JP2022135999A - Rosin phenol resin composition, tackifier resin composition, viscous adhesive composition and method for producing rosin phenol resin composition - Google Patents

Abstract

To provide a rosin phenol resin composition which has a good color tone.SOLUTION: A rosin phenol resin composition contains a rosin phenol resin that is a reactant of rosins (A) and phenols (B), and at least one compound (C) selected from the group consisting of xanthone, thioxanthone, acridone and anthrone.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a rosin phenolic resin composition, a tackifying resin composition, a pressure-sensitive adhesive/adhesive composition, and a method for producing a rosin phenolic resin composition.

Rosin-based resins are used as tackifiers for adhesives such as hot melts and pressure-sensitive adhesives, modifiers for rubbers and plastics, emulsifiers for synthetic rubbers, base materials for chewing gum, road marking paints and inks. It is used in various fields such as binder resins for paper and sizing agents for papermaking. Examples of such rosin resins include natural rosin, refined rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, acid-modified rosin, rosin ester, rosin phenolic resin, rosin-modified phenolic resin and metal salts thereof. be done.

Among them, rosin phenolic resin is used as a tackifier in acrylic adhesives, chloroprene adhesives, and hot-melt adhesives. properties and adhesion (Patent Documents 1 and 2).

Japanese Patent Publication No. 2007-504325 JP-A-10-287855

However, many conventional rosin phenolic resins have insufficient color tone, and most of them have a Gardner color number of 7 or more. For example, Patent Document 1 also discloses that the actually obtained rosin phenol resin has a color tone of 8 or more in terms of Gardner color number, and there is a problem in terms of color tone.

An object of the present invention is to provide a rosin phenol resin composition having good color tone.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by a rosin phenolic resin composition containing a specific polycyclic aromatic compound. That is, the present invention relates to the following rosin phenol resin composition, tackifier resin composition, pressure-sensitive adhesive/adhesive composition, and method for producing a rosin phenol resin composition.

1. A rosin phenolic resin composition comprising a rosin phenolic resin which is a reaction product of rosins (A) and phenols (B), and at least one compound (C) selected from the group consisting of xanthones, thioxanthones, acridones and anthrone. thing.

2. 2. The rosin phenol resin composition according to item 1, wherein the color tone of the rosin phenol resin composition is 6 or less in terms of Gardner color number.

3. The rosins (A) are rosins derived from at least one pine species selected from the group consisting of marsh pine (slash pine), merukusi pine, caribbean pine, daioh pine, taeda pine, yunnan pine and shijimatsu. 3. The rosin phenol resin composition according to item 1 or 2 above.

4. 4. The rosin phenolic resin composition according to any one of items 1 to 3 above, wherein the rosin (A) is a purified rosin.

5. in the presence of at least one compound (C) selected from the group consisting of xanthone, thioxanthone, acridone and anthrone,
A method for producing a rosin phenol resin composition, comprising the step of reacting rosins (A) and phenols (B).

6. 6. The manufacturing method according to item 5 above,
The amount of compound (C) used is 0.05 to 5% by mass with respect to 100% by mass of rosins (A).
A method for producing a rosin phenolic resin composition.

7. 7. The manufacturing method according to item 5 or 6,
A method for producing a rosin phenol resin composition, comprising the step of reacting a rosin (A) with a phenol (B) in the presence of a compound (C) and a phenol sulfide.

8. A tackifying resin composition comprising the rosin phenolic resin composition according to any one of items 1 to 4 above.

9. Item 8. The tackifying resin composition according to Item 8, which is an aqueous dispersion of the rosin phenol resin composition according to any one of Items 1 to 4.

10. A pressure-sensitive adhesive/adhesive composition comprising the tackifying resin composition according to item 8 or 9 and a base polymer.

The rosin phenol resin composition of the present invention has good color tone. In addition, since the tackifying resin composition and the pressure-sensitive adhesive/adhesive composition of the present invention contain the rosin phenol resin composition, coloring is suppressed and the appearance is excellent.

[Rosin phenolic resin composition]
The rosin phenol resin composition of the present invention is a rosin phenol resin which is a reaction product of rosins (A) (hereinafter referred to as component (A)) and phenols (B) (hereinafter referred to as component (B)), and at least one compound (C) selected from the group consisting of xanthone, thioxanthone, acridone and anthrone (hereinafter referred to as component (C)).

(Rosins (A))
Component (A) is not particularly limited, and various known components can be used. (A) component may be used individually by 1 type, and may use 2 or more types together.

Component (A) is, for example, Pinus massoniana, Pinus elliottii, Pinus merkusii, Pinus caribaea, Pinus palustris, Pinus Taeda), natural rosin derived from Pinus yunnanensis and Pinus kesiya (gum rosin, tall oil rosin, wood rosin), refined rosin (hereinafter, natural rosin and refined rosin are collectively referred to as undenatured rosin) ), disproportionated rosin, hydrogenated rosin, and the like.

The above purified rosin can be obtained using various known means. Specifically, for example, it can be obtained using various known purification means such as distillation, extraction, recrystallization, and adsorption. The distillation method includes, for example, a method of distilling the natural rosin at a temperature of about 200 to 300° C. under a reduced pressure of about 0.01 to 3 kPa. Examples of the extraction method include a method in which the natural rosin is made into an alkaline aqueous solution, insoluble and unsaponifiable substances are extracted with various organic solvents, and then the aqueous layer is neutralized. Examples of the recrystallization method include a method of dissolving the natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and adding an organic solvent as a poor solvent. Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, chlorinated hydrocarbon solvents such as chloroform, lower alcohols, ketones such as acetone, and acetic esters such as ethyl acetate. Poor solvents include, for example, n-hexane, n-heptane, cyclohexane, isooctane and the like. The adsorption method includes, for example, a method of bringing unmodified rosin in a molten state or a solution of unmodified rosin dissolved in an organic solvent into contact with a porous adsorbent. Porous adsorbents include, for example, activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and microporous porous clays.

The disproportionated rosin can be obtained using various known means. Specifically, for example, it can be obtained by a method (disproportionation) of heating the unmodified rosin in the presence of a disproportionation catalyst. As the disproportionation catalyst, supported catalysts such as palladium-carbon, rhodium-carbon and platinum-carbon; metal powders such as nickel and platinum; various known iodides such as iodine and iron iodide can be used. The amount of the catalyst used is usually about 0.01 to 5 parts by weight, preferably about 0.01 to 1 part by weight, per 100 parts by weight of the unmodified rosin. The reaction temperature is about 100 to 300°C, preferably about 150 to 290°C.

