient. The component (A) preferably has a softening point of about 130 to 160 ° C., more preferably about 140 to 160 ° C., from the viewpoint of excellent balance of curved surface adhesiveness, compatibility, adhesive strength and holding power. In this specification, the softening point is a value measured by the ring-and-ball method (JISK5902).

As the component (A), various known components can be used without particular limitation as long as the softening point is 120 to 180 ° C. Examples of the component (A) include polymerized rosin, α, β-unsaturated carboxylic acid-modified rosin, rosin esters, rosin phenol resin and the like. These may be used alone or in combination of two or more.

The polymerized rosin is a rosin derivative containing a dimerized resin acid.

As a method for producing the polymerized rosin, a known method can be adopted. Specifically, for example, natural rosin (gum rosin, tall oil rosin, wood rosin) and / or natural rosin derived from Mao pine, Slash pine, Merckushi pine, Shikaya pine, Theda pine, Daio pine, etc. are distilled off under reduced pressure. Purified rosin obtained by purification by steam distillation method, extraction method, recrystallization method, etc. (hereinafter, natural rosin and purified rosin are collectively referred to as raw material rosin) is referred to as sulfuric acid, hydrogen fluoride, aluminum chloride, titanium tetrachloride, etc. Examples thereof include a method of reacting in a solvent such as toluene and xylene containing the above catalyst at a temperature of about 40 to 160 ° C. for about 1 to 5 hours.

Specific examples of the polymerized rosin include gum-based polymerized rosin using gum rosin as the raw material rosin (for example, trade name "polymerized rosin B-140", manufactured by Shinshu (Takehira) Forestry Co., Ltd.) and tall oil rosin. Examples include the used tall oil-based polymerized rosin (for example, trade name "Silva Tack 140", manufactured by Arizona Chemical Co., Ltd.), wood-based polymerized rosin using wood rosin (for example, trade name "Dymalex", manufactured by ASHLAND), and the like. ..

Further, as the polymerized rosin, those obtained by subjecting the polymerized rosin to various treatments such as hydrogenation, disproportionation, acrylicization, mareinization, and fumarization may be used. Further, various treatments may be performed alone or in combination of two or more. The polymerized rosin is preferably acrylicated, mareinized, or fumarized.

The α, β-unsaturated carboxylic acid-modified rosin is a modified rosin obtained by addition-reacting the raw material rosin with α, β-unsaturated carboxylic acid.

The α, β-unsaturated carboxylic acid is not particularly limited, and various known ones can be used. Specific examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride and the like. Among these, acrylic acid, maleic acid, maleic anhydride, and fumaric acid are preferable. From the viewpoint of emulsifying property, the amount of α, β-unsaturated carboxylic acid used is usually about 1 to 20 parts by mass, preferably about 1 to 3 parts by mass with respect to 100 parts by mass of the raw material rosin.

The method for producing the α, β-unsaturated carboxylic acid-modified rosin is not particularly limited. For example, the α, β-unsaturated carboxylic acid is added to the raw material rosin melted under heating to obtain a temperature of 180. The reaction may be carried out at about 240 ° C. for about 1 to 9 hours. Further, the above reaction may be carried out while blowing an inert gas such as nitrogen into the closed reaction system. Further, in the above reaction, known catalysts such as Lewis acid such as zinc chloride, iron chloride and tin chloride, and blended acid such as paratoluenesulfonic acid and methanesulfonic acid may be used. The amount of these catalysts used is usually about 0.01 to 10% by mass with respect to the raw material rosin.

The obtained α, β-unsaturated carboxylic acid-modified rosin may contain a resin acid derived from the above-mentioned raw material rosin.

The above-mentioned rosin esters mean rosin esters, polymerized rosin esters, and unsaturated carboxylic acid-modified rosin esters, which will be described later.

The rosin ester is obtained by reacting alcohols with the raw material rosin, the hydrogenated rosin obtained by hydrogenating the raw material rosin, or the disproportionated rosin obtained by disproportionating the raw material rosin. Be done.

As the reaction conditions between the rosin and alcohols, an esterification catalyst is added to the rosin and alcohols in the presence or absence of a solvent, if necessary, at about 250 to 280 ° C. for about 1 to 8 hours. Just do it.

The alcohols are not particularly limited, and for example, monohydric alcohols such as methanol, ethanol, propanol and stearyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimerdiol and the like 2 Examples thereof include valent alcohols, trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, and hexahydric alcohols such as dipentaerythritol. Among these, polyhydric alcohols having two or more hydroxyl groups are preferable, and pentaerythritol is particularly preferable.

The polymerized rosin ester is obtained by reacting the polymerized rosin with alcohols.

As the reaction conditions between the polymerized rosin and alcohols, an esterification catalyst is added to the polymerized rosin and alcohols in the presence or absence of a solvent as necessary, and the temperature is about 250 to 280 ° C. for about 1 to 8 hours. You can do it with.

The alcohols used for esterifying the polymerized rosin are the same as above.

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

The physical properties of the polymerized rosin ester are not particularly limited. From the viewpoint of excellent curved surface adhesiveness, adhesive strength and holding power, the physical properties of the polymerized rosin ester preferably have a softening point of about 150 to 180 ° C.

The unsaturated carboxylic acid-modified rosin ester is obtained by reacting the α, β-unsaturated carboxylic acid-modified rosin with alcohols to esterify it.

The reaction conditions between the α, β-unsaturated carboxylic acid-modified rosin and the alcohols are not particularly limited, but for example, alcohol is added to the α, β-unsaturated carboxylic acid-modified rosin melted under heating. The reaction may be carried out at a temperature of about 250 to 280 ° C. for about 15 to 20 hours. Further, the above reaction may be carried out while blowing an inert gas such as nitrogen into the closed reaction system, or the above-mentioned catalyst may be used.

