TW202246418A - Rosin phenolic resin composition, tackifying resin composition, adhesive agent composition/binding agent composition, and manufacturing method of rosin phenolic resin composition to provide a rosin phenolic resin composition with good color tone - Google Patents

Abstract

The issue to be resolved by the present invention is to provide a rosin phenolic resin composition with good color tone. The solution of the invention is a rosin phenolic resin composition containing a rosin phenolic resin, which is a reaction product of rosin (A) and phenol (B); and at least one compound (C) selected from the group consisting of xanthone, thioxanthone, acridone and anthrone. The color tone of the rosin phenol resin composition is 6 or less on the Gardner color scale.

Description

Method for producing rosin phenol resin composition, tackifying resin composition, adhesive composition/adhesive composition and rosin phenol resin composition

The invention relates to a manufacturing method of a rosin phenol resin composition, a tackifying resin composition, an adhesive composition/adhesive composition and a rosin phenol resin composition.

Rosin-based resins are widely used as tackifiers for adhesives/adhesives such as hot melt adhesives and pressure-sensitive adhesives, modifiers for rubber and plastics, emulsifiers for synthetic rubber, base materials for chewing gum, It is used in various fields such as binder resins for road marking paints and inks, and sizing agents for papermaking. Examples of such rosin-based resins include natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, acid-modified rosin, rosin ester, rosin phenol resin, rosin-modified phenol resin, and metal salts of these resins.

Among them, rosin phenol resin is used as a tackifier in acrylic adhesives/adhesives, chloroprene-based adhesives/adhesives, and hot-melt adhesives/adhesives, which can give these adhesives/adhesives excellent thermal stability and adhesive force (Patent Document 1, Patent Document 2). [Prior Art Literature] (patent documents)

Patent Document 1: Japanese National Publication No. 2007-504325 Patent Document 2: Japanese Patent Application Laid-Open No. 10-287855

[Problem to be solved by the invention]

However, the conventional rosin phenol resin often lacks color tone, and the Gardner chroma is almost 7 or more. For example, Patent Document 1 discloses that the color tone of the actually obtained rosinol resin is 8 or more on the Gardner color scale, and that there is a problem in terms of color tone.

An object of the present invention is to provide a rosin phenol resin composition having a good color tone. [Technical means to solve the problem]

The inventors of the present invention have made intensive research and found that the above-mentioned problems can be solved by using a rosin phenol resin composition containing a specific polycyclic aromatic compound. That is, the present invention relates to the following methods for producing a rosin phenol resin composition, a tackifying resin composition, an adhesive composition/adhesive composition, and a rosin phenol resin composition.

1. a rosin phenolic resin composition, it comprises: a rosin phenolic resin which 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.

2. The rosin phenol resin composition according to item 1 above, wherein the color tone of the rosin phenol resin composition is 6 or less on the Gardner color scale.

3. The rosin phenol resin composition according to item 1 or 2 above, wherein the rosin (A) is a rosin derived from at least one pine species selected from the group consisting of wetland slash pine, merkusii pine, caribaea pine, king pine, loblolly pine, Yunnan pine and Simao pine.

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

5. A method for producing a rosin phenol resin composition, which comprises making rosin Steps for the reaction of species (A) and phenols (B).

6. The method for producing a rosin phenol resin composition according to item 5 above, wherein the compound (C) is used in an amount of 0.05% by mass to 5% by mass relative to 100% by mass of the rosin (A).

7. The manufacture method of the rosin phenol resin composition as described in item 5 or 6 above, wherein, the manufacture method comprises making rosin (A) and phenols ( B) Steps of the reaction.

8. A tackifying resin composition comprising the rosin phenol resin composition described in any one of items 1 to 4 above.

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

10. An adhesive composition/adhesive composition comprising the tackifying resin composition described in item 8 or 9 above, and a base polymer. [Efficacy of the invention]

The color tone of the rosin phenol resin composition of this invention is good. Furthermore, since the tackifier resin composition and adhesive composition/adhesive composition of the present invention contain the rosin phenol resin composition, coloring can be suppressed and the appearance is excellent.

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

(Rosin (A)) (A) Component is not specifically limited, Various well-known thing can be used. (A) The component may be used individually by 1 type, and may use 2 or more types together.

(A) Components, for example: derived from masson pine (Pinus massoniana), slash pine (Pinus elliottii), South Sea pine (Pinus merkusii), Caribbean pine (Pinus caribaea), king pine (Pinus palustris), loblolly pine (Pinus taeda), Yunnan pine (Pinus yunnanensis) and Simao pine (Pinus kesiya) and other natural rosins (gum rosin, tall oil rosin, wood rosin); refined rosin (hereinafter also referred to as unmodified rosin and refined rosin) quality rosin); disproportionated rosin; hydrogenated rosin, etc.

The above-mentioned purified rosin can be obtained by 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 above-mentioned natural rosin at a temperature of about 200° C. to 300° C. and a reduced pressure of about 0.01 kPa to 3 kPa. The extraction method includes, for example, a method in which the above-mentioned natural rosin is made into an alkaline aqueous solution, insoluble unsaponifiable matter is extracted with various organic solvents, and the aqueous layer is neutralized. The recrystallization method includes, for example, a method of dissolving the above-mentioned natural rosin in an organic solvent as a good solvent, distilling off the solvent to obtain a concentrated solution, and adding an organic solvent as a poor solvent. Good solvents include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; chlorinated hydrocarbon solvents such as chloroform; lower alcohols; ketones such as acetone; and acetates such as ethyl acetate. Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane. 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 and zirconia; silica, molecular sieves, zeolites, and microporous porous clays.

The above-mentioned disproportionated rosin can be obtained by various known means. Specifically, it can be obtained, for example, by a method (disproportionation) of heating the above-mentioned unmodified rosin in the presence of a disproportionation catalyst. As the disproportionation catalyst, the following various known substances can be used: supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; iodides such as iodine and iron iodide. The usage-amount of this catalyst is about 0.01-5 mass parts normally with respect to 100 mass parts of unmodified rosins, Preferably it is about 0.01-1 mass part. The reaction temperature is about 100°C to 300°C, preferably about 150°C to 290°C.

