JP7031633B2 - Adhesive-imparting resin emulsion and water-based adhesive / adhesive composition - Google Patents

Description

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

When manufacturing tapes, sheets, labels, etc., the adhesive / adhesive composition to be applied to paper, plastic film, etc., which is the base material, has conventionally been a tackifier resin for imparting adhesive strength (meth). A solution type in which a base polymer such as an acrylic polymer is dissolved in an organic solvent was generally used, but in recent years, an emulsion type water-based adhesive / adhesive has been taken into consideration for the environment, safety and health, resource saving, etc. Agent compositions are becoming mainstream.

As a water-based adhesive / adhesive composition, conventionally, the base polymer and the tackifier resin have been separately emulsified in the presence of various anionic emulsifiers and nonionic emulsifiers and mixed (Patent Documents). See 1 and 2). However, some of the tackifier resin emulsions obtained by using the emulsifier generate a large amount of agglomerates, and the emulsifying property of the emulsion is not yet sufficient. Further, even if an emulsifying adhesive resin emulsion having good emulsifying property is obtained, the water-based adhesive / adhesive containing the emulsion may be easily bound to water by the emulsifier, so that the emulsifier may easily bind to water under conditions of high water content and moisture. Adhesive strength to various substrates (hereinafter, also referred to as water resistant adhesive strength) may be low.

Japanese Unexamined Patent Publication No. 2001-139919 Japanese Unexamined Patent Publication No. 11-61087

An object of the present invention is to provide a novel tackifying resin emulsion which is excellent in emulsifying property and can impart high water-resistant adhesive force to a water-based viscous / adhesive composition.

As a result of diligent studies, the present inventor has found that a tackifier resin emulsion containing a specific resin and a specific multi-chain multi-hydrophilic group compound solves the above-mentioned problems. That is, the present invention relates to the following tackifier resin emulsion and water-based viscous / adhesive composition.

1. 1. 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 poly having at least two hydrophobic chains and hydrophilic groups in the molecule. A tackifier resin emulsion containing the chain polyhydrophilic group compound (B).

2. 2. Item (A) The tackifier resin emulsion according to Item 1, wherein the softening point of the component is 70 to 180 ° C.

3. 3. Item (a1) The tackifier resin emulsion according to Item 1 or 2, wherein the component is a rosin ester and / or a rosin phenol resin.

4. The tackifier according to any one of Items 1 to 3 above, wherein the component (B) is a compound having at least one hydrophobic chain and at least one hydrophilic group in the molecule, and (b) is a compound in which two molecules are bonded via a spacer. Resin emulsion.

5. A water-based adhesive / adhesive composition comprising the tackifier resin emulsion according to any one of Items 1 to 4 and a base polymer.

6. Item 5. The water-based adhesive / adhesive composition according to Item 5, wherein the base polymer is an acrylic polymer emulsion.

The tackifier resin emulsion of the present invention is excellent in emulsifying property because the generation of agglomerates is suppressed as compared with the case of using a conventional emulsifier. Further, the water-based adhesive / adhesive composition containing the tackifier resin emulsion has high water-resistant adhesive strength, and is suitable as a adhesive / adhesive in applications requiring water resistance. Further, the water-based adhesive / adhesive composition containing the tackifier resin emulsion has good whitening resistance (hereinafter, also referred to as water whitening resistance) of the adhesive / adhesive film under conditions of high moisture and humidity. It is suitable as a sticky / adhesive for applications where transparency and design are required in an environment with a lot of moisture and humidity, for example, a sticky / adhesive for a transparent label used for a cosmetic container or a shampoo container.

The tackifier resin emulsion of the present invention (hereinafter, also referred to as a tackifier resin emulsion) includes a rosin-based resin (a1) (hereinafter referred to as (a1) component), a petroleum resin (a2) (hereinafter referred to as (a2) component), and a petroleum resin (a2) component. At least one resin (A) (hereinafter referred to as (A) component) selected from the group consisting of a terpene resin (a3) (hereinafter referred to as (a3) component), and at least a hydrophobic chain and a hydrophilic group are contained in the molecule. It contains a multi-chain multi-hydrophilic group compound (B) having two each (hereinafter referred to as a component (B)).

The component (A) is at least one resin selected from the group consisting of the component (a1), the component (a2) and the component (a3).