The alcohols used for esterifying the α, β-unsaturated carboxylic acid-modified rosin are the same as above.

The rosin phenol resin is obtained by reacting the raw material rosin with phenols.

The phenols are not particularly limited, and various known phenols can be used. Specific examples thereof include alkylphenols such as cresol, butylphenol, octylphenol and nonylphenol, phenols, bisphenols and naphthols. These may be used alone or in combination of two or more. From the viewpoint of emulsifying property, the amount of phenols used may be about 0.8 to 1.5 mol with respect to 1 mol of the raw material rosin.

The method for producing the rosin phenol resin is not particularly limited, and examples thereof include heating and reacting the raw material rosin and phenols in the presence of an acid catalyst, if necessary. The reaction temperature is usually 180 to 350 ° C. for about 6 to 18 hours. The acid catalyst that can be used in the reaction is not particularly limited, and for example, an inorganic acid catalyst such as sulfuric acid, hydrogen chloride, or boron trifluoride, or an organic acid catalyst such as p-toluenesulfonic acid or methanesulfonic acid can be used. Can be mentioned. When an acid catalyst is used, it may be used in an amount of about 0.01 to 1.0 part by mass with respect to 100 parts by mass of the raw material rosin. Further, the rosin phenol resin may be an esterified resin obtained by further reacting alcohols with the resin obtained by the above reaction. The alcohols used at that time are the same as above.

The component (A) is preferably the above-mentioned rosin esters and / or rosin phenol resins from the viewpoint of excellent balance of curved surface adhesiveness, compatibility, adhesive force and holding power. Further, the polymerized rosin ester is more preferable from the viewpoint of excellent balance of curved surface adhesiveness, compatibility, adhesive force and holding power.

<Petroleum resin (B)>
Component (B), the ¹ H-NMR total peak area values in the spectrum peak area value of 6.3~7.6ppm for _{(S NMR) (S 'NMR} ) ratio _{(S' NMR / S NMR)} ( hereinafter , is the _{(S 'NMR / S NMR)} ), a 0 to 4.0% as a percentage. If the ( _S'NMR / S _NMR ) exceeds 4.0%, the curved surface adhesiveness of the water-based adhesive / adhesive composition becomes insufficient.

In the present specification, the above-mentioned "6.3 to 7.6 ppm" refers to a region in which a (signal) peak derived from an aromatic ring contained in the component (B) appears in the ¹ H-NMR spectrum. Further, if it is a peak considered to be derived from an aromatic ring, it may be a peak of "6.3 to 7.6 ppm". That is, the above ( _S'NMR / S _NMR ) means the content of an aromatic ring component such as a benzene ring in the component (B). In the present specification, peaks derived from the NMR measurement solvent (deuterated chloroform or the like) are excluded from all the peaks appearing in the above "6.3 to 7.6 ppm". Further, the "total peak area value (S _NMR )" does not include the integrated value of the peak derived from the NMR measurement solvent.

The tackifier resin emulsion of the present invention is compatible with the water-based adhesive / adhesive composition by using the component (A) and the component (B) in which ( _S'NMR / S _NMR ) is in a specific range in combination. While maintaining, the curved surface adhesiveness becomes excellent. The details are not clear, but the following reasons can be speculated. In the component (B), it means that it has a low content or the content of the aromatic ring component is 0 is the _{0~4.0% (S 'NMR / S} NMR), (B) It can be said that the components have low polarity. Then, it is presumed that the component (B) having low polarity has an improved affinity for the polyolefin resin having low polarity.

The above ( _S'NMR / S _NMR ) in the component (B) is preferably about 0 to 1.0% from the viewpoint of further excellent curved surface adhesiveness.

Component (B), if the _{(S 'NMR} / S _NMR) is from 0 to 4.0%, various known petroleum resins may used without particular limitation. The component (B) is preferably at least one petroleum resin selected from the group consisting of an aliphatic petroleum resin, an alicyclic petroleum resin, and a hydrogenated petroleum resin from the viewpoint of excellent curved adhesiveness.

Examples of the aliphatic petroleum resin include C5 petroleum resin obtained from the C5 petroleum distillate of naphtha. The C5 petroleum distillate is a conjugated diolefinically unsaturated hydrocarbon having 4 to 6 carbon atoms represented by, for example, isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, methylcyclopentadiene and the like. Hydrogens; Monoolefinically unsaturated hydrocarbons having 4 to 6 carbon atoms represented by butene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, cyclopentene and the like; Alibo-based saturated hydrocarbons such as cyclopentane, 2-methylpentane, 3-methylpentane, and n-hexane; mixtures thereof and the like can be mentioned.

Examples of the alicyclic petroleum resin include DCPD petroleum resins obtained from dicyclopentadiene petroleum distillates of naphtha. The dicyclopentadiene petroleum distillate has, for example, a cyclic aliphatic compound having 10 carbon atoms such as dicyclopentadiene; a cyclic aliphatic compound having 11 carbon atoms such as methyldicyclopentadiene; and having 12 carbon atoms such as dimethyldicyclopentadiene. Cyclic aliphatic compounds; examples thereof include mixtures thereof.

Examples of the hydrogenated petroleum resin include hydrides of petroleum resins such as the above-mentioned aliphatic petroleum resin, the above-mentioned alicyclic petroleum resin, aromatic petroleum resin, and aliphatic / aromatic petroleum resin.