In addition, as the above-mentioned disproportionated rosin, a disproportionated rosin obtained by subjecting a disproportionated rosin to the above-mentioned purification can also be used.

The above-mentioned hydrogenated rosin can be obtained by various known means. Specifically, it can be obtained, for example, by hydrogenating the aforementioned unmodified rosin using known hydrogenation conditions. The hydrogenation conditions include, for example, a method of heating the above-mentioned unmodified rosin to about 100° C. to 300° C. under a hydrogen pressure of about 2 MPa to 20 MPa in the presence of a hydrogenation catalyst. In addition, the hydrogen pressure is preferably set at about 5 MPa to 20 MPa, and the reaction temperature is preferably set at about 150°C to 300°C. As the hydrogenation catalyst, various known substances such as supported catalysts and metal powders can be used. Examples of the supported catalyst include palladium-carbon, rhodium-carbon, ruthenium-carbon, platinum-carbon, and the like. As metal powder, nickel, platinum, etc. are mentioned. Among them, palladium, rhodium, ruthenium, and platinum-based catalysts are preferable because the hydrogenation rate of the above-mentioned unmodified rosin becomes higher and the hydrogenation time becomes shorter. Moreover, the usage-amount of a hydrogenation catalyst is about 0.01-5 mass parts normally with respect to 100 mass parts of said unmodified rosins, Preferably it is about 0.01-2 mass parts.

The above-mentioned hydrogenation can be carried out in a state in which the above-mentioned unmodified rosin is dissolved in a solvent as needed. The solvent to be used is not particularly limited as long as it is inert to the reaction and easily dissolves the raw materials and products. Specifically, for example, cyclohexane, n-hexane, n-heptane, decahydronaphthalene, tetrahydrofuran, dioxane, etc. can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but usually it may be used so that the solid content is 10% by mass or more, preferably about 10% by mass to 70% by mass relative to the above-mentioned unmodified rosin.

In addition, hydrogenated rosin obtained by subjecting hydrogenated rosin to the above purification can also be used as the above-mentioned hydrogenated rosin.

The rosin phenolic resin composition of the present invention has a characteristic of being excellent in color tone even when rosins other than those derived from masson pine (Pinus massoniana) are used as the component (A).

Conventionally, pine species other than masson pine (such as slash pine (Pinus elliottii), southern pine (Pinus merkusii), Caribbean pine (Pinus caribaea) The color tone of the rosin phenolic resin composition obtained from the rosins of pine, king pine (Pinus palustris), loblolly pine (Pinus taeda), Yunnan pine (Pinus yunnanensis) and simao pine (Pinus kesiya)) tends to be insufficient. The rosin phenol resin composition of the present invention reacts in the presence of the following (C) component, and even if rosins derived from pine species other than masson pine are used as (A) component, the color tone becomes excellent.

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

(Phenols (B)) (B) Component is not specifically limited, Various well-known thing can be used. (B) The component may be used individually by 1 type, and may use 2 or more types together.

(B) As a component, phenol, naphthols, alkylphenols, arylphenols etc. are mentioned, for example.

The above-mentioned alkylphenols include, for example, o-cresol, o-n-butylphenol, o-isobutylphenol, o-tertiary butylphenol, o-amylphenol, o-(cyclohexyl)phenol, o-octylphenol, o-nonylphenol, m-cresol, m-n-butylphenol, m-isobutylphenol, m-tertiary butylphenol, m-amylphenol, m-(cyclohexyl)phenol, m-octylphenol, m-nonylphenol, p-cresol, p-n-butylphenol, p-isobutylphenol, p-tertiary butylphenol, p-amylphenol, p-(cyclohexyl)phenol, p-octylphenol, p-nonylphenol, etc.

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

(C) A component may have various substituents in the aromatic ring contained in it. The substituents include, for example: alkyl, aryl, arylalkyl, alkenyl, arylalkenyl, alkynyl, arylalkynyl, cycloalkyl, alkylene, cycloalkylalkylene, alkylene Alkynyl, phenyl, halogen, hydroxyl, carboxyl, acyl, alkoxy, amine, dialkylamine, etc.

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

In addition, content of (C)component means the residual amount of (C)component in the rosin phenol resin composition obtained by the following manufacturing method.

(additive) The above-mentioned rosinol resin composition may contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include dehydrating agents, crystal nucleating agents, plasticizers, fluidity improvers, weather resistance agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. These additives may be used alone or in combination of two or more.

(Antioxidants) Examples of the antioxidants include phenol sulfides, phosphorothioates, phosphorus compounds, hindered phenols, and the like.

The above-mentioned phenol sulfides include, for example: 4,4'-thiobis(6-tertiary butyl-3-methylphenol), 2,4-bis(dodecylthiomethyl)-6- Methylphenol, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, 4,4'-bisphenolthiolsulfin ester, 4,4'-bisphenol thiol sulfonate, 2,2'-bis(p-cresol) sulfide, 2,2'-bis(p-cresol) sulfide, 2,2'-bis (p-cresol) sulfide, 2,2'-bis(p-tertiary butylphenol)sulfide, 2,2'-bis(p-tertiary butylphenol)sulfide, 2,2'-bis(p-tri Grade butylphenol) sulfide, 4,4'-bis(6-tertiary butyl-m-cresol) sulfide, 4,4'-bis(6-tertiary butyl-m-cresol) sulfide, 4,4 '-Bis(6-tertiary butyl-o-cresol) phenylene, 4,4'-bis(6-tertiary butyl-o-cresol) phenylene, 4,4'-bis(6-tertiary butyl-o-cresol) Cresol) sulfide, 4,4'-bis(resorcinol) sulfide, 4,4'-bis(resorcinol) sulfide, 4,4'-bis(resorcinol) sulfide, 1,1'-bis(β-naphthol)sulfide, 1,1'-bis(β-naphthol)sulfide, 1,1'-bis(β-naphthol)sulfide, 4,4'-bis (α-naphthol)sulfide, 4,4'-bis(α-naphthol)sulfide, 4,4'-bis(α-naphthol)sulfide, tertiary amylphenol disulfide oligomer, Nonylphenol disulfide oligomer, tertiary butylphenol disulfide oligomer, etc.