As the disproportionated rosin, a disproportionated rosin subjected to the above purification may be used.

The hydrogenated rosin can be obtained using various known means. Specifically, for example, it can be obtained by hydrogenating the unmodified rosin using known hydrogenation conditions. Hydrogenation conditions include, for example, a method of heating the unmodified rosin to about 100 to 300° C. under a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst. Further, it is preferable that the hydrogen pressure is about 5 to 20 MPa and the reaction temperature is about 150 to 300.degree. As the hydrogenation catalyst, various known catalysts such as supported catalysts and metal powders can be used. Supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, platinum-carbon and the like. Metal powders include nickel, platinum, and the like. Among these, palladium, rhodium, ruthenium, and platinum-based catalysts are preferred because they increase the hydrogenation rate of the unmodified rosin and shorten the hydrogenation time. The amount of the hydrogenation catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, per 100 parts by mass of the unmodified rosin.

The hydrogenation may be carried out with the unmodified rosin dissolved in a solvent, if necessary. The solvent to be used is not particularly limited as long as it is inert to the reaction and easily dissolves the starting material and the product. Specifically, for example, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane and the like can be used singly or in combination of two or more. The amount of the solvent used is not particularly limited, but it may be used so that the solid content is usually 10% by mass or more, preferably in the range of about 10 to 70% by mass, based on the unmodified rosin.

As the hydrogenated rosin, hydrogenated rosin subjected to the above purification may be used.

The rosin phenol resin composition of the present invention is characterized by excellent color tone even when rosins other than rosins derived from Pinus massonia are used as the component (A).

Conventionally, pine species other than horsetail pine, such as wetland pine (Pinus elliottii), pine merkusii, pinus caribaea, pinus palustris, pinus taeda, Yunnan A rosin phenolic resin composition obtained using rosins derived from Pinus yunnanensis and Pinus kesiya has an insufficient color tone compared to the case of using rosins derived from Umaomatsu. tended to. The rosin phenol resin composition of the present invention is reacted in the presence of the component (C) described later, so that even if rosins derived from pine species other than Umaomatsu are used as the component (A), the color tone is excellent. It becomes a thing.

Component (A) is preferably the above-mentioned purified rosin from the viewpoint of excellent color tone of the rosin phenol resin composition.

(Phenols (B))
Component (B) is not particularly limited, and various known ones can be used. (B) component may be used individually by 1 type, and may use 2 or more types together.

Component (B) includes, for example, phenol, naphthols, alkylphenols, and arylphenols.

Examples of the above alkylphenols include o-cresol, o-normal-butylphenol, o-isobutylphenol, o-tert-butylphenol, o-pentylphenol, o-(cyclohexyl)phenol, o-octylphenol, o-nonylphenol, m -cresol, m-n-butylphenol, m-isobutylphenol, m-tert-butylphenol, m-pentylphenol, m-(cyclohexyl)phenol, m-octylphenol, m-nonylphenol, p-cresol, p-n-butylphenol, p-isobutylphenol, p-tertiarybutylphenol, p-pentylphenol, p-(cyclohexyl)phenol, p-octylphenol, p-nonylphenol and the like.

(Compound (C))
Component (C) is at least one compound selected from the group consisting of xanthone, thioxanthone, acridone and anthrone. (C) Component may be used individually by 1 type, and may use 2 or more types together.

Component (C) may have various substituents on the aromatic ring contained therein. The substituents include, for example, an alkyl group, an aryl group, an arylalkyl group, an alkenyl group, an arylalkenyl group, an alkynyl group, an arylalkynyl group, a cycloalkyl group, an alkylene group, a cycloalkylalkylene group, an alkynylene group, a phenyl group, a halogen , hydroxyl group, carboxyl group, acyl group, alkoxy group, amino group, dialkylamino group and the like.

The content of the component (C) in the rosin phenol resin composition is not particularly limited, but from the point of view of the excellent color tone of the rosin phenol resin composition, it is 0.05 to 5% by mass with respect to 100% by mass of the rosin phenol resin composition. %, more preferably about 0.1 to 0.5 mass %.

The content of component (C) means the residual amount of component (C) in the rosin phenol resin composition obtained by the production method described below.

(Additive)
The rosin phenol resin composition may contain various additives as long as they do not impair the effects of the present invention. Examples of such additives include dehydrating agents, crystal nucleating agents, plasticizers, fluidity improvers, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, and the like. These additives may be used singly or in combination of two or more.

(Antioxidant)
Examples of the antioxidant include phenol sulfides, thiophosphites, phosphorus compounds, hindered phenols, and the like.

The phenol sulfides are, for example, 4,4'-thiobis(6-t-butyl-3-methylphenol), 2,4-bis(dodecylthiomethyl)-6-methylphenol, 4,4'-bis( phenol) sulfide, 4,4'-bis(phenol) sulfoxide, 4,4'-bis(phenol) sulfone, 4,4'-bis(phenol) thiolsulfinate, 4,4'-bis(phenol) thiol sulfonate, 2,2′-bis(p-cresol) sulfide, 2,2′-bis(p-cresol) sulfoxide, 2,2′-bis(p-cresol) sulfone, 2,2′-bis(p -t-butylphenol) sulfide, 2,2'-bis(pt-butylphenol) sulfoxide, 2,2'-bis(pt-butylphenol) sulfone, 4,4'-bis(6-t-butyl- m-cresol) sulfoxide, 4,4′-bis(6-t-butyl-m-cresol) sulfide, 4,4′-bis(6-t-butyl-o-cresol) sulfoxide, 4,4′-bis (6-t-butyl-o-cresol) sulfone, 4,4′-bis(6-t-butyl-o-cresol) sulfide, 4,4′-bis(resorcinol) sulfide, 4,4′-bis( resorcinol) sulfoxide, 4,4′-bis(resorcinol) sulfone, 1,1′-bis(β-naphthol) sulfide, 1,1′-bis(β-naphthol) sulfoxide, 1,1′-bis(β- naphthol) sulfone, 4,4′-bis(α-naphthol) sulfide, 4,4′-bis(α-naphthol) sulfoxide, 4,4′-bis(α-naphthol) sulfone, t-amylphenol disulfide oligomer, nonylphenol disulfide oligomers, t-butylphenol disulfide oligomers, and the like.