The component (a1) is not particularly limited, and various known components can be used. For example, natural rosin (gum rosin, tall oil rosin, wood rosin) derived from Mao pine, slush pine, Merck pine, Shikaya pine, Theda pine, Daio pine, etc., natural rosin under reduced pressure distillation method, steam distillation method, extraction method, etc. Purified rosin obtained by purification by recrystallization method (hereinafter, natural rosin and purified rosin are collectively referred to as raw material rosin), hydride obtained by hydrogenating raw material rosin, and disproportionate reaction of raw material rosin. Α, β-unsaturated carboxylic acid-modified rosins such as disproportionated rosin, polymerized rosin, acrylicized rosin, maleated rosin, and fumarized rosin, or esterified products thereof (hereinafter referred to as rosin esters). , Rosin phenol resin and the like. These may be used alone or in combination of two or more. Among them, rosin esters and / or rosin phenol resins are preferable because they are excellent in water-resistant adhesive strength, water-whitening resistance, and adhesive performance.

The component (a2) is not particularly limited, and various known components can be used. For example, C5 based petroleum resin obtained from C5 distillate of naphtha such as penten, pentadiene and isoprene; C9 obtained from C9 distillate of naphtha such as inden, methyl inden, vinyl toluene, styrene, α-methyl styrene and β-methyl styrene. Based petroleum resin; C5-C9 copolymerized petroleum resin obtained from the C5 distillate and C9 distillate; pure monomer resin obtained by polymerizing styrene or the like as a main component; DCPD based petroleum obtained from cyclopentadiene and dicyclopentadiene. Resin; Examples thereof include hydrides of these petroleum resins. These may be used alone or in combination of two or more. Among these, C9-based petroleum resin is preferable because it is excellent in water-resistant adhesive strength, water-whitening resistance, and adhesive performance.

The component (a3) is not particularly limited, and examples thereof include a resin obtained by copolymerizing known terpenes and phenols, a polyterpene resin, and the like. The component (a3) may be hydrogenated. Among these, the terpene phenol resin is preferable because it is excellent in water-resistant adhesive strength, water-whitening resistance, and adhesive performance.

Hereinafter, the rosin esters and the rosin phenol resin will be described with respect to the component (a1). As used herein, the rosin esters mean rosin esters, polymerized rosin esters, and unsaturated carboxylic acid-modified rosin esters. As the rosin esters, polymerized rosin esters are more preferable because they are excellent in water-resistant adhesive strength, water-whitening resistance and adhesive performance.

The rosin ester is obtained by reacting the raw material rosin, hydrogenated rosin, and disproportionated rosin with alcohols.

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

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. 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, the raw material rosin is placed in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride or titanium tetrachloride at a temperature of about 40 to 160 ° C. for about 1 to 5 hours. Examples thereof include a method of reacting.

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 thereof include 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, maleinization, 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, maleated, or fumarized.

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

The alcohols used for esterifying the polymerized rosin are the same as described 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 characteristics of the polymerized rosin ester are not particularly limited. From the viewpoint of excellent water resistance and adhesive performance, the physical properties of the polymerized rosin ester preferably have a softening point of about 150 to 180 ° C. In the present invention, the softening point is a value measured by the ring-and-ball method (JISK5902).

The unsaturated carboxylic acid-modified rosin ester is an ester obtained by further reacting alcohols with a modified rosin (α, β-unsaturated carboxylic acid-modified rosin) obtained by addition-reacting the raw material rosin with α, β-unsaturated carboxylic acid. It is an esterification.

The α, β-unsaturated dicarboxylic 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, and muconic anhydride. 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 dicarboxylic acid used is usually about 1 to 20 parts by weight, preferably about 1 to 3 parts by weight, based on 100 parts by weight of the raw material rosin.

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

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

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 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 described 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. As for the amount of phenol used, from the viewpoint of emulsifying property, usually, about 0.8 to 1.5 mol of phenol may be reacted with 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. As the reaction temperature, usually, the reaction may be carried out at 180 to 350 ° C. for about 6 to 18 hours. The acid catalyst that can be used in the reaction is not particularly limited, but for example, an inorganic acid catalyst such as sulfuric acid, hydrogen chloride, or boron trifluoride, or an organic acid catalyst such as paratoluenesulfonic 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 weight with respect to 100 parts by weight of the raw material rosin. Further, the rosin phenol resin may be one obtained by further reacting the resin obtained in the above reaction with alcohols to esterify it. The alcohols used at that time are the same as described above.

The softening point of the component (A) is not particularly limited, but is preferably about 70 to 180 ° C. from the viewpoint of excellent water resistance and adhesive performance. In the present invention, the softening point is a value measured by the ring-and-ball method (JISK5902).