The above-mentioned thiophosphites include, for example: trilauryl trithiophosphite, tridecyl trithiophosphite, tribenzyl trithiophosphite, tricyclohexyl trithiophosphite, trisulfide ginseng (2-ethylhexyl) phosphite, trinaphthyl trithiophosphite, diphenyldecyl trithiophosphite, diphenyllauryl trithiophosphite, tetralauryl-4- Oxaheptyl-1,7-tetrathiophosphite, tetrakis(mercaptolauryl)-1,6-dimercaptohexylenediphosphite, Wu(mercaptolauryl)bis(1,6-extene Hexyl-dimercapto)trithiophosphite, tetrakis(mercaptolauryl)-2,9-dimercapto-p-methylene diphosphite, bis(mercaptolauryl)-1,6-dimercaptohexylene -Bis(phenyl phosphite), Dioctyl dithioneopentyl erythritol diphosphite, Dilauryl dithio neopentyl erythritol diphosphite, Phenyl lauryl dithio neopentyl erythritol diphosphite Alcohol diphosphite, etc.

The above-mentioned phosphorus-based compounds include, for example: phosphorous acid, hypophosphorous acid, and their neutralized products such as metal salts, amine salts, and ammonium salts; triphenyl phosphite, ginseng (nonylphenyl) phosphite, phosphorous acid Ginseng (2-ethylhexyl) ester, tridecyl phosphite, tri(tridecyl) phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite ester, diphenyl mono(tridecyl) phosphite, 3,9-bis(2,6-di-tertiary butyl-4-methylphenoxy)-2,4,8,10- Tetraoxa-3,9-diphosphaspiro[5.5]undecane, dilauryl phosphite, diphenyl phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetrakis(tridecyl) ) Neopentylthritol tetraphosphite, tetrakis (tridecyl) -4,4'-isopropylidene diphenyl diphosphite, bis (tertiary butylphenyl) neopentylthritol diphosphite Phosphate, bis(2,4-di-tertiary butylphenyl) neopentylthritol diphosphite, bis(2,6-di-tertiary butyl-4-methylphenyl) neopentyl tetra Alcohol diphosphite, bis(nonylphenyl) neopentylthritol diphosphite, distearyl neopentylthritol diphosphite, ginseng (2,4-di-tertiary butylphenyl) Phosphite, hydrogenated bisphenol A/neopentylthritol phosphite polymer, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

The aforementioned hindered phenols, for example: 2,5-di-tertiary butyl hydroquinone, anthraquinone, triethylene glycol bis{3-(3-tertiary butyl-5-methyl-4- hydroxyphenyl)propionate}, 1,6-hexanediol bis{3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate}, neopentylthritol tetra{3 -(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate}, octadecyl-3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propane ester}, 3,9-bis[2-{3-(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro[5.5]undecane, N,N'-hexamethylenebis(3,5-di-tertiary butyl-4-hydroxy-hydrocinnamamide ), 1,3,5-trimethyl-2,4,6-ginseng (3,5-di-tertiary butyl-4-hydroxybenzyl)benzene, Irganox (registered trademark) 565 and the like.

From the viewpoint of an excellent color tone of the rosin phenol resin composition, the antioxidant is preferably the above-mentioned phenol sulfides.

The content of the aforementioned additives in the rosin phenol resin composition is not particularly limited, but from the viewpoint of excellent color tone of the rosin phenol resin composition, it is preferably 0.01% by mass to 10% by mass relative to 100% by mass of the rosin phenol resin composition. %, more preferably about 0.01% by mass to 1% by mass.

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

(Manufacturing method of rosin phenol resin composition) The method for producing the rosin phenol resin composition of the present invention is not particularly limited, and examples thereof include a method including the steps of reacting (A) component and (B) in the presence of (C) component and, if necessary, an acid catalyst. ) ingredients are heated to cause them to react. In this reaction, the reaction temperature is 180° C. to 350° C. and the reaction time is about 6 to 18 hours.

As the manufacture method of the rosin phenol resin composition of the present invention, preferably comprise the manufacture method of following steps: (1) A step of reacting the (A) component and the (B) component at a temperature of about 100° C. to 200° C. for about 4 to 10 hours in the presence of an acid catalyst as needed (addition step); and, (2) A step of reacting the substance (adduct) obtained in the above step (1) at a temperature of about 250°C to 350°C for about 2 to 8 hours (condensation step); In the above step (1) and/or the above step (2), the reaction is performed in the presence of the component (C).

In the above production method, a step of neutralizing the acid catalyst by adding an alkaline substance after the above step (1) (neutralization step) may be included. As an alkaline substance, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide etc. are mentioned, for example.

In the above production method, the reaction may also be performed under reduced pressure in the above step (2). The decompression condition is not particularly limited, but is preferably about 0.1 kPa to 10 kPa.

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

In the said manufacturing method, although the usage-amount of (B) component is not specifically limited, Preferably it is about 50-200 mass parts with respect to 100 mass parts of (A) components.

In the above production method, the amount of component (C) used is not particularly limited, but is preferably 0.05% by mass to 5% by mass relative to 100% by mass of component (A) from the viewpoint of excellent color tone of the rosin phenol resin composition. % by mass, more preferably about 0.1% by mass to 0.5% by mass.

In the said manufacturing method, although the usage-amount of the said acid catalyst is not specifically limited, Preferably it is about 0.01-2.0 mass parts with respect to 100 mass parts of (A) components.

In the above production method, the reaction may also be performed in the presence of the above antioxidant.

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

In the above production method, the antioxidant is not particularly limited, but phenol sulfides are preferred from the viewpoint of excellent color tone of the rosin phenol resin composition.

In the above production method, the amount of the antioxidant used is not particularly limited, but is preferably 0.01% by mass to 10% by mass relative to 100% by mass of component (A) from the viewpoint of excellent color tone of the rosin phenol resin composition. %, more preferably about 0.05% by mass to 5% by mass.