The thiophosphites include, for example, trilauryltrithiophosphite, tridecyltrithiophosphite, tribenzyltrithiophosphite, tricyclohexyltrithiophosphite, tri(2-ethylhexyl)trithiophosphite, trinaphthyltrithiophosphite, diphenyl Decyltrithiophosphite, diphenyllauryltrithiophosphite, tetralauryl-4-oxaheptylene-1,7-tetrathiophosphite, tetrakis(mercaptolauryl)-1,6-dimercaptohexylene diphosphite, pentakis(mercaptolauryl) Bis(1,6-hexylene-dimercapto) trithiophosphite, tetrakis(mercaptolauryl)-2,9-dimercapto-p-methylenediphosphite, bis(mercaptolauryl)-1,6-dimercaptohexylene-bis( benzene phosphite), dioctyldithiopentaerythritol diphosphite, dilauryldithiopentaerythritol diphosphite, phenyllauryldithiopentaerythritol diphosphite and the like.

The phosphorus compounds include, for example, phosphorous acid, hypophosphorous acid and their metal salts, amine salts, neutralized products such as ammonium salts, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2- ethylhexyl)phosphite, tridecylphosphite, tris(tridecyl)phosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, diphenylmono(tridecyl)phosphite, 3,9-bis(2,6 -di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenyl diphosphite, bis(t-butylphenyl)pentaerythritol diphosphite, bis(2 ,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, Distearyl pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide and the like.

The above hindered phenols include, for example, 2,5-di-tert-butylhydroquinone, anthraquinone, triethylene glycol bis{3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate}, 1, 6-hexanediol bis {3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, pentaerythrityl tetrakis {3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate}, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methyl Phenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, N,N'-hexamethylenebis(3,5-di-t-butyl -4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, Irganox® 565, etc. is mentioned.

The above antioxidant is preferably the above phenol sulfides because the color tone of the rosin phenol resin composition is excellent.

The content of the additive in the rosin phenol resin composition is not particularly limited, but in terms of the excellent color tone of the rosin phenol resin composition, 0.01 to 10% by mass with respect to 100% by mass of the rosin phenol resin composition. About 0.01 to 1% by mass is more preferable.

The content of the antioxidant in the rosin phenol resin composition is not particularly limited, but in view of the excellent color tone of the rosin phenol resin composition, it is 0.01 to 10% by mass with respect to 100% by mass of the rosin phenol resin composition. %, more preferably about 0.01 to 1 mass %.

(Method for producing rosin phenolic resin composition)
The method for producing the rosin phenolic resin composition of the present invention is not particularly limited, but for example, the components (A) and (B) are heated and reacted in the presence of the component (C) and, if necessary, an acid catalyst. A method including a process, etc. are mentioned. The reaction may be carried out at a reaction temperature of 180 to 350° C. for a reaction time of 6 to 18 hours.

As a method for producing the rosin phenol resin composition of the present invention,
(1) a step of reacting components (A) and (B) in the presence of an acid catalyst as necessary at a temperature of about 100 to 200° C. for about 4 to 10 hours (addition step); A step (condensation step) of reacting the product (adduct) obtained in step (1) at a temperature of about 250 to 350 ° C. for about 2 to 8 hours,
In the step (1) and/or the step (2), a production method is preferred in which the reaction is carried out in the presence of the component (C).

In the above production method, a step of adding a basic substance to neutralize the acid catalyst (neutralization step) may be included after step (1). Basic substances include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

In the above production method, the step (2) may be reacted under reduced pressure. Although the reduced pressure condition is not particularly limited, it is preferably about 0.1 to 10 kPa.

The acid catalyst is not particularly limited, and various known ones can be used. Examples of acid catalysts include inorganic acid catalysts such as sulfuric acid, hydrogen chloride and boron trifluoride, and organic acid catalysts such as para-toluenesulfonic acid and methanesulfonic acid.

In the production method described above, the amount of component (B) used is not particularly limited, but it is preferably about 50 to 200 parts by mass per 100 parts by mass of component (A).

In the above production method, the amount of component (C) used is not particularly limited, but it is about 0.05 to 5% by mass with respect to 100% by mass of component (A) in terms of excellent color tone of the rosin phenolic resin composition. is preferable, and about 0.1 to 0.5% by mass is more preferable.

In the production method described above, the amount of the acid catalyst used is not particularly limited, but it is preferably about 0.01 to 2.0 parts by mass per 100 parts by mass of component (A).

In the above production method, the reaction may be carried out in the presence of the above antioxidant.

When the production method includes the step (1) and the step (2), the antioxidant may be used in both or one of the steps (1) and (2). .

In the production method, the antioxidant is not particularly limited, but phenol sulfides are preferable in that the color tone of the rosin phenol resin composition is excellent.

In the production method described above, the amount of the antioxidant used is not particularly limited, but is about 0.01 to 10% by mass with respect to 100% by mass of the component (A) in view of the excellent color tone of the rosin phenolic resin composition. is preferable, and about 0.05 to 5% by mass is more preferable.

(Physical properties of rosin phenolic resin composition)
The physical properties of the rosin phenol resin composition are not particularly limited. The color tone of the rosin phenol resin composition is preferably 6 or less in Gardner color number, more preferably 5 or less in Gardner color number. In the present invention, color tone means the value of Gardner unit color number measured according to JIS K 0071-2.

The number of Gardner colors used in the present invention is as follows. The Gardner color number "between 5 and 6" indicates that the Gardner color number is 5, 5+, 5-6, 6-, 6, and in this case, "5+" is darker than 5. , "6-" means lighter in tone than 6, and "5-6" means darker in tone than 5+ but lighter than 6-. In addition, the Gardner color number "6 or less" means that the Gardner color number is 6, 6-, 5-6, 5+, 5 or less natural numbers, and 6+, 6-7, 7 or more natural numbers indicates that it does not contain

[Tackifying resin composition]
The tackifying resin composition of the present invention contains the rosin phenolic resin composition of the present invention. The rosin phenol resin composition of the present invention can function as a tackifier by being used in a pressure sensitive adhesive (including the pressure sensitive adhesive composition described below).

As long as the desired properties are not impaired, the tackifying resin composition may optionally include a plasticizer, the antioxidant, the ultraviolet absorber, the heat stabilizer, the light stabilizer, and a tackifying agent other than the rosin phenolic resin composition. Various additives such as agents may be included.

The content of the rosin phenol resin composition in the tackifying resin composition is not particularly limited, but is preferably about 95 to 100 parts by mass based on 100 parts by mass of the tackifying resin composition in terms of solid content. The content of the additive in the tackifying resin composition is not particularly limited, but is preferably about 0 to 5 parts by mass based on 100 parts by mass of the tackifying resin composition in terms of solid content.