The component (B) is a multi-chain multi-hydrophilic group compound having at least two hydrophobic chains and two hydrophilic groups in the molecule. The structure is such that at least two molecules of the compound (b) (hereinafter, also referred to as the component (b)) having at least one hydrophobic chain and one hydrophilic group in the molecule are bonded via a spacer. The component (B) may be used alone or in combination of two or more.

The component (B) is used to emulsify the component (A) in water in a tackifier resin emulsion. The conventional tackifier resin emulsion is obtained by emulsifying with a known anionic emulsifier or nonionic emulsifier, but it may be difficult to obtain one having both excellent emulsifying property and water-resistant adhesive force. It has been clarified that the tackifier resin emulsion of the present invention is excellent in both emulsifying property and water resistance by using the component (B) containing a plurality of hydrophobic chains and hydrophilic groups. It was also clarified that the tackifier resin emulsion containing the component (B) has good water whitening resistance.

The component (B) is not particularly limited as long as it has the above-mentioned structure, but it is preferably a compound in which two molecules of the component (b) are bonded via a spacer from the viewpoint of easy availability and excellent emulsifying property. It is preferably a compound represented by bs-b (in the formula, b represents the component (b), s represents the spacer described later, and the two bs may be the same or different from each other). Further, from the same point of view, the component (b) has a compound having one hydrophobic chain and one hydrophilic group in the molecule (hereinafter, also referred to as a 1-chain 1-hydrophilic group compound) or 1 hydrophobic chain in the molecule. It is preferably a compound having two hydrophilic groups (hereinafter, also referred to as a 1-chain 2-hydrophilic group compound). Examples of the 1-chain 1-hydrophilic group-type compound or the 1-chain 2-hydrophilic group-type compound include various known 1-chain 1-hydrophilic group-type surfactants (emulsifiers) and 1-chain 2-hydrophilic group-type surfactants (emulsifiers). Can be mentioned.

The hydrophobic chain contained in the component (B) is preferably a hydrophobic chain having a saturated or unsaturated linear chain, a branched chain, or a cyclic chain having 2 to 20 carbon atoms independently. Specific examples of the hydrophobic chain include, for example, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n. -Dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, phenyl, linear or branched phenyl substituted with an alkyl group. , Each residue such as phenyl substituted with an aromatic vinyl compound oligomer residue and their branched isomers, and the corresponding unsaturated residue having unsaturated moieties at one, two or three locations. Group etc. can be mentioned. Among them, from the viewpoint of excellent emulsifying property, the hydrophobic chain is a saturated or unsaturated linear chain having 10 to 16 carbon atoms, a saturated or unsaturated branched chain having 10 to 16 carbon atoms, and 10 to 16 carbon atoms. 16 saturated or unsaturated cyclic chains, phenyl substituted with 10-16 saturated or unsaturated linear alkyl groups, 10-16 saturated or unsaturated branched alkyl groups Phenyl substituted with, phenyl substituted with an aromatic vinyl compound oligomer residue is more preferable, and n-dodecyl group, n-tridecyl group, dodecylphenyl, hexadecylphenyl, and tristyrene phenyl are particularly preferable.

The hydrophilic groups contained in the component (B) are independently carboxyl groups, sulfonic acid groups, sulfuric acid residues, phosphate groups or salts thereof, or polyoxyalkylenes such as polyoxyethylene groups and polyoxypropylene groups. It is preferably a group. When used as a salt, examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts and the like, and specific examples thereof include alkali metals such as sodium, potassium and lithium, and calcium. , Alkaline earth metals such as magnesium, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, and basic amino acids such as arginine and lysine. It is a salt with one or more kinds. Among them, the hydrophilic group is a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or a polyoxyethylene group because of its excellent emulsifying property, water adhesion resistance and water whitening resistance. More preferred.

The spacer contained in the component (B) is not particularly limited as long as it is a divalent linking group that links the component (b) by a covalent bond. Examples of the linking group include a single bond, a saturated or unsaturated linear or branched chain having 1 to 20 carbon atoms, a branched chain, a cyclic chain alkylene group, an alkenylene group, an ether group, a thioether group, an imino group, a carbonyl group, and phosphorus. Acid residues, or various known amino acid residues, hydroxycarboxylic acid residues, dicarboxylic acid residues, polycarboxylic acid residues, diamine residues, polyamine residues, diisocyanate residues, polyisocyanate residues, diol residues, Examples include polyol residues.

The component (B) is not particularly limited as long as it has the above-mentioned structure, and specific examples thereof include compounds represented by the following general formulas (1) to (4).