(Physical properties of rosin phenolic resin composition) The physical properties of the above-mentioned rosin phenol resin composition are not particularly limited. The hue of the rosin phenol resin composition is preferably 6 or less on the Gardner colorimeter, more preferably 5 or less on the Gardner colorimeter. In addition, in the present invention, the hue refers to the value of Gardner unit chromaticity measured in accordance with Japanese Industrial Standards (JIS) K 0071-2.

In addition, the Gardner chromaticity in this invention is as follows. The so-called Gardner chroma is "between 5 and 6", which means that the Gardner chroma is 5, 5+, 5-6, 6-, 6. In this case, "5+" means that the hue is more intense than 5. Dark, "6-" means the hue is lighter than 6, and "5-6" means the hue is darker than 5+ but brighter than 6-. In addition, the so-called Gardner chromaticity "6 or less" means that the Gardner chromaticity is a natural number of 6, 6-, 5-6, 5+, or 5 or less, and does not include 6+, 6-7, or 7 or more. Natural number.

[Tackifying resin composition] The tackifying resin composition of the present invention includes the rosin phenol resin composition of the present invention. The rosin phenol resin composition of the present invention can function as a tackifier by being used in an adhesive/adhesive (including the following adhesive composition/adhesive composition).

As long as the desired characteristics are not impaired, the above-mentioned tackifying resin composition may contain plasticizers, the above-mentioned antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, tackifiers other than the above-mentioned rosin phenol resin composition, etc. various additives, etc.

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 in terms of solid content relative to 100 parts by mass of the tackifying resin composition. The content of the additives in the tackifying resin composition is not particularly limited, but is preferably about 0 to 5 parts by mass in terms of solid content relative to 100 parts by mass of the tackifying resin composition.

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

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

The above-mentioned emulsifier is not particularly limited, and various known emulsifiers can be used. Specifically, a high molecular weight emulsifier obtained by polymerizing a monomer, a low molecular weight anionic emulsifier, a low molecular weight nonionic emulsifier, etc. are mentioned. The said emulsifier may be used individually by 1 type, and may use 2 or more types together.

The monomers used in the production of the above-mentioned high molecular weight emulsifier include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate (meth)acrylic monomers such as isobornyl (meth)acrylate and polyoxyethylene (meth)acrylate; monocarboxylic acid vinyl monomers such as (meth)acrylic acid and crotonic acid Classes; maleic acid, maleic anhydride, fumaric acid, itaconic acid, muconic acid and other dicarboxylic acid vinyl monomers; vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2- Sulfonic acid-based vinyl monomers such as methylpropanesulfonic acid; phosphate esters such as 2-(meth)acryloxyethyl acid phosphate, diphenyl-2(meth)acryloxyphosphate, etc. Phosphate-based vinyl monomers such as vinyl monomers; and alkali metal salts, alkaline earth metal salts, ammonium salts, and organic base salts of various organic acids; (meth)acrylamide, N-methylol (meth)acrylamide monomers such as (meth)acrylamide; nitrile monomers such as (meth)acrylonitrile; vinyl ester monomers such as vinyl acetate; (meth)acrylic acid Hydroxyl-containing (meth)acrylate monomers such as 2-hydroxyethyl ester and 2-hydroxypropyl (meth)acrylate; styrene, α-methylstyrene, vinyltoluene and other styrenes; Vinyl ether, glycidyl (meth)acrylate, urethane acrylate, α-olefins with 6 to 22 carbon atoms, vinylpyrrolidone and other monomers. These monomers may be used alone or in combination of two or more.

From the viewpoint of polymerizability and the emulsifying properties of the obtained high molecular weight emulsifier, the monomers used in the production of the above high molecular weight emulsifier are preferably methyl (meth)acrylate, sulfonic acid vinyl monomers Alkali metal salts, styrenes.

The polymerization method of the above-mentioned high-molecular-weight emulsifier includes solution polymerization, suspension polymerization, and emulsion using the following reactive emulsifiers other than high-molecular-weight emulsifiers, non-reactive emulsifiers other than high-molecular-weight emulsifiers, etc. Aggregation etc. As a non-reactive emulsifier, the following low-molecular-weight anionic emulsifier, low-molecular-weight nonionic emulsifier, etc. are mentioned, for example.

Although the weight average molecular weight of the said high molecular weight emulsifier is not specifically limited, Usually, it is preferable to set it as about 1,000-500,000 from a viewpoint of the adhesive characteristic of the aqueous dispersion obtained. In addition, in this specification, the said weight average molecular weight means the polyoxyethylene conversion value in the gel permeation chromatography (GPC) method.

Reactive emulsifiers other than the above-mentioned high molecular weight emulsifiers include, for example, emulsifiers that have hydrophilic groups such as sulfonic acid groups and carboxyl groups and hydrophobic groups such as alkyl groups and phenyl groups, and have carbon-carbon double bonds in their molecules. . Examples of carbon-carbon double bonds include functional groups such as (meth)allyl, 1-propenyl, 2-methyl-1-propenyl, vinyl, isopropenyl, and (meth)acryl. base.

The above reactive emulsifiers include, for example: polyoxyethylene alkyl ethers having at least one of the above-mentioned functional groups in the molecule, polyoxyethylene phenyl ethers having at least one of the above-mentioned functional groups in the molecule, and the like Sulfosuccinate salts and sulfate ester salts, etc.; further, polyoxyethylene alkylphenyl ethers having at least one of the above-mentioned functional groups in the molecule and their sulfosuccinate salts, sulfate ester salts, Its phosphate ester salt, its aliphatic or aromatic carboxylate, etc. In addition, acidic phosphoric acid (meth)acrylate-based emulsifiers, acid anhydride modified products of rosin glycidyl acrylate (see Japanese Patent Laid-Open No. 4-256429), Japanese Patent Laid-Open No. 63-23725, Japanese Various emulsifiers such as those described in JP-A-63-240931 and JP-A-62-104802. Further, emulsifiers obtained by replacing polyoxyethylene in the above reactive emulsifiers with the following substances: polyoxypropylene, or block copolymerization or random copolymerization of polyoxyethylene and polyoxypropylene By.