Examples of the aromatic petroleum resin include a C9 petroleum resin obtained from a C9 petroleum distillate of naphtha, a copolymer obtained by polymerizing one or more of the C9 petroleum resins, and the like. The C9 petroleum distillate is, for example, an aromatic compound having 8 carbon atoms such as styrene; an aromatic compound having 9 carbon atoms such as α-methylstyrene, β-methylstyrene, vinyltoluene, and indene; 1-methylindene, 2-. Examples thereof include aromatic compounds having 10 carbon atoms such as methyl indene and 3-methyl indene; aromatic compounds having 11 carbon atoms such as 2,3-dimethyl indene and 2,5-dimethyl indene; and mixtures thereof.

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

When the above aromatic petroleum resin and aliphatic / aromatic petroleum resin are used as the component (B), most of them have ( _S'NMR / S _NMR ) exceeding 4.0%, so that they are water-based sticky. -The curved adhesiveness of the adhesive composition is insufficient, which is not preferable.

The physical properties of the component (B) are not particularly limited except for the above ( _S'NMR / S _NMR ). The softening point of the component (B) is preferably about 60 to 160 ° C. from the viewpoint of high adhesiveness and holding power to polyolefin and excellent curved surface adhesiveness.

The weight average molecular weight of the component (B) is preferably about 500 to 4,000 from the viewpoint of excellent compatibility with the base polymer. The weight average molecular weight of the component (B) is more preferably about 500 to 3,500 from the viewpoint of not only excellent compatibility but also high holding power, and further, not only excellent compatibility and holding power, but also excellent holding power. About 500 to 2,500 is particularly preferable from the viewpoint of excellent curved surface adhesiveness. In the present specification, the weight average molecular weight refers to a polystyrene-equivalent value in the gel permeation chromatography (GPC) method.

The mass ratio of the component (A) to the component (B) ((A) / (B)) is not particularly limited, but is 60/40 to 99 / in terms of solid content because of its excellent compatibility with the base polymer. 1 is preferable. Further, (A) / (B) is more preferably 70/30 to 95/5 from the viewpoint of not only excellent compatibility and high holding power, and further, not only excellent compatibility and holding power, but also 80/20 to 90/10 is particularly preferable because it is also excellent in curved surface adhesiveness.

<Emulsifier (C)>
The component (C) is not particularly limited, and various known emulsifiers can be used. Specific examples thereof include a high molecular weight emulsifier obtained by polymerizing a monomer, a low molecular weight anionic emulsifier, and a low molecular weight nonionic emulsifier. These may be used alone or in combination of two or more.

Examples of the monomer used for producing the high molecular weight emulsifier include (meth) acrylic acid ester-based monomers such as methyl (meth) acrylate and ethyl (meth) acrylate; (meth) acrylate, crotonic acid and the like. Monocarboxylic acid-based vinyl monomers; Dicarboxylic acid-based vinyl monomers such as maleic acid and maleic anhydride; and sulfonic acid-based vinyl monomers such as vinyl sulfonic acid and styrene sulfonic acid; and alkalis of these various organic acids. Metal salts, alkaline earth metal salts, ammonium salts, organic base salts; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol (meth) acrylamide; nitrile-based monomers such as (meth) acrylonitrile Classes; Vinyl ester-based monomers such as vinyl acetate; Hydroxy group-containing (meth) acrylic acid ester-based monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Methylvinyl ether, glycidyl Examples thereof include (meth) acrylate, urethane acrylate, α-olefin having 6 to 22 carbon atoms, and other monomers such as vinylpyrrolidone. These may be used alone or in combination of two or more.

Examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization using a reactive emulsifier other than the high molecular weight emulsifier described later, and a non-reactive emulsifier other than the high molecular weight emulsifier.

The weight average molecular weight of the high molecular weight emulsifier thus obtained is not particularly limited, but it is usually preferably about 1,000 to 500,000 in terms of the adhesive properties of the obtained tackifier resin emulsion. The weight average molecular weight referred to here refers to a polystyrene-equivalent value in the gel permeation chromatography (GPC) method.

Reactive emulsifiers other than the above high molecular weight emulsifiers include, for example, hydrophilic groups such as sulfonic acid groups and carboxyl groups and hydrophobic groups such as alkyl groups and phenyl groups, and have carbon-carbon double bonds in the molecule. Those having a bond.

Examples of the low molecular weight anionic emulsifier include dialkyl sulfosuccinate salt, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate salt, polyoxyethylene styrylphenyl ether sulfosuccinate salt, and naphthalene. Examples thereof include formalin sulfonic acid condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene dialkyl ether sulfate, polyoxyethylene trialkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate and the like. These may be used alone or in combination of two or more.

Examples of the low molecular weight nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitan fatty acid ester. These may be used alone or in combination of two or more.

The amount of the component (C) used is not particularly limited, but from the viewpoint of excellent emulsifying property, about 1 to 20 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B) in terms of solid content. Is preferable, and about 2 to 10 parts by mass is more preferable.

The tackifier resin emulsion of the present invention can be used as a defoaming agent, a thickener, a filler, an antioxidant, a water resistant agent, a film-forming aid, ammonia water, baking soda, etc., as required, as long as the desired properties are not impaired. May include a pH adjuster and the like.

In the tackifier resin emulsion of the present invention, the components (A) and (B) are separately emulsified in the presence of the component (C) (hereinafter, also referred to as "emulsifier"), and the obtained emulsion is mixed. Alternatively, it can be obtained by emulsifying component (A) and component (B) together. The emulsification method is not particularly limited, and known emulsification methods such as a high-pressure emulsification method and a phase inversion emulsification method can be adopted.