（式（１）中、Ｒ_１は炭素数８～２０の直鎖又は分枝鎖のアルキル基を表し、Ｒ_１’は水素又は炭素数８～２０の直鎖若しくは分枝鎖のアルキル基を表し、Ｘは、カルボキシル基、スルホン酸基、硫酸残基若しくはリン酸基、又はそれらのアルカリ金属塩若しくはアンモニウム塩を表す。）

(In the formula ( ₁ ), R ₁ represents a linear or branched alkyl group having 8 to 20 carbon atoms, and R 1'is hydrogen or a linear or branched alkyl group having 8 to 20 carbon atoms. Representing, X represents a carboxyl group, a sulfonic acid group, a sulfuric acid residue or a phosphoric acid group, or an alkali metal salt or an ammonium salt thereof.)

（式（２）中、Ｒ_２は炭素数８～２０の直鎖若しくは分枝鎖のアルキル基、又はトリスチレン化フェニル基を表し、Ｘ_４は、水素原子、アルカリ金属又はアンモニウムを表す。また、ｊは２～２０の整数を表す。２つのＲ_２は互いに同一又は異なっていてもよい。）

(In the formula (2), R ₂ represents a linear or branched alkyl group having 8 to 20 carbon atoms or a tristyrene phenyl group, and X ₄ represents a hydrogen atom, an alkali metal or ammonium. , J represent an integer of 2 to 20. The _two R2s may be the same or different from each other.)

（式（３）中、Ｒ_３は炭素数８～２０の直鎖又は分枝鎖のアルキル基を表し、Ｘ_５は水素原子、アルカリ金属又はアンモニウムを表わす。２つのＲ_３は互いに同一又は異なっていてもよく、２つのＸ_５は互いに同一又は異なっていてもよい。）

(In formula (3), R ₃ represents a linear or branched alkyl group having 8 to 20 carbon atoms, X ₅ represents a hydrogen atom, an alkali metal or ammonium. Two R _3s are the same or different from each other. The two _X5s may be the same or different from each other.)

（式（４）中、Ｘ_１、Ｘ_２、及びＸ_３は、それぞれ独立して水素原子、アルカリ金属又はアンモニウムを表し、ｄ及びｅはそれぞれ独立して０または２を表すが、ｄ及びｅが同時に０または２となることはなく、ｆ及びｇは、それぞれ独立して０または２を表すが、ｆ及びｇが同時に０または２となることはなく、ｈ及びｉは、８～１８の整数を表す。）

(In formula (4), X ₁ , X ₂ and X ₃ independently represent a hydrogen atom, alkali metal or ammonium, respectively, and d and e independently represent 0 or 2, respectively, but d and e. Will not be 0 or 2 at the same time, and f and g will independently represent 0 or 2, respectively, but f and g will not be 0 or 2 at the same time, and h and i will be 8-18. Represents an integer.)

The component (B) is preferably a compound represented by the general formulas (1) to (4) from the viewpoint of excellent emulsifying property. Among the compounds represented by the general formula (1), dodecyldiphenyl ether disulfonic acid or hexadecyldiphenyl ether disulfonic acid (dodecylphenylsulfonic acid or hexadecylphenylsulfonic acid and phenyl) in which R ₁ in the formula is a dodecyl group or a hexadecyl group. Sulfonic acid corresponds to the component (b) and the ether group corresponds to the spacer), or a sodium salt or an ammonium salt thereof is preferable. Among the compounds represented by the general formula (2), polyoxyethylene tridecyl ether phosphoric acid or polyoxyethylene (R ₂ in the formula is tridecyl or a tristyrene phenyl group and j is 3, 6 or 10). Tristyrene phenyl) ether phosphoric acid (polyoxyethylene tridecyl ether or polyoxyethylene (tristyrene phenyl) ether corresponds to component (b), phosphoric acid residue corresponds to spacer) or its sodium salt and ammonium salt. Preferably, as commercially available products, Rhodafac RS-410, Rhodafac RS-610, and Rhodafac RS-710 (all manufactured by Solvay Nikka Co., Ltd.) are more preferable. Among the compounds represented by the general formula (4), lysine dilauroyl glutamate (N-lauroyl-L-glutamic acid corresponds to component (b), lysine residue corresponds to spacer) or a sodium salt thereof is more preferable, and as a commercially available product. Is more preferably Pericea (registered trademark) L-30 (manufactured by Asahi Kasei Finechem Co., Ltd.).