(Aqueous dispersion of rosin phenolic resin composition)
The tackifying resin composition of the present invention may be an aqueous dispersion of the rosin phenolic resin composition of the present invention (hereinafter also simply referred to as an aqueous dispersion).

The aqueous dispersion is a composition (emulsion) containing the rosin phenol resin composition and an emulsifier.

The emulsifier is not particularly limited, and various known ones can be used. Specific examples include high-molecular-weight emulsifiers obtained by polymerizing monomers, low-molecular-weight anionic emulsifiers, and low-molecular-weight nonionic emulsifiers. One of the emulsifiers may be used alone, or two or more may be used in combination.

Monomers used in the production of the above high-molecular-weight emulsifiers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -Butyl, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, polyoxyalkylene (meth)acrylate, etc. (meth)acrylic acid ester monomers; monocarboxylic acid vinyl monomers such as (meth)acrylic acid and crotonic acid; dicarboxylic acid vinyl monomers such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and muconic acid Monomers; sulfonic acid-based vinyl monomers such as vinylsulfonic acid, styrenesulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid; 2-(meth)acryloyloxyethyl acid phosphate, diphenyl-2(meth)acryloyloxyphosphate Phosphoric acid-based vinyl monomers such as phosphoric acid ester-based vinyl monomers such as; and alkali metal salts, alkaline earth metal salts, ammonium salts, salts of organic bases of these various organic acids; (meth)acrylamide monomers such as (meth)acrylamide; nitrile monomers such as (meth)acrylonitrile; vinyl ester monomers such as vinyl acetate; 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid Hydroxy group-containing (meth)acrylic acid ester monomers such as 2-hydroxypropyl; styrenes such as styrene, α-methylstyrene, and vinyltoluene; methyl vinyl ether, glycidyl (meth)acrylate, urethane acrylate, carbon number 6 to 22 and other monomers such as α-olefin and vinylpyrrolidone. These may be used alone or in combination of two or more.

From the standpoint of polymerizability and emulsifiability of the obtained polymer emulsifier, the monomers used in the production of the above polymer emulsifier are preferably methyl (meth)acrylate, alkali metal salts of sulfonic acid-based vinyl monomers, and styrenes.

Examples of the method for polymerizing the high-molecular-weight emulsifier 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. Non-reactive emulsifiers include, for example, low-molecular-weight anionic emulsifiers and low-molecular-weight nonionic emulsifiers, which will be described later.

Although the weight-average molecular weight of the high-molecular-weight emulsifier is not particularly limited, it is generally preferably about 1,000 to 500,000 from the viewpoint of the adhesion properties of the resulting aqueous dispersion. In addition, in this specification, said weight average molecular weight means the polyethylene-oxide conversion value in a gel permeation chromatography (GPC) method.

Examples of reactive emulsifiers other than the above-mentioned high molecular weight emulsifiers include those having a hydrophilic group such as a sulfonic acid group and a carboxyl group and a hydrophobic group such as an alkyl group and a phenyl group, and having a carbon-carbon double It means something that has a bond. Examples of carbon-carbon double bonds include functional groups such as (meth)allyl, 1-propenyl, 2-methyl-1-propenyl, vinyl, isopropenyl, and (meth)acryloyl groups. .

The reactive emulsifiers are, for example, polyoxyethylene alkyl ethers having at least one functional group in the molecule, polyoxyethylene phenyl ethers having at least one functional group in the molecule, and sulfosuccinic acid esters thereof. salts and sulfate ester salts, and furthermore, polyoxyethylene alkylphenyl ether systems having at least one of the above functional groups in the molecule, and their sulfosuccinic acid ester salts, their sulfate ester salts, their phosphoric acid ester salts, their Aliphatic or aromatic carboxylic acid salts and the like can be mentioned. In addition, acidic phosphoric acid (meth)acrylic acid ester emulsifier, acid anhydride-modified rosin glycidyl ester acrylate (see JP-A-4-256429), JP-A-63-23725, JP-A-63-240931 JP-A-62-104802 and various emulsifiers described in JP-A-62-104802. Furthermore, those obtained by replacing the polyoxyethylene in the reactive emulsifier with polyoxypropylene or block copolymerization or random copolymerization of polyoxyethylene and polyoxypropylene are also included.

Commercially available products of the above reactive emulsifiers include, for example, "KAYAMER PM-1", "KAYAMER PM-2", "KAYAMER PM-21" (manufactured by Nippon Kayaku Co., Ltd.), "SE-10N", " NE-10”, “NE-20”, “NE-30”, “Adekari Soap SR-10”, “Adekari Soap SR-20”, “Adekari Soap ER-20” (above, ADEKA Co., Ltd. ), "New Frontier A229E", "New Frontier N117E", "New Frontier N250Z", "Aqualon RN-10", "Aqualon RN-20", "Aqualon RN-50", "Aqualon HS-10", " Aqualon KH-05", "Aqualon KH-10" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Eminol JS-2" (manufactured by Sanyo Chemical Industries Co., Ltd.), "Latherm K-180" (Kao ( Co., Ltd.) and the like are typical examples.

The reactive emulsifier is preferably polyoxyethylene alkyl ether or polyoxyethylene phenyl ether from the viewpoint of polymerizability and emulsifiability of the obtained polymer emulsifier.

Examples of the low-molecular-weight anionic emulsifier include dialkylsulfosuccinate, alkanesulfonate, α-olefinsulfonate, polyoxyethylene alkylsulfosuccinate, polyoxyethylene alkylether sulfosuccinate, and polyoxyethylene. Styrylphenyl ether sulfosuccinate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene dialkyl ether sulfate, polyoxyethylene trialkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate Ester salts etc. are mentioned. 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, polyoxyethylene sorbitan fatty acid ester, and the like. These may be used alone or in combination of two or more.

The content of the emulsifier in the aqueous dispersion is not particularly limited, but from the viewpoint of excellent emulsifiability, it is preferably about 1 to 20 parts by mass based on 100 parts by mass of the rosin phenol resin composition in terms of solid content. About 10 parts by mass is more preferable.

As long as the desired properties are not impaired, the aqueous dispersion may optionally contain a cross-linking agent, antifoaming agent, thickener, filler, ultraviolet absorber, light stabilizer, antioxidant, water resistance agent, and film-forming agent. Auxiliaries, preservatives, pH adjusters such as ammonia water and sodium bicarbonate may be included.

Examples of the antiseptics include thiazoline antiseptics, benzoisothiazole antiseptics, and the like.