Commercially available products of the above-mentioned reactive emulsifier include, for example, "KAYAMER PM-1", "KAYAMER PM-2", "KAYAMER PM-21" (the above are manufactured by Nippon Kayaku Co., Ltd.), "SE-10N" , "NE-10", "NE-20", "NE-30", "ADEKA REASOAP SR-10", "ADEKA REASOAP SR-20", "ADEKA REASOAP ER-20" (the above are manufactured by 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 Pharmaceutical Co., Ltd.), "ELEMINOL JS-2" (manufactured by Sanyo Chemical Industry Co., Ltd.), "Raterumu K-180" (manufactured by Kao Co., Ltd. company) etc. as a representative example.

The reactive emulsifier is preferably polyoxyethylene alkyl ethers or polyoxyethylene phenyl ethers from the viewpoint of polymerizability and emulsifying properties of the obtained high-molecular-weight emulsifier.

Examples of the aforementioned low-molecular-weight anionic emulsifier include dialkyl sulfosuccinate, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl sulfosuccinate, polyoxyethylene Alkyl ether sulfosuccinate, polyoxyethylene styrene phenyl ether sulfosuccinate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene disulfide Alkyl ether sulfates, polyoxyethylene trialkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, etc. These low-molecular-weight anionic emulsifiers may be used alone or in combination of two or more.

As said low molecular weight nonionic emulsifier, polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester, etc. are mentioned, for example. These low-molecular-weight nonionic emulsifiers 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 is preferably about 1 to 20 parts by mass in terms of solid content relative to 100 parts by mass of the rosin phenol resin composition from the viewpoint of excellent emulsifying properties. , more preferably about 2 to 10 parts by mass.

As long as the desired characteristics are not impaired, the above-mentioned aqueous dispersion may contain a crosslinking agent, an antifoaming agent, a thickener, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, a water-resistant agent, a film-forming aid, etc. pH regulators such as preservatives, preservatives, ammonia and sodium bicarbonate, etc.

Examples of the above-mentioned preservatives include thiazoline-based preservatives, benzisothiazole-based preservatives, and the like.

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

The above-mentioned high-pressure emulsification method is a method of pre-mixing an emulsifier and water after making the rosin phenol resin composition into a molten state, performing microemulsification using a high-pressure emulsifier, and removing the solvent as necessary. The method of bringing the emulsified substance into a molten state may be performed by heating alone, or may be dissolved in a solvent and then heated, or may be mixed with a nonvolatile substance such as a plasticizer and heated, but it is preferably carried out only by heating. Moreover, as a solvent, the organic solvent which can melt|dissolve the emulsified material, such as toluene, xylene, methylcyclohexane, and ethyl acetate, is mentioned.

The above-mentioned phase inversion emulsification method is a method of heating and melting the rosin phenol resin composition, adding emulsifier/water while stirring, first forming a W/O emulsion, and then inverting the phase by adding water and changing the temperature, etc. It is an O/W emulsion.

The concentration of the aqueous dispersion obtained in this way is not particularly limited, and is usually adjusted appropriately so that the solid content is about 20% by mass to 70% by mass, and used. In addition, from the viewpoint of storage stability, the volume average particle diameter of the obtained aqueous dispersion is preferably less than about 0.7 μm. In addition, the obtained aqueous dispersion has a white to milky white appearance, and its viscosity is usually about 10 mPa·s to 1000 mPa·s (temperature 25° C., concentration 50 mass %).

The pH of the aqueous dispersion obtained above is usually about 2-10. In addition, the aqueous dispersion can be appropriately added with inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; alkanolamines such as monomethylamine, monoethanolamine, diethanolamine, and diisopropanolamine; ethylamine, n-butylamine, triethylamine, etc. Aliphatic amines such as amines; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, etc. to adjust the pH value.

[Adhesive composition/Adhesive composition] The adhesive composition/adhesive composition of the present invention comprises the rosin phenol resin composition of the present invention (or the tackifying resin composition of the present invention), and a base polymer. In addition, the adhesive composition/adhesive composition of the present invention can be used as an adhesive/adhesive. In addition, in this specification, it is disclosed that the so-called "adhesive/adhesive" includes either or both of the adhesive and the adhesive.

Examples of the aforementioned base polymer include acrylic polymers, synthetic rubber-based elastomers, olefin-based polymers, acrylic polymer emulsions, rubber-based latexes, and synthetic resin-based emulsions. This base polymer can be used individually by 1 type or in combination of 2 or more types. The base polymer can be further used as required: pH regulators such as crosslinking agent, defoamer, viscosity regulator, filler, antioxidant, water resistance agent, film-forming aid, preservative, ammonia and sodium bicarbonate , leveling agent, peeling regulator, plasticizer, softener, colorant (pigment, dye, etc.), surfactant, antistatic agent, antiaging agent, ultraviolet absorber, light stabilizer, etc.

In the adhesive composition/adhesive composition of the present invention, when the above-mentioned aqueous dispersion is used as the tackifying resin composition, it is preferable to use an acrylic polymer emulsion, a rubber latex, a synthetic resin emulsion, or the like. The water-based composition serves as the base polymer.

In the adhesive composition/adhesive composition of the present invention, when the above-mentioned aqueous dispersion as a tackifying resin composition and the above-mentioned water-based composition as a base polymer are included, the adhesive composition/adhesive composition The concentration of the solids is usually about 40% by mass to 70% by mass, preferably 55% by mass to 70% by mass.

(acrylic polymer) As the above-mentioned acrylic polymer, those generally used in various acrylic adhesives/acrylic adhesives can be used, and examples thereof include polymers containing monomer components of alkyl (meth)acrylates. Various well-known polymerization methods can be used for the manufacturing method of the said acrylic polymer, For example, the method of radically polymerizing the said monomer component in presence of a polymerization initiator is mentioned. As a polymerization method, solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization etc. are mentioned, for example. The said acrylic polymer may be used individually by 1 type, and may use 2 or more types together.

The above-mentioned alkyl (meth)acrylates include, for example: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) n-butyl acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylic acid Isononyl, Decyl (meth)acrylate, Isodecyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate, Tridecyl (meth)acrylate Alkyl esters, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, (meth)acrylate base) octadecyl acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. These alkyl (meth)acrylates may be used individually by 1 type, and may use 2 or more types together.