The amount of the component (B) used is not particularly limited, but from the viewpoint of being excellent in emulsifying property, water-resistant adhesive force and water-whitening resistance, 0.75 to 2 weight by weight with respect to 100 parts by weight of the component (A) in terms of solid content. About 1 to 1.5 parts by weight is preferable, and about 1 to 1.5 parts by weight is more preferable. When the amount of the component (B) used is 0.75 parts by weight or more, the tackifying resin emulsion has excellent emulsifying property, and when the amount is 2 parts by weight or less, the water-based viscosity containing the emulsion is used. -The adhesive has excellent water resistance and adhesive strength. Further, the component (B) has a feature that a tackifier resin emulsion having excellent emulsifying property can be obtained even if the amount used is smaller than that of the conventional anionic emulsifier or nonionic emulsifier.

The tackifier resin emulsion of the present invention may contain an emulsifier (C) (hereinafter, also referred to as a component (C)), if necessary, for the purpose of improving the emulsifying property of the emulsion. The component (C) is different from the component (B).

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. Among these, a low molecular weight anionic emulsifier is preferable because it is excellent in emulsifying property.

Examples of the monomer used for producing the high molecular weight emulsifier include (meth) acrylic acid ester-based monomers such as methyl (meth) acrylic acid and ethyl (meth) acrylic acid; (meth) acrylic acid, 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 (meth) 2-hydroxyethyl acrylate, (meth) 2-hydroxypropyl 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 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 is a polystyrene-equivalent value obtained by a gel permeation chromatography (GPC) method.

The reactive emulsifier other than the high molecular weight emulsifier has, for example, a hydrophilic group such as a sulfonic acid group or a carboxyl group and a hydrophobic group such as an alkyl group or a phenyl group, and has a carbon-carbon double bond in the molecule. Those having a bond.

Examples of the low molecular weight anionic emulsifier include dialkyl sulfosuccinic acid ester salt, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinic acid ester salt, polyoxyethylene styrylphenyl ether sulfosuccinic acid ester salt, and naphthalene. Examples thereof include formalin sulfonic acid condensate, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene dialkyl ether sulfate ester salt, polyoxyethylene trialkyl ether sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt and the like.

Examples of the low molecular weight nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitan fatty acid ester.

As the emulsifier other than the high molecular weight emulsifier, one or two or more kinds may be appropriately selected and used.

The amount of the component (C) used is preferably about 1 to 10 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content, from the viewpoint of excellent emulsifying property and water resistance, and 2 to 8 parts by weight. The degree is more preferable.

The tackifier resin emulsion of the present invention may 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.

The tackifier resin emulsion of the present invention is obtained by emulsifying the component (A) in the presence of the component (B) and, if necessary, the component (C) (hereinafter collectively referred to as "emulsifier"). , Can be used as a tackifier resin.

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.

The high-pressure emulsification method is a method in which the component (A) is put into a liquid state, an emulsifier and water are premixed, finely emulsified using a high-pressure emulsifier, and then the solvent is removed if necessary. The method of making the component (A) into a liquid state may be heated only by heating, dissolved in a solvent and then heated, or mixed with a non-volatile substance such as a plasticizer and heated, but it is performed only by heating. Is preferable. Examples of the solvent include organic solvents capable of dissolving the component (A) such as toluene, xylene, methylcyclohexane, and ethyl acetate.

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

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 weight. The volume average particle size of the obtained tackifier resin emulsion is usually about 0.1 to 2 μm, and most of the particles are uniformly dispersed as particles of 1 μm or less, but may be 0.7 μm or less. , Preferred from the viewpoint of storage stability. The component (A) 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 weight). The pH is usually about 2 to 10, but if necessary, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; alkanolamines such as monomethylamine, monoethanolamine, diethanolamine, and diisopropanolamine; ethylamine, n-. An aliphatic amine such as butylamine or triethylamine; an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide; an alkaline earth metal hydroxide such as calcium hydroxide may be appropriately added to adjust the pH. ..

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 viscous / adhesive composition of the present invention can be used as a water-based viscous / adhesive.

Examples of the base polymer include acrylic polymer emulsions, rubber latexes, 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 regulators 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 viscous / adhesive compositions is usually about 40 to 70% by weight, preferably 55 to 70% by weight, in terms of solid content. At least one base polymer may be used.

As the acrylic polymer emulsion, those generally used for various acrylic adhesives / adhesives can be used, and a batch charging polymerization method of monomers 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 may be 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 (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. As the emulsifier used in the acrylic polymer emulsion, an anionic emulsifier, partially saponified polyvinyl alcohol, or the like can be used, and the amount used is based on 100 parts by weight of the (meth) acrylic acid ester polymer in terms of solid content. It is about 0.1 to 5 parts by weight, preferably about 0.5 to 3 parts by weight.