In the above high-pressure emulsification method, the component (A) and / or the component (B) are melted, the emulsifier and water are premixed, finely emulsified using a high-pressure emulsifier, and then a solvent is required. Is a method of removing. The method of melting the emulsion may be by heating only, by dissolving it in a solvent and then heating it, or by mixing a non-volatile substance such as a plasticizer and heating it, but it should be performed only by heating. Is preferable. Examples of the solvent include organic solvents capable of dissolving an emulsion such as toluene, xylene, methylcyclohexane, and ethyl acetate.

In the phase inversion emulsification method, after the component (A) and / or the component (B) is heated and melted, an emulsifier and water are added while stirring to form a W / O emulsion first, and then water is added and the temperature is changed. This is a method of inversion to an O / W emulsion by means of the above.

The concentration of the tackifier resin emulsion thus obtained is not particularly limited, but is usually adjusted appropriately so that the solid content is about 20 to 70% by mass. The volume average particle size of the obtained tackifier resin emulsion is usually about 0.1 to 2 μm. Most of the tackifier resin emulsion is uniformly dispersed as particles of 1 μm or less, but the volume average particles are preferably 0.7 μm or less from the viewpoint of storage stability. Further, the obtained tackifier resin emulsion has a white to milky white appearance, and the viscosity is usually about 10 to 1,000 mPa · s (temperature 25 ° C., concentration 50% by mass).

The pH of the tackifier resin emulsion obtained above is usually about 2 to 10. Further, the tackifier resin emulsion may be prepared from an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc .; an alkanol amine such as monomethylamine, monoethanolamine, diethanolamine, diisopropanolamine; ethylamine, n-butylamine, triethylamine, etc. The pH may be adjusted by appropriately adding an aliphatic amine; an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide; and an alkaline earth metal hydroxide such as calcium hydroxide.

[Water-based adhesive / adhesive composition]
The water-based adhesive / adhesive composition of the present invention contains the tackifier resin emulsion and the base polymer of the present invention. Further, the water-based adhesive / adhesive composition of the present invention can be used as a water-based adhesive / adhesive. In addition, in this specification, "adhesive / adhesive" is clarified to include either one or both of adhesive and adhesive.

Examples of the base polymer include acrylic polymer emulsions, rubber latexs, synthetic resin emulsions and the like, and each of them can be used in combination, and if necessary, a cross-linking agent, a defoaming agent, a thickener and a filling agent can be used. Agents, antioxidants, water resistant agents, film-forming aids, pH adjusters such as ammonia water and baking soda can also be used. Further, a known tackifier resin emulsion may be further used. The concentration of these water-based adhesive / adhesive compositions is usually about 40 to 70% by mass, preferably 55 to 70% by mass, in terms of solid content.

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

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. Meta) 2-hydroxyethyl acrylate and the like can be mentioned, and these are used alone or in combination of two or more. Further, in order to impart storage stability to the obtained emulsion, (meth) acrylic acid may be used instead of a part of the above (meth) acrylic acid ester. Further, if desired, a copolymerizable monomer such as vinyl acetate or styrene can be used in combination to the extent that the adhesive properties of the (meth) acrylic acid ester polymer are not impaired. Anionic emulsifier, partially saponified polyvinyl alcohol, etc. can be used as the emulsifier used in the acrylic polymer emulsion, and the amount used is 100 parts by mass of the (meth) acrylic acid ester polymer in terms of solid content. It is about 0.1 to 5 parts by mass, preferably about 0.5 to 3 parts by mass.

The content ratio of the acrylic polymer emulsion and the tackifier resin emulsion is not particularly limited, but the effect of modification by the tackifier resin emulsion can be sufficiently exhibited, and the heat retention and tackiness can be reduced due to excessive use. As an appropriate range of use that does not cause the problem, it is preferable that the pressure-sensitive resin emulsion is usually about 2 to 40 parts by mass with respect to 100 parts by mass of the acrylic polymer emulsion in terms of solid content.

As the rubber-based latex, various known rubber-based latexes used in the water-based adhesive / adhesive composition can be used. For example, natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex and the like can be mentioned.

The content ratio of the rubber latex and the tackifying resin emulsion is not particularly limited, but it is appropriate that the effect of modification by the tackifying resin emulsion can be sufficiently exhibited and the adhesive strength, tack, etc. are not deteriorated due to excessive use. The range of use is preferably about 10 to 150 parts by mass of the tackifier resin emulsion with respect to 100 parts by mass of the rubber latex in terms of solid content.

As the synthetic resin emulsion, various known emulsions used in water-based adhesive / adhesive compositions can be used, and for example, synthetic resin emulsions such as vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, and urethane emulsion can be used. Can be mentioned.

The content ratio of the synthetic resin emulsion and the tackifier resin emulsion is not particularly limited, but the effect of modifying the tackifier resin emulsion can be sufficiently exhibited, and excessive use does not cause deterioration of adhesive strength, tack, etc. As an appropriate usage ratio, it is preferable that the pressure-imparting resin emulsion is usually about 2 to 40 parts by mass with respect to 100 parts by mass of the synthetic resin emulsion in terms of solid content.

The water-based adhesive / adhesive composition of the present invention can be obtained by mixing the tackifier resin emulsion and the base polymer. The mixing method is not particularly limited, and various known methods can be used.

[Adhesive / adhesive sheet]
The adhesive / adhesive sheet of the present invention contains the adhesive / adhesive layer and the base material made of the above water-based adhesive / adhesive composition. The sticky / adhesive sheet of the present invention may be a sticky / adhesive sheet with a base material having the sticky / adhesive layer on one side or both sides of the base material, and the sticky / adhesive layer is a release liner (peeling surface). It may be a base material-less adhesive / adhesive sheet such as a form held in (which can also be grasped as a base material to be provided). The concept of the adhesive / adhesive sheet referred to herein may include what is called an adhesive / adhesive tape, an adhesive / adhesive label, an adhesive / adhesive film, or the like.