The aqueous dispersion is obtained by emulsifying the rosin phenol resin composition in the presence of the emulsifier. The emulsification method is not particularly limited, and known emulsification methods such as high-pressure emulsification and phase inversion emulsification can be employed.

The high-pressure emulsification method is a method in which the rosin phenol resin composition is melted, pre-mixed with an emulsifier and water, finely emulsified using a high-pressure emulsifier, and then the solvent is removed as necessary. . The method of making the material to be emulsified into a molten state may be heating alone, dissolving in a solvent and then heating, or mixing a nonvolatile substance such as a plasticizer and heating. is preferred. Examples of the solvent include organic solvents such as toluene, xylene, methylcyclohexane, and ethyl acetate that can dissolve the material to be emulsified.

In the phase inversion emulsification method, after heating and melting the rosin phenol resin composition, an emulsifier and water are added while stirring to first form a W/O emulsion, and then an O/W emulsion is formed by adding water or changing the temperature. It is a method of phase inversion to

Although the concentration of the aqueous dispersion thus obtained is not particularly limited, it is usually used after being appropriately adjusted so that the solid content is about 20 to 70% by mass. Moreover, the volume average particle size of the resulting aqueous dispersion is preferably less than about 0.7 μm from the viewpoint of storage stability. The aqueous dispersion thus obtained has a white to milky appearance and usually has a viscosity of about 10 to 1,000 mPa·s (at a temperature of 25° C. and a concentration of 50% by mass).

The pH of the aqueous dispersion obtained above is usually about 2-10. In addition, if necessary, the aqueous dispersion may contain inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; alkanolamines such as monomethylamine, monoethanolamine, diethanolamine and diisopropanolamine; Aliphatic amines; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and the like may be appropriately added to adjust the pH.

[Phesive/adhesive composition]
The pressure-sensitive adhesive/adhesive composition of the present invention contains the rosin phenolic resin composition of the present invention (or the tackifying resin composition of the present invention) and a base polymer. Moreover, the pressure-sensitive adhesive/adhesive composition of the present invention can be used as a pressure-sensitive adhesive/adhesive. In addition, in this specification, it is clarified that the term "stick/adhesive" includes either one or both of pressure sensitive adhesives and adhesives.

Examples of the base polymer include acrylic polymers, synthetic rubber elastomers, olefin polymers, acrylic polymer emulsions, rubber latexes, and synthetic resin emulsions. The base polymer may be used alone or in combination of two or more. The base polymer further contains, if necessary, a cross-linking agent, an antifoaming agent, a viscosity modifier, a filler, an antioxidant, a water resistance agent, a film-forming aid, a preservative, a pH adjuster such as aqueous ammonia or sodium bicarbonate, Leveling agents, release modifiers, plasticizers, softeners, colorants (pigments, dyes, etc.), surfactants, antistatic agents, antiaging agents, ultraviolet absorbers, light stabilizers, etc. can also be used.

In the pressure-sensitive adhesive/adhesive composition of the present invention, when the aqueous dispersion is used as the tackifying resin composition, aqueous compositions such as acrylic polymer emulsion, rubber latex and synthetic resin emulsion are used as the base polymer. is preferred.

When the pressure-sensitive adhesive/adhesive composition of the present invention contains the aqueous dispersion as the tackifying resin composition and the water-based composition as the base polymer, the concentration of the pressure-sensitive adhesive/adhesive composition is usually 40% solids. It is about 70% by mass, preferably 55 to 70% by mass.

(Acrylic polymer)
As the acrylic polymer, those generally used in various acrylic pressure-sensitive adhesives/adhesives can be used, and examples thereof include polymers of monomer components containing alkyl (meth)acrylates. Various known polymerization methods are used as the method for producing the acrylic polymer, and examples thereof include a method of radically polymerizing the monomer component in the presence of a polymerization initiator. Examples of the polymerization method include solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like. The above acrylic polymers may be used singly or in combination of two or more.

The above alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s- Butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl ( meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and the like. These alkyl (meth)acrylates may be used singly or in combination of two or more.

The monomer component in the acrylic polymer may further contain other monomers copolymerizable with the alkyl (meth)acrylate. Examples of such monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, keto group-containing monomers, and monomers having a nitrogen atom-containing ring. , alkoxysilyl group-containing monomers, polyfunctional monomers, and the like.

The carboxyl group-containing monomers include, for example, ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), and crotonic acid; ethylenically unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and citraconic acid; Anhydrides thereof (maleic anhydride, itaconic anhydride, etc.) can be mentioned.

The hydroxyl group-containing monomers include, for example, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. acrylates; unsaturated alcohols such as vinyl alcohol and allyl alcohol;

Examples of the amide group-containing monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N -Methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide and the like.

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

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

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

The alkoxysilyl group-containing monomers include, for example, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth) ) acryloxypropylmethyldiethoxysilane and the like.

The polyfunctional monomers include, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth) ) acrylate, (poly)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin di(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyl di(meth)acrylate , hexyl di(meth)acrylate and the like.

The content of the other monomer copolymerizable with the alkyl (meth)acrylate in the monomer component is not particularly limited, but is preferably about 40% by mass or less with respect to 100% by mass of the monomer component.

The above monomer components further include vinyl ester monomers such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.) and vinyltoluene; ) acrylate, cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate; aryl (meth)acrylate (e.g. phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (e.g. phenoxyethyl (meth)acrylate), arylalkyl aromatic ring-containing (meth)acrylates such as (meth)acrylates (e.g., benzyl (meth)acrylate); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; 2-(meth)isocyanate group-containing monomers such as acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; can include Although the content of these monomers is not particularly limited, it is preferably about 10% by mass or less with respect to 100% by mass of the monomer component.

The polymerization initiator is not particularly limited. -methylpropionamidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate , 2,2′-azobis(N,N′-dimethyleneisobutyramidine), 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, etc.;1 , 1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2 -ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxy- Peroxide-based initiators such as 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, benzoyl peroxide, t-butyl hydroperoxide, hydrogen peroxide; potassium persulfate, ammonium persulfate, etc. Examples include persulfate-based initiators. The polymerization initiators may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the acrylic polymer is not particularly limited, but is usually in the range of about 100,000 to 5,000,000. The weight-average molecular weight (Mw) of the acrylic polymer is preferably 1,500,000 or less, more preferably 1,000,000 or less, from the viewpoint of improving adhesive properties, and from the viewpoint of cohesiveness, etc. is 200,000 or more, more preferably 300,000 or more. In addition, in this specification, said weight average molecular weight means the polystyrene conversion value in a gel permeation chromatography (GPC) method.