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 weight with respect to 100 parts by weight of the acrylic polymer emulsion in terms of solid content.

As the rubber-based latex, various known ones used in the water-based viscous / 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-based latex and the tack-imparting resin emulsion is not particularly limited, but it is appropriate that the effect of modification by the tack-imparting resin emulsion can be sufficiently exhibited and the adhesive strength, tack, etc. are not deteriorated due to excessive use. As a range of use, it is preferable that the pressure-sensitive resin emulsion is usually about 10 to 150 parts by weight with respect to 100 parts by weight of the rubber-based latex in terms of solid content.

As the synthetic resin emulsion, various known emulsions used for water-based viscous / 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-based emulsion and the tack-imparting resin emulsion is not particularly limited, but the effect of modifying the tack-imparting resin emulsion can be sufficiently exhibited, and the adhesive strength, tack, etc. do not decrease due to excessive use. As an appropriate range of use, it is preferable that the pressure-sensitive resin emulsion is usually about 2 to 40 parts by weight with respect to 100 parts by weight 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. For example, the tackifier resin emulsion may be emulsified and mixed, or the tackifier resin emulsion may be added to the base polymer and subjected to high shear rotation. You may mix using a mixer.

Since the water-based adhesive / adhesive composition of the present invention contains the tackifier resin emulsion, it has high water-resistant adhesive strength and is suitable as a water-based adhesive / adhesive in applications requiring water resistance. The water-based adhesive / adhesive composition of the present invention is suitable for, for example, adhesives / adhesives for building materials, adhesives / adhesives for automobile interior members, adhesives / adhesives for film labels, and the like. Further, since the water-based adhesive / adhesive composition of the present invention has good water whitening resistance, the adhesive / adhesive in applications where transparency and designability are required in an environment with high moisture and humidity, for example, It is suitable as a sticky / adhesive for transparent labels used in cosmetic containers and shampoo containers.

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 weight.

[Manufacturing of base polymer]
Production Example 1
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 43.4 parts of water and polyoxyethylene alkyl ether sulfate ammonium salt (anionic emulsifier: trade name) under a nitrogen gas stream. An aqueous solution consisting of 0.92 parts of "HITENOL LA-16" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was charged and the temperature was raised to 70 ° C. Next, 90 parts of butyl acrylate, 7 parts of 2-ethylhexyl acrylate and 3 parts of acrylic acid, 0.24 parts of potassium persulfate (polymerization initiator), 0.11 part of 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. Then, the remaining 9/10 of the mixture and the aqueous initiator 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
After charging 100 parts of polymerized rosin (acid value 145 mgKOH / g, softening point 140 ° C.) and 14 parts of pentaerythritol into a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction tube / steam introduction tube, nitrogen gas After reacting in an air stream at 250 ° C. 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 esterification. Then, water and the like were removed under reduced pressure to obtain a polymerized rosin ester having a softening point of 160 ° C.

[Manufacturing of rosin phenol resin]
Production example 3
After charging 100.0 parts of gum rosin and 100.0 parts of phenol in the same reaction vessel as in Production Example 2, 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 having a softening point of 150 ° C.

[Manufacturing of adhesive resin emulsion]
Example 1
After dissolving 100 parts of the polymerized rosin ester of Production Example 2 in 70 parts of methylcyclohexane at 80 ° C. for 3 hours, sodium dilauroyl glutamate lysine (trade name "Pericea (registered trademark) L-30" Asahi Kasei Finechem Co., Ltd. ) (Hereinafter referred to as (B) -1 component) 0.75 parts (in terms of solid content) and 120 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 perform high-pressure emulsification 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 tackifier resin emulsion having a solid content concentration of 50%.

Examples 2-5
In Example 1, the same procedure was carried out except that the amount of component (B) -1 used was changed to the number of copies shown in Table 1, to obtain a tackifier resin emulsion (both having a solid content concentration of 50%).

Example 6
In Example 1, the amount of (B) -1 component used is shown in place of sodium dodecyldiphenyl ether disulfonate (trade name "DowFax 8390" manufactured by Dow Chemical Co., Ltd.) (hereinafter referred to as (B) -2 component). The same procedure was carried out except that the number of copies was changed to that shown in 1, to obtain a tackifier resin emulsion (both having a solid content concentration of 50%).

Example 7
In Example 1, the polymerized rosin ester was replaced with the rosin phenol resin of Production Example 3, and the same procedure was carried out except that the amount used was changed to the number of copies shown in Table 1. 50%) was obtained.