The above-mentioned monomer component in the above-mentioned acrylic polymer may further contain other monomers copolymerizable with the above-mentioned alkyl (meth)acrylate. Examples of such monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, and cyano group-containing monomers. Monomers, monomers containing ketone groups, monomers with rings containing nitrogen atoms, monomers containing alkoxysilyl groups, multifunctional monomers, etc.

The above carboxyl group-containing monomers include, for example: ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), and crotonic acid; ethylenically unsaturated monocarboxylic acids such as maleic acid, itaconic acid, and citraconic acid; Dicarboxylic acids and their anhydrides (maleic anhydride, itaconic anhydride, etc.).

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

The above-mentioned amide group-containing monomers include, for example: (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(methyl)acrylamide ) acrylamide, etc.

The above amino group-containing monomers include, for example: aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, tertiary butylaminoethyl (meth)acrylate ethyl ester etc.

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, methacrylonitrile, and the like. The above-mentioned ketone group-containing monomers include, for example: diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetylacetate, Acetyl vinyl acetate, etc.

The above-mentioned monomers having a nitrogen atom ring include, for example: N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N -Vinylpyrimidine, N-vinylpiperone, N-vinylpyrrole, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylpyrroline, N-vinylhexyl Lactamide, N-(meth)acrylamide, etc.

The above-mentioned alkoxysilyl-containing monomers include, for example: 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane , 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, etc.

The above-mentioned polyfunctional monomers include, for example: 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, di(meth)acrylate, Triethylene glycol methacrylate, tetraethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, di(meth)acrylate (Poly)propylene glycol acrylate, Neopentyl glycol di(meth)acrylate, Neopentylthritol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Tri(meth)acrylic acid Neopentylthritol ester, dipenteopentylthritol hexa(meth)acrylate, glyceryl di(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, di( Butyl methacrylate, hexyl di(meth)acrylate, etc.

The content of other monomers copolymerizable with the alkyl (meth)acrylate in the above-mentioned monomer components is not particularly limited, but is preferably about 40% by mass or less based on 100% by mass of the above-mentioned monomer components.

The above-mentioned monomer components may further include the following monomers: vinyl ester-based monomers such as vinyl acetate and vinyl propionate; aromatic vinyl such as styrene, substituted styrene (α-methylstyrene, etc.), vinyl toluene, etc. Cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, etc.; aryl (meth)acrylate (such as Phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (such as phenoxyethyl (meth)acrylate), arylalkyl (meth)acrylate (such as (meth) (meth)acrylic esters containing aromatic rings such as benzyl acrylate); olefin-based monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; Isocyanate-containing monomers such as 2-(meth)acryloxyethyl isocyanate; alkoxy-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Monomers; vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether. The content of these monomers is not particularly limited, but is preferably about 10% by mass or less with respect to 100% by mass of the above-mentioned monomer components.

The above-mentioned polymerization initiator is not particularly limited, and examples thereof include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2' -Azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[N-(2 -carboxyethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[2 -(2-imidazolin-2-yl)propane] dihydrochloride and other azo initiators; 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane , tertiary hexyl peroxypivalate, tertiary butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, peroxy -Tertiary hexyl 2-ethylhexanoate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxyisobutyrate, peroxy-3,5,5-trimethylhexanoic acid Tertiary butyl ester, tertiary butyl peroxylaurate, benzoyl peroxide, tertiary butyl hydroperoxide, hydrogen peroxide and other peroxide initiators; potassium persulfate, ammonium persulfate and other persulfuric acid Salt starter, etc. A polymerization initiator may be used individually or in combination of 2 or more types.

The weight average molecular weight (Mw) of the said acrylic polymer is not specifically limited, Usually, it exists in the range of about 100000-5000000. The weight-average molecular weight (Mw) of the acrylic polymer is preferably at most 1,500,000, more preferably at most 1,000,000 from the viewpoint of improving adhesive properties, and preferably at least 200,000, more preferably 300,000 from the viewpoint of cohesiveness. above. In addition, in this specification, the said weight average molecular weight means the polystyrene conversion value in the gel permeation chromatography (GPC) method.

The content ratio of the above-mentioned acrylic polymer and the rosin phenol resin composition is not particularly limited, as long as the modification effect by the rosin phenol resin composition can be fully exhibited and the heat-resistant holding power and stickiness caused by excessive use will not be caused. The appropriate range of use of the reduction in the amount of rosin phenol resin composition can generally be set at about 2 to 40 parts by mass in terms of solid content relative to 100 parts by mass of the acrylic polymer.

(synthetic rubber-based elastomer) As the aforementioned synthetic rubber-based elastic body, various known ones used in adhesive compositions/adhesive compositions can be used. The aforementioned synthetic rubber-based elastomers may be used alone or in combination of two or more.

The aforementioned synthetic rubber-based elastomers include, for example, polyisoprene, styrene/butadiene rubber (SBR), styrene/isoprene (SI) rubber, styrene/isoprene/styrene Block copolymer (SIS) rubber, styrene/butadiene/styrene block copolymer (SBS) rubber, styrene/ethylene/butylene/styrene block copolymer (SEBS) rubber, styrene/ethylene /Propylene/styrene block copolymer (SEPS) rubber, styrene/ethylene/propylene block polymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, styrene/butadiene/vinylpyridine rubber , polybutadiene, methacrylate/butadiene rubber, acrylonitrile/butadiene rubber (NBR), polychloroprene (CR), etc.

The content ratio of the synthetic rubber-based elastomer and the rosin phenol resin composition is not particularly limited, as long as the modification effect of the rosin phenol resin composition can be fully exhibited and the adhesive force and stickiness caused by excessive use are not caused. The appropriate usage range of the reduction in the amount of the rosin phenol resin composition is generally about 15 to 210 parts by mass in terms of solid content relative to 100 parts by mass of the synthetic rubber-based elastomer.