The content ratio of the acrylic polymer and the rosin phenol resin composition is not particularly limited, but the effect of the modification by the rosin phenol resin composition can be sufficiently exhibited, and the heat resistance holding power, tack, etc. are reduced due to excessive use. As an appropriate range of use that does not cause , it is preferable to use the rosin phenolic resin composition at about 2 to 40 parts by mass in terms of solid content with respect to 100 parts by mass of the acrylic polymer.

(Synthetic rubber elastomer)
As the synthetic rubber-based elastomer, various known ones used for pressure-sensitive adhesive compositions can be used. The above synthetic rubber-based elastomers may be used singly or in combination of two or more.

Examples of the synthetic rubber elastomer include polyisoprene, styrene-butadiene rubber (SBR), styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, and styrene-butadiene-styrene block copolymer. Coalesced (SBS) rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, styrene-butadiene-vinylpyridine rubber, polybutadiene, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber (NBR), polychloroprene (CR), and the like.

The content ratio of the synthetic rubber-based elastomer and the rosin phenol resin composition is not particularly limited, but the effect of the modification by the rosin phenol resin composition can be sufficiently expressed, and the decrease in adhesive strength, tack, etc. due to excessive use can be prevented. As an appropriate range of use that does not cause such problems, the rosin phenolic resin composition should normally be about 15 to 210 parts by mass in terms of solid content per 100 parts by mass of the synthetic rubber elastomer.

(Olefin polymer)
The olefin-based polymer is not particularly limited as long as it is a polymer of monomer components containing various olefins, and various known polymers can be used. Examples of the olefin polymer include olefin homopolymers that are homopolymers of various olefins, olefin copolymers that are copolymers of various olefins and copolymerizable monomers, and the like. be done. The olefin polymer may be used singly or in combination of two or more.

Examples of the above olefins include ethylene, propylene, butene, butylene, isoprene, pentene, pentadiene, octene, isooctene, various isomers of hexene and hexadiene, various isomers of heptene and heptadiene; various α-olefins; cyclopentene, cyclohexene, and norbornene. , and dicyclopentadienyl. The above olefins may be used singly or in combination of two or more.

Examples of the monomers copolymerizable with the olefins include vinyl acetate and the (meth)acrylic acid esters. The copolymerizable monomer is preferably vinyl acetate. The copolymerizable monomers may be used singly or in combination of two or more.

The amount of the copolymerizable monomer used in the olefinic copolymer is not particularly limited, but is in the range of about 20 to 45% by mass with respect to 100% by mass of the olefinic copolymer. preferable.

Examples of the olefin homopolymer include polyethylene, polypropylene, ethylene-α olefin copolymer, amorphous atactic polypropylene, and the like. Examples of the olefin copolymer include ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMAA), ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), Ethylene methyl acrylate copolymer (EMA), ethylene methyl methacrylate copolymer (EMMA) and the like can be mentioned. The olefin-based copolymer is preferably an ethylene-vinyl acetate copolymer (EVA).

The content ratio of the olefin polymer and the rosin phenol resin composition is not particularly limited, but the effect of modification by the rosin phenol resin composition can be sufficiently exhibited, and the decrease in adhesive strength, tack, etc. due to excessive use can be prevented. As a suitable range of use that does not cause such problems, the rosin phenolic resin composition should be normally about 50 to 150 parts by mass in terms of solid content per 100 parts by mass of the olefinic polymer.

(Acrylic polymer emulsion)
As the acrylic polymer emulsion, various known emulsions used for water-based pressure-sensitive adhesives can be used, and examples thereof include emulsions of acrylic polymers from monomer components containing alkyl (meth)acrylates. Various known emulsion polymerization methods are used as the method for producing the above acrylic polymer emulsion. It can be easily produced by a known emulsion polymerization method such as a polymerization method or a seed polymerization method. The acrylic polymer emulsion may be used alone or in combination of two or more.

Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates used in the acrylic polymer.

The monomer component in the acrylic polymer emulsion may further contain other monomers copolymerizable with the alkyl (meth)acrylate. Examples of such monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, and keto group-containing monomers used in the acrylic polymer. , nitrogen atom-containing ring-containing monomers, alkoxysilyl group-containing monomers, polyfunctional monomers, and the like.

The content of the other monomer copolymerizable with the alkyl (meth)acrylate in the monomer component is not particularly limited, but is preferably about 40% by mass or less with respect to 100% by mass of the monomer component.

The above monomer components further include vinyl ester monomers such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.) and vinyltoluene; ) acrylate, cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate; aryl (meth)acrylate (e.g. phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (e.g. phenoxyethyl (meth)acrylate), arylalkyl aromatic ring-containing (meth)acrylates such as (meth)acrylates (e.g., benzyl (meth)acrylate); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; 2-(meth)isocyanate group-containing monomers such as acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; can include Although the content of these monomers is not particularly limited, it is preferably about 10% by mass or less with respect to 100% by mass of the monomer component.

The polymerization initiator is not particularly limited, and examples thereof include polymerization initiators used in the acrylic polymer.

Although the weight average molecular weight (Mw) of the acrylic polymer in the acrylic polymer emulsion is not particularly limited, it is usually in the range of about 100,000 to 5,000,000. The weight-average molecular weight (Mw) of the acrylic polymer is preferably 1,500,000 or less, more preferably 1,000,000 or less, from the viewpoint of improving adhesive properties, and from the viewpoint of cohesiveness, etc. is 200,000 or more, more preferably 300,000 or more. In addition, in this specification, said weight average molecular weight means the polystyrene conversion value in a gel permeation chromatography (GPC) method.

The content ratio of the acrylic polymer emulsion and the rosin phenol resin composition is not particularly limited, but the effect of the modification by the rosin phenol resin composition can be sufficiently expressed, and the heat resistance, tackiness, etc. due to excessive use can be improved. As an appropriate usage range that does not cause a decrease, it is preferable that the rosin phenolic resin composition is usually about 2 to 40 parts by mass in terms of solid content with respect to 100 parts by mass of the acrylic polymer emulsion.

(rubber latex)
As the rubber-based latex, various known ones used for water-based pressure-sensitive adhesive compositions can be used. Examples of the rubber latex include natural rubber latex and synthetic rubber latex. The natural rubber latex may be a modified natural rubber obtained by grafting (meth)acrylic acid alkyl ester or the like to natural rubber. The rubber-based latex may be used singly or in combination of two or more.

The synthetic rubber latex is an aqueous dispersion of a synthetic polymer. Examples of such synthetic polymers include the synthetic rubber elastomers described above.