Example 8
In Example 1, the polymerized rosin ester was replaced with a C9-based petroleum resin (trade name “Neopolymer 140”, softening point 140 ° C. manufactured by JXTG Energy Co., Ltd.), and the amount used was changed to the number of copies shown in Table 1. In the same manner, a tackifier resin emulsion (both having a solid content concentration of 50%) was obtained.

Example 9
In Example 1, the polymerized rosin ester was replaced with the polymerized rosin ester and a C9-based petroleum resin (trade name "Neopolymer 140" manufactured by JXTG Energy Co., Ltd.), and the amount used was changed to the number of copies shown in Table 1. Except for the change, the same procedure was carried out to obtain a tackifier resin emulsion (both having a solid content concentration of 50%). When 70 parts of the polymerized rosin ester and 30 parts of the C9 petroleum resin were used in combination, the softening point was 155 ° C.

Example 10
In Example 1, the polymerized rosin ester was replaced with terpenephenol (trade name “Dertophene T115”, softening point 125 ° C. manufactured by DRT), and the amount used was changed to the number of copies shown in Table 1, but the same procedure was carried out. A tackifying resin emulsion (both having a solid content concentration of 50%) was obtained.

Example 11
In Example 1, the component (B) -1 is sodium polyoxyethylene tridecyl ether phosphate (trade name "Rhodafac RS-610" manufactured by Solvay Nikka Co., Ltd.) (hereinafter referred to as the component (B) -3). Instead, the same procedure was carried out except that the amount used was changed to the number of copies shown in Table 1, to obtain a tackifier resin emulsion (both having a solid content concentration of 50%).

Comparative Examples 1-2
In Example 1, the component (B) -1 was replaced with polyoxyethylene alkyl (12 to 14 carbon atoms) disodium sulfosuccinate (hereinafter referred to as the component (B) ′ -1), and the amount used was shown in Table 1. The same procedure was carried out except that the number of copies was changed to that indicated by (1), to obtain a tackifier resin emulsion (both having a solid content concentration of 50%).

Comparative Example 3
Similarly, in Example 1, the component (B) -1 was replaced with sodium lauroyl glutamate (hereinafter referred to as the component (B)'-2) and the amount used was changed to the number of copies shown in Table 1. This was carried out to obtain a tackifier resin emulsion (both having a solid content concentration of 50%).

(Evaluation of emulsifying property)
The volume average particle size of the tackifier resin emulsion of each example and comparative example was measured with a laser diffraction type particle size measuring device (manufactured by Shimadzu Corporation, trade name "SALD-7500no") and a refractive index of 1.70-0. Measured under the conditions of .20i and absorbance 0.06. The obtained volume average particle size was evaluated according to the following criteria. The results are shown in Table 1. The smaller the volume average particle size, the better the emulsifying property and storage stability of the tackifying resin emulsion.
◯: Volume average particle diameter less than 0.7 μm Δ: Volume average particle diameter 0.7 μm or more and less than 1.0 μm ×: Volume average particle diameter 1.0 μm or more or cannot be emulsified

Further, the tackifier resin emulsions of each Example and Comparative Example were filtered through a wire mesh of 150 mesh, and the weight% of the obtained residue with respect to the resin (A) was weighed. The weight% of the residue was evaluated according to the following criteria. The results are shown in Table 1. The smaller the weight% of the residue is, the more the generation of agglomerates is suppressed in the tackifier resin emulsion, and the emulsifying property is good.
◯: Less than 0.1% by weight Δ: 0.1% by weight or more and less than 1.0% by weight ×: 1.0% by weight or more or cannot be emulsified

[Manufacturing of water-based viscous / adhesive composition]
80 parts (solid content equivalent) of the acrylic polymer emulsion synthesized in Production Example 1 and 20 parts (solid content equivalent) of the tackifier resin emulsion of Example 1 were mixed to obtain an aqueous viscous / adhesive composition. .. For each of the tackifier resin emulsions of Examples 2 to 5 and Comparative Examples 1 and 2, water-based adhesive / adhesive compositions were produced in the same manner.

[Preparation of sample tape]
Using a dice type applicator (manufactured by Taiyu Equipment Co., Ltd.), the water-based viscous / adhesive composition is applied to a polyester film (trade name "S-100", manufactured by Mitsubishi Chemical Corporation, thickness: 38 μm) with a thickness of about 50 μm. Then, it was dried in a circulation dryer at 105 ° C. for 5 minutes to prepare a sample tape.