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

The aforementioned olefins include, for example, ethylene, propylene, butene, butene, isoprene, pentene, pentadiene, octene, isooctene, various isomers of hexene and hexadiene, heptene And various isomers of heptadiene; various alpha olefins; cyclopentene, cyclohexene, norbornene, dicyclopentadiene and other cyclic olefins. The above-mentioned olefins may be used alone or in combination of two or more.

As a monomer copolymerizable with the above-mentioned olefins, vinyl acetate, the above-mentioned (meth)acrylates, etc. are mentioned, for example. The above-mentioned copolymerizable monomer is preferably vinyl acetate. The said copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

The amount of the copolymerizable monomer used in the olefin-based copolymer is not particularly limited, but is preferably in the range of about 20% by mass to 45% by mass relative to 100% by mass of the olefin-based copolymer.

Examples of the above-mentioned olefin-based homopolymer include polyethylene, polypropylene, ethylene/α-olefin copolymer, amorphous random polypropylene, and the like. The above-mentioned olefin-based copolymers include, for example: 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), etc. The above-mentioned olefin-based copolymer is preferably an ethylene/vinyl acetate copolymer (EVA).

The content ratio of the above-mentioned olefin-based polymer and the rosin phenol resin composition is not particularly limited, as long as the modification effect of the rosin phenol resin composition can be fully exhibited and the adhesive force, stickiness, etc. caused by excessive use will not be caused. The appropriate usage range of the reduction is usually about 50 to 150 parts by mass of the rosin phenol resin composition per 100 parts by mass of the olefin-based polymer in terms of solid content.

(acrylic polymer emulsion) As the above-mentioned acrylic polymer emulsion, various known substances used in water-based adhesives/water-based adhesives can be used, for example, acrylic polymers derived from monomer components containing alkyl (meth)acrylates Lotions etc. Various well-known emulsion polymerization methods can be used for the production method of the above-mentioned acrylic polymer emulsion. For example, a one-time addition polymerization method according to the monomer component in the presence of a polymerization initiator, a monomer stepwise addition polymerization method, an emulsification monomer It can be easily produced by well-known emulsion polymerization methods, such as a stepwise addition polymerization method and a seed polymerization method. The said acrylic polymer emulsion may be used individually by 1 type, and may use 2 or more types together.

The said alkyl (meth)acrylate is mentioned, for example: the alkyl (meth)acrylate used for the said acrylic-type polymer.

The above-mentioned monomer component in the above-mentioned acrylic polymer emulsion may further contain other monomers copolymerizable with the above-mentioned alkyl (meth)acrylate. Examples of such monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, etc. monomers, cyano-containing monomers, ketone-containing monomers, nitrogen-containing ring monomers, alkoxysilyl-containing monomers, multifunctional monomers, etc.

The content of other monomers copolymerizable with the alkyl (meth)acrylate in the above-mentioned monomer components is not particularly limited, but is preferably about 40% by mass or less based on 100% by mass of the above-mentioned monomer components.

The above-mentioned monomer components may further include the following monomers: vinyl ester-based monomers such as vinyl acetate and vinyl propionate; aromatic vinyl such as styrene, substituted styrene (α-methylstyrene, etc.), vinyl toluene, etc. Cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, etc.; aryl (meth)acrylate (such as Phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (such as phenoxyethyl (meth)acrylate), arylalkyl (meth)acrylate (such as (meth) (meth)acrylic esters containing aromatic rings such as benzyl acrylate); olefin-based monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; Isocyanate-containing monomers such as 2-(meth)acryloxyethyl isocyanate; alkoxy-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Monomers; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether, etc. The content of these monomers is not particularly limited, but is preferably about 10% by mass or less with respect to 100% by mass of the above-mentioned monomer components.

The said polymerization initiator is not specifically limited, For example, the thing used for the said acrylic-type polymer is mentioned.

The weight average molecular weight (Mw) of the acrylic polymer in the said acrylic polymer emulsion is not specifically limited, Usually, it exists in the range of about 100,000-5,000,000. The weight-average molecular weight (Mw) of the acrylic polymer is preferably at most 1,500,000, more preferably at most 1,000,000 from the viewpoint of improving adhesive properties, and preferably at least 200,000, more preferably 300,000 from the viewpoint of cohesiveness. above. In addition, in this specification, the said weight average molecular weight means the polystyrene conversion value in the gel permeation chromatography (GPC) method.

The content ratio of the above-mentioned acrylic polymer emulsion and the rosin phenol resin composition is not particularly limited, as long as the modification effect by the rosin phenol resin composition can be fully expressed and the heat-resistant retention and stickiness caused by excessive use will not be caused. The appropriate use range of the reduction in the amount of the rosin phenol resin composition can be generally set at about 2 to 40 parts by mass in terms of solid content relative to 100 parts by mass of the acrylic polymer emulsion.

(rubber-based latex) As the above-mentioned rubber-based latex, various known ones used in water-based adhesive compositions/water-based adhesive compositions can be used. Examples of the aforementioned rubber-based latex include natural rubber latex and synthetic rubber-based latex. The natural rubber latex may be modified natural rubber obtained by grafting alkyl (meth)acrylate or the like on natural rubber. The aforementioned rubber-based latexes may be used alone or in combination of two or more.

The aforementioned synthetic rubber-based latex is an aqueous dispersion of synthetic polymers. Examples of such synthetic polymers include the aforementioned synthetic rubber-based elastomers.

The content ratio of the above-mentioned rubber-based latex and the rosin phenol resin composition is not particularly limited, as long as the modification effect by the rosin phenol resin composition can be fully expressed and the adhesive force, viscosity, etc. will not be reduced due to excessive use. The appropriate use range is usually about 10 to 150 parts by mass of the rosin phenol resin composition in terms of solid content relative to 100 parts by mass of the rubber-based latex.

(synthetic resin emulsion) As the above-mentioned synthetic resin emulsion, various well-known substances used in water-based adhesive compositions/water-based adhesive compositions can be used, for example: vinyl acetate-based emulsion, ethylene/vinyl acetate copolymer emulsion, urethane-based emulsion, etc. Emulsion and other synthetic resin emulsion. The aforementioned synthetic resin emulsions may be used alone or in combination of two or more.