The content ratio of the rubber-based latex and the rosin phenolic resin composition is not particularly limited, but the effect of modification by the rosin phenolic resin composition can be sufficiently exhibited, and excessive use causes a decrease in adhesive strength, tackiness, etc. As an appropriate range of use, the rosin phenolic resin composition should be normally about 10 to 150 parts by mass in terms of solid content with respect to 100 parts by mass of the rubber-based latex.

(synthetic resin emulsion)
As the synthetic resin emulsion, various known emulsions used in water-based pressure-sensitive adhesive compositions can be used. Examples thereof include synthetic resin emulsions such as vinyl acetate emulsions, ethylene-vinyl acetate copolymer emulsions, and urethane emulsions. mentioned. The above synthetic resin emulsions may be used alone or in combination of two or more.

The content ratio of the synthetic resin emulsion and the rosin phenolic resin composition is not particularly limited, but the effect of modifying the rosin phenolic resin composition can be sufficiently expressed, and the decrease in adhesive strength, tackiness, etc. due to excessive use can be prevented. As an appropriate range of use that does not cause such problems, the rosin phenolic resin composition should normally be about 2 to 40 parts by mass in terms of solid content per 100 parts by mass of the synthetic resin emulsion.

When acrylic polymers, synthetic rubber elastomers, and olefin polymers are used as the base polymer in the pressure-sensitive adhesive/adhesive composition, it can be used in either a varnish type or a hot-melt type.

Various organic solvents can be used when a pressure-sensitive adhesive/adhesive composition is used as the varnish type. The organic solvent is not particularly limited, but specific examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, ethyl acetate, cyclohexane, methylcyclohexane, methanol, ethanol, propanol, isopropanol, hexylene glycol. etc. The amount of the organic solvent to be used is not particularly limited, but it is usually about 100 to 500 parts by weight per 100 parts by weight of the base polymer.

When using a pressure-sensitive adhesive/adhesive composition as the hot-melt type, the organic solvent that can be used in the above-described varnish type is not particularly required.

The pressure-sensitive adhesive/adhesive composition of the present invention may optionally contain cross-linking agents, oils, waxes, antifoaming agents, viscosity modifiers, fillers, antioxidants, water-resistant agents, and modifiers as long as the desired properties are not impaired. Film auxiliaries, preservatives, pH adjusters such as aqueous ammonia and sodium bicarbonate, leveling agents, release adjusters, plasticizers, softeners, coloring agents (pigments, dyes, etc.), surfactants, antistatic agents, anti-aging agents , ultraviolet absorbers, light stabilizers, and other additives.

Examples of the cross-linking agent include isocyanate-based cross-linking agents and epoxy-based cross-linking agents. The content of the cross-linking agent is not particularly limited, but is usually 10 parts by mass or less, preferably about 0.01 to 1.0 parts by mass, per 100 parts by mass of the base polymer.

Examples of the isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. , hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; group polyisocyanates; and their biuret, isocyanurate, allophanate, adduct, and two or more selected from the group consisting of biuret, isocyanurate, allophanate and adduct react to obtain and the like.

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

Examples of the above oils include naphthenic oils, paraffinic oils, and plasticizing oils such as aromatic oils. The oil is preferably naphthenic process oil, paraffinic process oil, liquid polybutene, or the like.

Although the content of the oil is not particularly limited, it is usually preferably about 4 to 200 parts by mass with respect to 100 parts by mass of the base polymer.

The waxes include, for example, animal-derived waxes such as beeswax, spermaceti and shellac wax; plant-based waxes such as carnauba wax, Japan wax, rice bran wax and candelilla wax; petroleum-based waxes such as paraffin wax and microcrystalline wax; Synthetic waxes such as Tropsch wax, low molecular weight polyethylene wax; and mineral derived waxes such as montan wax and ozokerite. The above waxes may be used singly or in combination of two or more.

Although the content of the wax is not particularly limited, it is usually preferably about 10 to 100 parts by mass with respect to 100 parts by mass of the base polymer.

The pressure-sensitive adhesive/adhesive composition of the present invention is obtained by mixing the rosin phenol resin composition (or the tackifying resin composition), the base polymer, and, if necessary, various organic solvents and additives. . The mixing method is not particularly limited, and various known methods can be used.

[Adhesive/adhesive sheet]
The pressure-sensitive adhesive/adhesive sheet of the present invention includes a pressure-sensitive adhesive/adhesive layer and a substrate comprising the above pressure-sensitive adhesive/adhesive composition. The pressure-sensitive adhesive/adhesive sheet of the present invention may be a pressure-sensitive adhesive/adhesive sheet with a substrate having the pressure-sensitive adhesive/adhesive layer on one or both sides of the substrate. It can also be grasped as a base material provided.). The concept of adhesive/adhesive sheet as used herein can include what is referred to as adhesive/adhesive tape, adhesive/adhesive label, adhesive/adhesive film, and the like.

Examples of the base material include polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.) films, polyester (polyethylene terephthalate, etc.) films, vinyl chloride resin films, vinyl acetate resin films, polyimide films. Resin films, polyamide resin films, fluororesin films, and other plastic films such as cellophane; Japanese paper, kraft paper, glassine paper, fine paper, synthetic paper, top coat paper, etc. Woven fabrics and non-woven fabrics made of fibrous materials such as staple fiber, manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, polyolefin fiber, semi-synthetic fiber or synthetic fiber, either singly or blended Cloths; rubber sheets made of natural rubber, butyl rubber, etc.; foam sheets made of foams such as foamed polyurethane, foamed polychloroprene rubber; metal foils such as aluminum foil and copper foil; be able to. The above film may be of a non-stretched type or a stretched type (uniaxially stretched type or biaxially stretched type). The substrate may have a monolayer morphology or may have a laminated morphology.

If necessary, the base material may contain fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, UV absorbers, lubricants, plasticizers, colorants (pigments, dyes, etc.). Various additives such as may be blended.

The surface of the substrate (especially the surface on the polymer layer side) may be subjected to appropriate known or conventional surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, chemical treatments such as undercoat treatment and back surface treatment. may be applied.

The adhesive/adhesive sheet of the present invention can be produced by a known method. First, the pressure-sensitive adhesive/adhesive composition is applied to one or both sides of a base material to form a coating layer composed of the pressure-sensitive adhesive/adhesive composition. A known coating method can be applied, 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 tacky/adhesive layer composed of the tacky/adhesive composition. The conditions for heating or drying can be appropriately set according to the thickness of the tacky/adhesive layer, etc. The temperature is, for example, 10 to 120° C., and the time is, for example, 0.1 to 10 hours. The thickness (thickness after drying) of the adhesive/adhesive layer varies depending on the application, but is preferably 5 to 200 μm.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these. "Parts" and "%" in the examples are based on mass unless otherwise specified.