Examples of the base material include a polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.) film, a polyester (polyethylene terephthalate, etc.) film, a vinyl chloride resin film, a vinyl acetate resin film, and a polyimide film. Resin films, polyamide-based resin films, fluorine-based resin films, and other plastic films such as cellophane; Japanese paper, kraft paper, glassin paper, high-quality paper, synthetic paper, top-coated paper, and other papers; various fibers Fabrics such as woven fabrics and non-woven fabrics made of a single or blended material; rubber sheets made of natural rubber, butyl rubber, etc .; foam sheets made of foams such as foamed polyurethane and foamed polychloroprene rubber; aluminum foil, copper A metal foil such as a foil; a composite thereof; or the like can be used.

The adhesive / adhesive sheet of the present invention can be produced by a known method. First, the water-based adhesive / adhesive composition is applied to one side or both sides of the base material to form a coating layer composed of the water-based adhesive / adhesive composition. A known method can be applied as the coating method, and examples thereof 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. Next, the coating layer is heated or dried to form a viscous / adhesive layer made of the above water-based viscous / adhesive composition. The conditions for heating or drying can be appropriately set depending on the thickness of the adhesive layer and the like, and the temperature is, for example, 10 to 120 ° C., and the time is, for example, 0.1 to 10 hours. The thickness of the adhesive / adhesive layer (thickness after drying) varies depending on the application, but is preferably 5 to 200 μm.

Since the adhesive / adhesive sheet of the present invention contains the adhesive / adhesive layer made of the above water-based adhesive / adhesive composition, it has excellent curved adhesiveness. For example, it is a polyolefin-based material for building materials, automobile interior members, film labels, etc. It is suitable as an adhesive / adhesive sheet for applications where it is attached to a curved surface of a resin. Further, since the adhesive / adhesive sheet of the present invention is also excellent in transparency, the adhesive / adhesive sheet for applications requiring transparency and design, for example, a transparent label used for a cosmetic container or a shampoo container. Is also suitable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" in the examples are based on mass.

<Measurement of weight average molecular weight>
The weight average molecular weights of the petroleum resins (B-1) to (B'-3) in Production Examples 14 to 22 were determined by using gel permeation chromatography (manufactured by Tosoh Corporation, trade name "HLC-8320GPC"). The measurement was performed by connecting three columns (manufactured by Tosoh Corporation, trade name "TSKgelSuperHM-L"), and determined by polystyrene conversion.

<Calculation of ( _S'NMR / S _NMR )>
Each of the petroleum resins (B-1) to (B'-3) in Production Examples 14 to 22 was dissolved in a deuterated chloroform solvent to prepare a 5% (w / v) solution, and this solution was used as a commercially available 1H solution. A ¹ H-NMR spectrum was obtained using a NMR apparatus (product name "Varian Unity INOVA-400", 400 MHz type, manufactured by Varian). Then, the value (%) of ( _S'NMR / S _NMR ) in each petroleum resin was calculated from the following mathematical formula. The calculated value was regarded as the content of the aromatic ring component in the component (B).

_{(S 'NMR / S NMR)} (%) = [peak area value of 6.3~7.6ppm area (S' _NMR) / total peak area value _{(S NMR)]} × 100

[Manufacturing of base polymer]
Manufacturing example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 43.4 parts of water and an ammonium salt of polyoxyethylene alkyl ether sulfate (anionic emulsifier: trade name) under a nitrogen gas stream. An aqueous solution consisting of 0.92 parts of "Hitenol LA-16" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was charged 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, 0.24 part of potassium persulfate (polymerization initiator), 0.11 part of baking soda (pH adjuster) and water. A 1/10 amount of an initiator aqueous solution consisting of 8.83 parts was 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 initiator aqueous solution were added to the reaction vessel for 2 hours to carry out emulsion polymerization, and then held at 70 ° C. for 1 hour to complete the polymerization reaction. The acrylic polymer emulsion thus obtained was cooled to room temperature and then filtered using a 100-mesh wire mesh to obtain an acrylic polymer emulsion having a solid content concentration of 47.8%.

(Manufacturing of polymerized rosin ester)
Manufacturing example 2
In a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction pipe / steam introduction pipe,
After charging 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140 ° C.) and 14 parts of pentaerythritol, the reaction was carried out at 250 ° C. for 2 hours under a nitrogen gas stream, and then the temperature was further raised to 280 ° C. and the same temperature. The reaction was carried out in 12 hours to complete the esterification. Then, water and the like were removed under reduced pressure to obtain a polymerized rosin ester (A-1) having a softening point of 160 ° C.

Manufacturing example 3
In a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction pipe / steam introduction pipe,
After charging 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140 ° C.) and 13 parts of pentaerythritol, the reaction was carried out at 250 ° C. for 2 hours under a nitrogen gas stream, and then the temperature was further raised to 280 ° C. to the same temperature. Was reacted for 14 hours to complete esterification. Then, 0.1 MPa of steam was blown in for 4 hours to obtain a polymerized rosin ester (A-2) having a softening point of 180 ° C.

Manufacturing example 4
In a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction pipe / steam introduction pipe,
After charging 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140 ° C.), 50 parts of gum rosin (acid value 160 mgKOH / g, softening point 70 ° C.), and 12 parts pentaerythritol, at 250 ° C. under a nitrogen gas stream. After the reaction for 2 hours, the temperature was further raised to 280 ° C. and the reaction was carried out at the same temperature for 12 hours to complete the esterification. Then, water and the like were removed under reduced pressure to obtain a polymerized rosin ester (A-3) having a softening point of 125 ° C.