(Evaluation of water resistance adhesive strength)
The sample tape was cut to a width of 25 mm, and a 2 kg roller was reciprocated twice on an adherend (stainless steel plate (SS)) to be bonded and allowed to stand for one day. Next, the adherend to which the sample tape was attached was allowed to stand for 7 days in a high-temperature and high-humidity machine (60 ° C., 90% RH), and then the adherend was taken out from the high-temperature and high-humidity machine and immediately subjected to a 180-degree peeling test. Was carried out under the conditions of a tensile speed of 300 mm / min and a measurement temperature of 23 ° C., and the adhesive force (N / 25 mm) was measured. The results are shown in Table 1.

(Evaluation of water whitening resistance)
The sample tape is cut into an appropriate size, immersed in water at 20 ° C. for 24 hours, and then the degree of whitening of the sample tape is measured using a haze meter (HM-150, manufactured by Murakami Color Technology Laboratory). , The difference in haze value before and after immersion in water was calculated. The results are shown in Table 1. The smaller the difference in the haze value of the sample tape, the more the whitening of the adhesive / adhesive film is suppressed in an environment with high moisture and humidity, and the water whitening resistance is good.
◯: Difference in haze value is less than 10% Δ: Difference in haze value is 10% or more and less than 20% ×: Difference in haze value is 20% or more

※表１の各成分の使用量は固形分換算の値であり、注釈は、以下の通りである。
１）乳化ができず粘着付与樹脂エマルジョンが得られなかったので、耐水接着力及び耐水白化性が評価出来なかった。

* The amount of each component used in Table 1 is the value in terms of solid content, and the notes are as follows.
1) Since emulsification was not possible and a tackifying resin emulsion could not be obtained, the water-resistant adhesive strength and water-whitening resistance could not be evaluated.

Claims (7)

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 poly having at least two hydrophobic chains and hydrophilic groups in the molecule. Contains the chain polyhydrophilic group compound (B) ,
A tackifier resin emulsion in which the multi-chain multi-hydrophilic group compound (B) is a compound represented by the following general formulas (3) to (4) .

(In formula (3), R ₃ represents a linear or branched alkyl group having 8 to 20 carbon atoms, X ₅ represents a hydrogen atom, an alkali metal or ammonium. Two R 3s _are the same or different from each other . The two X5s _may be the same or different from each other.)

(In formula (4), X ₁ , X ₂ and X ₃ independently represent a hydrogen atom, alkali metal or ammonium, respectively, and d and e independently represent 0 or 2, respectively, but d and e. Will not be 0 or 2 at the same time, and f and g will independently represent 0 or 2, respectively, but f and g will not be 0 or 2 at the same time, and h and i will be 8-18. Represents an integer.) (A) The tackifier resin emulsion according to claim 1, wherein the softening point of the component is 70 to 180 ° C. The tackifier resin emulsion according to claim 1 or 2, wherein the component (a1) is a rosin ester and / or a rosin phenol resin. 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 poly having at least two hydrophobic chains and hydrophilic groups in the molecule. Contains the chain polyhydrophilic group compound (B),
The softening point of the resin (A) is 70 to 180 ° C.
The rosin-based resin (a1) is a rosin ester and / or a rosin phenol resin.
The multi-chain, multi-hydrophilic group compound (B) is a compound represented by the following general formula (2).
Adhesive-imparting resin emulsion.

(In equation (2), R ₂ Represents a linear or branched alkyl group having 8 to 20 carbon atoms or a tristyrenated phenyl group, and X ₄ Represents a hydrogen atom, alkali metal or ammonium. Further, j represents an integer of 2 to 20. Two Rs ₂ May be the same or different from each other. ) 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 poly having at least two hydrophobic chains and hydrophilic groups in the molecule. Contains the chain polyhydrophilic group compound (B),
The softening point of the resin (A) is 70 to 180 ° C.
The rosin-based resin (a1) is a rosin ester and / or a rosin phenol resin.
The multi-chain, multi-hydrophilic group compound (B) is a compound represented by the following general formula (1).
The amount of the multi-chain, multi-hydrophilic group compound (B) used is 0.75 parts by weight or more and less than 2.0 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content.
Adhesive-imparting resin emulsion.

(In the formula (1), R1 represents a linear or branched alkyl group having 8 to 20 carbon atoms, and R1'represents hydrogen or a linear or branched alkyl group having 8 to 20 carbon atoms. X represents a carboxyl group, a sulfonic acid group, a sulfuric acid residue or a phosphoric acid group, or an alkali metal salt or an ammonium salt thereof.) 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.