[Production of rosin phenolic resin composition]
Example 1
A reactor equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet tube and a steam inlet tube was charged with 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol, and then heated to 100°C. and 2.1 parts of 96% sulfuric acid were charged and reacted for 4 hours under a nitrogen gas stream. 3.0 parts of slaked lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 2
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.2 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 3
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Mao pine from China and 150.0 parts of phenol were charged, then the temperature was raised to 100 ° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.1 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 4
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 2.0 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 5
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 4.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 6
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of thioxanthen-9-one (thioxanthone) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol ) (trade name “Lowinox TBM-6”, manufactured by Addivant) was added, and then the temperature was raised to 280° C. under reduced pressure of 10 kPa and reacted at the same temperature for 4 hours to obtain a rosin phenolic resin composition. got

Example 7
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of anthrone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 8
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of 9 (10H)-acridone (acridone) (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) ( After adding 0.1 part of lowinox TBM-6 (trade name, manufactured by Addivant), the temperature was raised to 280° C. under reduced pressure of 10 kPa, and the mixture was reacted at the same temperature for 4 hours to obtain a rosin phenolic resin composition. rice field.

Example 9
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese wetland pine and 150.0 parts of phenol were charged, then the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 10
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese Yunnan pine and 150.0 parts of phenol were charged, then the temperature was raised to 100 ° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 11
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Sichuan pine produced in China and 150.0 parts of phenol were charged, then the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 12
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Brazilian pine caribbean and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 1
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. After adding 3.0 parts of slaked lime and 0.1 part of 4,4′-thiobis(6-t-butyl-3-methylphenol) (trade name “Lowinox TBM-6”, manufactured by Addivant), the pressure was adjusted to 10 kPa. The temperature was raised to 280° C. under reduced pressure, and the mixture was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 2
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of anthraquinone (manufactured by Kawasaki Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6" , manufactured by Addivant) was added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 3
Into the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese horse pine and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. 3.0 parts of slaked lime, 0.5 parts of 9-fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name "Lowinox TBM- 6", manufactured by Addivant) was added, the temperature was raised to 280° C. under reduced pressure of 10 kPa, and reaction was carried out at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 4
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese wetland pine and 150.0 parts of phenol were charged, then the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. After adding 3.0 parts of slaked lime and 0.1 part of 4,4′-thiobis(6-t-butyl-3-methylphenol) (trade name “Lowinox TBM-6”, manufactured by Addivant), the pressure was adjusted to 10 kPa. The temperature was raised to 280° C. under reduced pressure, and the mixture was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 5
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Chinese Yunnan pine and 150.0 parts of phenol were charged, then the temperature was raised to 100 ° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. After adding 3.0 parts of slaked lime and 0.1 part of 4,4′-thiobis(6-t-butyl-3-methylphenol) (trade name “Lowinox TBM-6”, manufactured by Addivant), the pressure was adjusted to 10 kPa. The temperature was raised to 280° C. under reduced pressure, and the mixture was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 6
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Sichuan pine from China and 150.0 parts of phenol were charged, then the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. After adding 3.0 parts of slaked lime and 0.1 part of 4,4′-thiobis(6-t-butyl-3-methylphenol) (trade name “Lowinox TBM-6”, manufactured by Addivant), the pressure was adjusted to 10 kPa. The temperature was raised to 280° C. under reduced pressure, and the mixture was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 7
In the same reaction vessel as in Example 1, 100.0 parts of gum rosin derived from Brazilian pine caribbean and 150.0 parts of phenol were charged, then heated to 100° C., 2.1 parts of 96% sulfuric acid was charged, and nitrogen gas was added. The reaction was allowed to proceed for 4 hours under an air stream. After adding 3.0 parts of slaked lime and 0.1 part of 4,4′-thiobis(6-t-butyl-3-methylphenol) (trade name “Lowinox TBM-6”, manufactured by Addivant), the pressure was adjusted to 10 kPa. The temperature was raised to 280° C. under reduced pressure, and the mixture was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

(Measurement of color tone)
The color tone (Gardner color number) of the rosin phenolic resin compositions and raw material natural rosin in Examples 1 to 12 and Comparative Examples 1 to 7 was measured according to JIS K0071-2. Table 1 shows the results.

表１中の注釈は以下の通りである。
※各実施例及び比較例におけるロジン類（Ａ）１００質量％に対する化合物（Ｃ）の使用量（質量％）の値である。

Notes in Table 1 are as follows.
* The value is the amount (% by mass) of compound (C) used relative to 100% by mass of rosin (A) in each example and comparative example.

Claims (10)

A rosin phenolic resin composition comprising a rosin phenolic resin which is a reaction product of rosins (A) and phenols (B), and at least one compound (C) selected from the group consisting of xanthones, thioxanthones, acridones and anthrone. thing. 2. The rosin phenol resin composition according to claim 1, wherein the color tone of the rosin phenol resin composition is 6 or less on the Gardner color scale. Claim that the rosins (A) are rosins derived from at least one pine species selected from the group consisting of Marsh pine, Merkushi pine, Caribia pine, Daio pine, Teda pine, Yunnan pine and Shijo pine. 3. The rosin phenol resin composition according to 1 or 2. The rosin phenolic resin composition according to any one of claims 1 to 3, wherein the rosins (A) are purified rosins. in the presence of at least one compound (C) selected from the group consisting of xanthone, thioxanthone, acridone and anthrone,
A method for producing a rosin phenol resin composition, comprising the step of reacting rosins (A) and phenols (B). The manufacturing method according to claim 5,
The amount of compound (C) used is 0.05 to 5% by mass with respect to 100% by mass of rosins (A).
A method for producing a rosin phenolic resin composition. The manufacturing method according to claim 5 or 6,
A method for producing a rosin phenol resin composition, comprising the step of reacting a rosin (A) with a phenol (B) in the presence of a compound (C) and a phenol sulfide. A tackifying resin composition comprising the rosin phenolic resin composition according to any one of claims 1 to 4. The tackifying resin composition according to claim 8, which is an aqueous dispersion of the rosin phenolic resin composition according to any one of claims 1 to 4. A pressure-sensitive adhesive/adhesive composition comprising the tackifier resin composition according to claim 8 or 9 and a base polymer.