(Manufacturing of rosin phenol resin)
Production example 5
In a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction pipe / steam introduction pipe,
After charging 50 parts of gum rosin (acid value 160 mgKOH / g, softening point 70 ° C.) and 100 parts of phenol, the temperature was raised to 100 ° C., 2.1 parts of 96% sulfuric acid was charged, and the mixture was reacted under a nitrogen gas stream for 3 hours. Then, after adding 3.0 parts of slaked lime, the temperature was raised to 280 ° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 4 hours. Then, water and the like were removed to obtain a rosin phenol resin (A-4) having a softening point of 150 ° C.

(Manufacture of unsaturated carboxylic acid-modified polymerized rosin ester)
Production example 6
In a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction pipe / steam introduction pipe,
After charging 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140 ° C.) and 5 parts of maleic anhydride, reacting under a nitrogen gas stream at 220 ° C. for 2 hours, and then charging 16 parts of pentaerythritol. After reacting at 250 ° C. for 2 hours under a nitrogen gas stream, the temperature was further raised to 280 ° C. and the reaction was carried out at the same temperature for 10 hours to complete esterification. Then, 0.1 MPa of water vapor was blown in for 4 hours to obtain an unsaturated carboxylic acid-modified polymerized rosin ester (A'-1) having a softening point of 190 ° C.

(Manufacturing of gum rosin ester)
Production example 7
In a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction pipe / steam introduction pipe,
After charging 100 parts of gumrosin (acid value 160 mgKOH / g, softening point 70 ° C.) and 1 part of fumaric acid, the mixture was heated under a nitrogen gas stream until the temperature inside the system reached 220 ° C. and reacted for 1 hour. Then, after charging 13 parts of pentaerythritol, the reaction was carried out at 250 ° C. for 2 hours, then the temperature was further raised to 280 ° C. and the reaction was carried out at the same temperature for 12 hours to complete the esterification. Then, water and the like were removed under reduced pressure to obtain a gum rosin ester (A'-2) having a softening point of 100 ° C.

(Manufacturing of polymerized rosin ester emulsion)
Production Example 8
After dissolving 100 parts of the polymerized rosin ester (A-1) of Production Example 2 in 80 parts of methylcyclohexane at 80 ° C. for 3 hours, polyoxyethylene alkyl (12 to 14 carbon atoms) disodium sulfosuccinate (hereinafter , Emulsifier (C-1)) 3 parts (in terms of solid content) and 140 parts of water were added, and the mixture was stirred for 1 hour. Then, a high-pressure emulsifier (manufactured by Menton Gaulin Co., Ltd.) was used to high-pressure emulsify at a pressure of 30 MPa to obtain an emulsion. Then, distillation was carried out under reduced pressure for 6 hours under the conditions of 70 ° C. and 2.93 × 10 ⁻² MPa to obtain a polymerized rosin ester emulsion having a solid content concentration of 50%.

Manufacturing example 9
In Production Example 8, the same procedure was carried out except that the polymerized rosin ester (A-1) was changed to the polymerized rosin ester (A-2) to obtain a polymerized rosin ester emulsion having a solid content concentration of 50%.

Production Example 10
In Production Example 8, the same procedure was carried out except that the polymerized rosin ester (A-1) was changed to the polymerized rosin ester (A-3) to obtain a polymerized rosin ester emulsion having a solid content concentration of 50%.

(Manufacturing of rosin phenol resin emulsion)
Production Example 11
In Production Example 8, the same procedure was carried out except that the polymerized rosin ester (A-1) was changed to a rosin phenol resin (A-4) to obtain a rosin phenol resin emulsion having a solid content concentration of 50%.

(Manufacturing of polymerized rosin ester emulsion)
Production Example 12
In Production Example 8, the same procedure was carried out except that the polymerized rosin ester (A-1) was changed to the polymerized rosin ester (A'-1) to obtain a polymerized rosin ester emulsion having a solid content concentration of 50%.

(Manufacture of gum rosin ester emulsion)
Production Example 13
In Production Example 8, the same procedure was carried out except that the polymerized rosin ester (A-1) was changed to a gum rosin ester (A'-2) to obtain a gum rosin ester emulsion having a solid content concentration of 50%.

(Manufacturing of C5 petroleum resin emulsion)
Production example 14
_{(S 'NMR} / S _NMR) is the C5 is 0.6% petroleum resin (trade name "HIKOREZ A-1100", KOLON Co., weight average molecular weight of 2,000) (hereinafter, petroleum resin (B-1) After dissolving 100 parts in 80 parts of methylcyclohexane at 80 ° C. for 3 hours, 3 parts of emulsifier (C-1) (in terms of solid content) and 140 parts of water were added, and the mixture was stirred for 1 hour. Then, a high-pressure emulsifier (manufactured by Menton Gaulin Co., Ltd.) was used to high-pressure emulsify at a pressure of 30 MPa to obtain an emulsion. Next, vacuum distillation was carried out under the conditions of 70 ° C. and 2.93 × ^10-2 MPa for 6 hours to obtain a C5 petroleum resin emulsion having a solid content concentration of 50%.

Production example 15
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is C5-based petroleum resin is 0.2% (trade name "T-REZ RC-100", JXTG Energy Company A C5-based petroleum resin emulsion having a solid content concentration of 50% was obtained in the same manner except that the product was changed to petroleum resin (B-2), which has a weight average molecular weight of 1,800).

Production example 16
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is C5-based petroleum resin is 0.1% (trade name "T-REZ RA-100", JXTG Energy Company A C5 petroleum resin emulsion having a solid content concentration of 50% was obtained in the same manner except that the product was changed to petroleum resin (B-3) having a weight average molecular weight of 3,000).

Production example 17
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is C5-based petroleum resin is 0.1% (trade name "T-REZ RB-100", JXTG Energy Company A C5 petroleum resin emulsion having a solid content concentration of 50% was obtained in the same manner except that the product was changed to petroleum resin (B-4) having a weight average molecular weight of 3,300).

(Manufacturing of hydrogenated petroleum resin emulsion)
Production Example 18
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is hydrogenated petroleum resin is 0.1% (trade name "ESCOREZ 5300", ExxonMobile manufactured, the weight-average molecular weight 700) ( Hereinafter, the same procedure was carried out except that the mixture was changed to petroleum resin (B-5)) to obtain a hydrogenated petroleum resin emulsion having a solid content concentration of 50%.

Production example 19
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is 2.1% hydrogenated petroleum resin (trade name "ARKON P-115", manufactured by Arakawa Chemical Industries, Ltd. , Weight average molecular weight 1,600) (hereinafter referred to as petroleum resin (B-6)) was carried out in the same manner to obtain a hydrogenated petroleum resin emulsion having a solid content concentration of 50%.

(Manufacture of C5 / C9 copolymerized petroleum resin emulsion)
Production example 20
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is 5.0% C5 / C9 copolymer petroleum resin (trade name "Quintone G-115", Nippon Zeon ( C5 / C9 copolymer petroleum resin emulsion with a solid content concentration of 50%, except that it was changed to petroleum resin (B'-1), manufactured by Co., Ltd., with a weight average molecular weight of 4,300). Got

(Manufacturing of C9 petroleum resin emulsion)
Production example 21
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is C9 petroleum resin is 45.0% (trade name "HIKOTACK P-120", KOLON Co., weight average molecular weight A C9 petroleum resin emulsion having a solid content concentration of 50% was obtained in the same manner except that the mixture was changed to 1,900) (hereinafter referred to as petroleum resin (B'-2)).

(Manufacturing of hydrogenated petroleum resin emulsion)
Production example 22
Production Example 14, the petroleum resin (B-1), (S 'NMR / S NMR) is 7.1% hydrogenated petroleum resin (trade name "Arkon M-100", manufactured by Arakawa Chemical Industries, Ltd. , Weight average molecular weight 1,300) (hereinafter referred to as petroleum resin (B'-3)) was carried out in the same manner to obtain a hydrogenated petroleum resin emulsion having a solid content concentration of 50%.

[Preparation of adhesive resin emulsion]
Example 1
80 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 20 parts (solid content equivalent) of the C5 petroleum resin emulsion of Production Example 14 were blended to obtain a tackifier resin emulsion.

Example 2
In Example 1, the same procedure was carried out except that the polymerized rosin ester emulsion of Production Example 8 was changed to the polymerized rosin ester emulsion of Production Example 9 to obtain a tackifier resin emulsion.

Example 3
In Example 1, the same procedure was carried out except that the polymerized rosin ester emulsion of Production Example 8 was changed to the polymerized rosin ester emulsion of Production Example 10 to obtain a tackifier resin emulsion.

Example 4
In Example 1, the same procedure was carried out except that the polymerized rosin ester emulsion of Production Example 8 was changed to the rosin phenol resin emulsion of Production Example 11 to obtain a tackifier resin emulsion.

Example 5
In Example 1, the C5 petroleum resin emulsion of Production Example 14 was changed to the C5 petroleum resin emulsion of Production Example 15 in the same manner, to obtain a tackifier resin emulsion.

Example 6
In Example 1, the same procedure was carried out except that the C5 petroleum resin emulsion of Production Example 14 was changed to the C5 petroleum resin emulsion of Production Example 16 to obtain a tackifier resin emulsion.

Example 7
In Example 1, the C5 petroleum resin emulsion of Production Example 14 was changed to the C5 petroleum resin emulsion of Production Example 17, but the same procedure was carried out to obtain a tackifier resin emulsion.

Example 8
In Example 1, the C5 petroleum resin emulsion of Production Example 14 was changed to the hydrogenated petroleum resin emulsion of Production Example 18, but the same procedure was carried out to obtain a tackifier resin emulsion.

Example 9
In Example 1, the C5-based petroleum resin emulsion of Production Example 14 was changed to the hydrogenated petroleum resin emulsion of Production Example 19 in the same manner to obtain a tackifier resin emulsion.

Example 10
90 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 10 parts (solid content equivalent) of the C5 petroleum resin emulsion of Production Example 14 were blended to obtain a tackifier resin emulsion.

Example 11
70 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 30 parts (solid content equivalent) of the C5 petroleum resin emulsion of Production Example 14 were blended to obtain a tackifier resin emulsion.

Example 12
60 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 40 parts (solid content equivalent) of the C5 petroleum resin emulsion of Production Example 14 were blended to obtain a tackifier resin emulsion.

Example 13
After dissolving 80 parts of the polymerized rosin ester (A-1) and 20 parts of the petroleum resin (B-1) of Production Example 2 in 80 parts of methylcyclohexane at 80 ° C. for 3 hours, the emulsifier (C-1) 3 Parts (in terms of solid content) and 140 parts of water were added, and the mixture was stirred for 1 hour. Then, a high-pressure emulsifier (manufactured by Menton Gaulin Co., Ltd.) was used to high-pressure emulsify at a pressure of 30 MPa to obtain an emulsion. Next, vacuum distillation was carried out under the conditions of 70 ° C. and 2.93 × ^10-2 MPa for 6 hours to obtain a tackifier resin emulsion having a solid content concentration of 50%.

Comparative Example 1
The polymerized rosin ester emulsion of Production Example 8 was used as a tackifier resin emulsion.

Comparative Example 2
The C5-based petroleum resin emulsion of Production Example 14 was used as a tackifier resin emulsion.

Comparative Example 3
80 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 12 and 20 parts (solid content equivalent) of the C5 petroleum resin emulsion of Production Example 14 were blended to obtain a tackifier resin emulsion.

Comparative Example 4
80 parts (solid content equivalent) of the gum rosin ester emulsion of Production Example 13 and 20 parts (solid content equivalent) of the C5 petroleum resin emulsion of Production Example 14 were blended to obtain a tackifier resin emulsion.

Comparative Example 5
80 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 20 parts (solid content equivalent) of the C5 / C9 copolymer petroleum resin emulsion of Production Example 20 were blended to obtain a tackifier resin emulsion.

Comparative Example 6
80 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 20 parts (solid content equivalent) of the C9 petroleum resin emulsion of Production Example 21 were blended to obtain a tackifier resin emulsion.

Comparative Example 7
80 parts (solid content equivalent) of the polymerized rosin ester emulsion of Production Example 8 and 20 parts (solid content equivalent) of the hydrogenated petroleum resin emulsion of Production Example 22 were blended to obtain a tackifier resin emulsion.

[Manufacturing of water-based adhesive / adhesive composition]
95 parts (solid content equivalent) of the acrylic polymer emulsion synthesized in Production Example 1 and 5 parts (solid content equivalent) of the tackifier resin emulsion of Example 1 were mixed to obtain an aqueous viscous / adhesive composition. .. Water-based adhesive / adhesive compositions were produced in the same manner for the tackifier resin emulsions of Examples 2 to 13 and Comparative Examples 1 to 7.

[Preparation of sample tape]
Using a dice type applicator (manufactured by Daisuke Kikai Co., Ltd.), the above water-based adhesive / adhesive composition was applied to a polyester film (trade name "S-100", manufactured by Mitsubishi Chemical Co., Ltd., thickness: 38 μm) with a thickness of about 35 μm. Then, it was dried in a circulation dryer at 105 ° C. for 5 minutes to prepare a sample tape.

[Curved surface adhesiveness]
The sample tape (width 20 mm x length 35 mm) is bent and attached to a polypropylene cylinder having a diameter of 15 mm, and after 3 days, the distance (hereinafter, adhesion distance) (mm) of the portion of the sample tape that is adhered to the cylinder is determined. It was measured and evaluated by the adhesion ratio (%) represented by the following formula. The results are shown in Table 1. It can be said that the higher the adhesive ratio, the higher the curved surface adhesiveness.
Adhesion rate (%) = Adhesion distance (mm) / 35mm x 100
⊚: Adhesive rate (%) is 70% or more ○: Adhesive rate (%) is 50% or more and less than 70% Δ: Adhesive rate (%) is 40% or more and less than 50% ×: Adhesive rate (%) is less than 40%

[Compatibility]
Using a spectrophotometer (manufactured by Hitachi, Ltd., trade name "U-3210 type self-recording spectrophotometer"), the sample tape was irradiated with light of 500 nm, and the transmittance (%) was measured. The results are shown in Table 1. It can be said that the higher the transmittance, the more excellent the tackifier resin emulsion has in compatibility with the base polymer in the water-based adhesive / adhesive composition, and the water-based adhesive / adhesive composition has higher transparency.
◯: Transmittance (%) is 84% or more Δ: Transmittance (%) is 80% or more and less than 84% ×: Transmittance (%) is less than 80%

[Evaluation of adhesive strength]
The sample tape was cut into a width of 25 mm, and a 2 kg roller was reciprocated once on an adherend (polyethylene plate) to be attached and allowed to stand for one day. Next, a 180-degree peeling test was performed under the conditions of a tensile speed of 300 mm / min and a measurement temperature of 23 ° C., and the adhesive strength (N / 25 mm) was measured. The results are shown in Table 1.

[Evaluation of holding power]
The sample tape (25 mm × 25 mm) was superposed on a stainless steel plate and reciprocated once with a roller weighing 2 kg to be bonded. A load of 1.0 kg was applied to the sample tape at 60 ° C., and the time (h) until the sample tape fell was measured. The results are shown in Table 1. It can be said that the longer it takes to fall, the higher the holding power.

The notes in Table 1 are as follows.
* Indicates the mass ratio converted to solid content.

Claims (8)

Rosin resin (A) with a softening point of 120 to 180 ° C,
Total peak area values in ¹ H-NMR spectrum 'ratio of _(NMR (S peak area values of 6.3~7.6ppm for _{(S NMR) S)' NMR} / S NMR) is from 0 to 4.0% Petroleum resin (B),
as well as,
A tackifier resin emulsion containing the emulsifier (C). The tackifier resin emulsion according to claim 1, wherein the component (A) is a polymerized rosin ester and / or a rosin phenol resin. The tackifier resin according to claim 1 or 2, wherein the component (B) is at least one petroleum resin selected from the group consisting of an aliphatic petroleum resin, an alicyclic petroleum resin, and a hydrogenated petroleum resin. Emulsion. The tackifier resin emulsion according to any one of claims 1 to 3, wherein the component (B) has a weight average molecular weight of 500 to 4,000. The item according to any one of claims 1 to 4, wherein the mass ratio ((A) / (B)) of the component (A) to the component (B) is 60/40 to 99/1 in terms of solid content. Adhesive-imparting resin emulsion. A water-based adhesive / adhesive composition comprising the tackifier resin emulsion according to any one of claims 1 to 5 and a base polymer. The water-based adhesive / adhesive composition according to claim 6, wherein the base polymer is an acrylic polymer emulsion. A viscous / adhesive sheet containing a viscous / adhesive layer and a base material comprising the water-based adhesive / adhesive composition according to claim 6 or 7.