The content ratio of the above-mentioned synthetic resin emulsion and the rosin phenol resin composition is not particularly limited, as long as the modification effect brought by the rosin phenol resin composition can be fully expressed and the adhesive force, viscosity, etc. will not be reduced due to excessive use. The appropriate range of use of the rosin phenol resin composition is usually about 2 to 40 parts by mass in terms of solid content relative to 100 parts by mass of the synthetic resin emulsion.

In the above-mentioned adhesive composition/adhesive composition, in the case of using an acrylic polymer, a synthetic rubber-based elastomer, or an olefin-based polymer as the base polymer, any of the varnish type and the hot-melt adhesive type may be used. use in the state.

In the case of using the adhesive composition/adhesive composition in the above-mentioned varnish type, various organic solvents can be used. 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, hexanediol, etc. The usage-amount of an organic solvent is not specifically limited, Usually, it is about 100-500 mass parts with respect to 100 mass parts of said base polymers.

In the case of using the adhesive composition/adhesive composition in the above-mentioned hot-melt type, the organic solvent that can be used in the above-mentioned varnish type is not particularly required.

As long as the desired properties are not impaired, the adhesive composition/adhesive composition of the present invention may contain, as required: crosslinking agent, oil, wax, antifoaming agent, viscosity modifier, filler, antioxidant, water resistance Agents, film-forming aids, preservatives, pH regulators such as ammonia and sodium bicarbonate, leveling agents, stripping regulators, plasticizers, softeners, colorants (pigments, dyes, etc.), surfactants, antistatic Agents, anti-aging agents, UV absorbers, light stabilizers and other additives.

As said crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent etc. are mentioned, for example. The content of the above-mentioned crosslinking agent is not particularly limited, but is usually 10 parts by mass or less, preferably about 0.01 to 1.0 parts by mass, based on 100 parts by mass of the base polymer.

The above-mentioned isocyanate-based crosslinking agents include, for example, lower aliphatic polyisocyanates such as 1,2-ethylidene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; Cyclopentyl diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-toluene diisocyanate, 2,6-toluene Aromatic polyisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylene diisocyanate; and their biuret, isocyanurate, allophanate, and addition compounds, and complexes obtained by reacting two or more species selected from the group consisting of biurets, isocyanurates, allophanates and adducts.

The above-mentioned epoxy-based crosslinking agent includes, for example: bisphenol A epichlorohydrin type epoxy-based resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, triglyceride Glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetra Glycidyl-m-xylylenediamine, 1,3-bis(N,N'-diamineglycidylaminomethyl)cyclohexane and other compounds with two or more epoxy groups in the molecule.

Examples of the above-mentioned oils include plasticizing oils such as naphthene oils, paraffin oils, and aromatic oils. The oil is preferably naphthene-based processing oil, paraffin-based processing oil, liquid polybutene, or the like.

The content of the above-mentioned oil is not particularly limited, but generally, it is preferably about 4 to 200 parts by mass with respect to 100 parts by mass of the above-mentioned base polymer.

Examples of the aforementioned waxes include animal-derived waxes such as beeswax, spermaceti wax, and shellac wax; plant-based waxes such as carnauba wax, Japanese wax, rice bran wax, and candelilla wax; petroleum-based waxes such as paraffin wax and microcrystalline wax. waxes; synthetic waxes such as Fischer-Tropsch waxes and low molecular weight polyethylene waxes; and waxes of mineral origin such as montan waxes and ozokerite waxes. The above-mentioned waxes may be used alone or in combination of two or more.

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

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

[Adhesive Sheet/Adhesive Sheet] The adhesive sheet/adhesive sheet of the present invention includes an adhesive layer/adhesive layer and a base material composed of the above-mentioned adhesive composition/adhesive composition. The adhesive sheet/adhesive sheet of the present invention may be an adhesive sheet/adhesive sheet with a substrate in the form of the adhesive layer/adhesive layer on one or both sides of the substrate, or the adhesive layer/adhesive sheet Adhesive sheet/adhesive sheet without a substrate such as a form in which the adhesive layer is held on a release liner (it can also be understood as a substrate with a release surface). The concept of adhesive sheet/adhesive sheet mentioned here may include so-called adhesive tape/adhesive tape, adhesive label/adhesive label, adhesive film/adhesive film, and the like.

As the substrate, for example, films made of polyolefin (polyethylene, polypropylene, ethylene/propylene copolymer, etc.), films made of polyester (polyethylene terephthalate, etc.), films made of vinyl chloride-based resins, etc., can be used. , vinyl acetate-based resin film, polyimide-based resin film, polyamide-based resin film, fluorine-based resin film, other plastic films such as cellophane; Japanese paper, kraft paper, cellophane (glassine ), Daolin paper, synthetic paper, surface coated paper and other papers; made of cotton fiber, staple fiber, Manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, Fabrics such as woven and non-woven fabrics made of natural fibers such as polyamide fibers and polyolefin fibers, semi-synthetic fibers or synthetic fibers, etc. alone or blended; rubber sheets composed of natural rubber, butyl rubber, etc. foam sheets made of foamed polyurethane foam, polychloroprene foamed rubber, etc.; metal foils such as aluminum foil and copper foil; composites of these, etc. The above-mentioned film may be any of non-oriented type and oriented type (uniaxially oriented type or biaxially oriented type). The base material may have a single-layer form or may have a laminated form.

In addition, fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, ultraviolet absorbers, lubricants, plasticizers, colorants (pigments, dyes, etc.) ) and other additives.

On the surface of the substrate (especially the surface of the polymer layer side), for example, the following suitable known or customary surface treatments can be implemented: physical treatments such as corona discharge treatment and plasma treatment; chemical treatments such as primer treatment and back treatment Wait.

The adhesive sheet/adhesive sheet of the present invention can be produced by a known method. First, the above-mentioned adhesive composition/adhesive composition is coated on one or both surfaces of a substrate to form a coating layer composed of the adhesive composition/adhesive composition. As the coating method, a known method can be applied, and examples thereof include a roll coater method, a cutaway wheel coater method, a die coater method, a reverse coater method, a screen method, and a gravure coater method. Next, by heating or drying the coating layer, an adhesive layer/adhesive layer composed of the above adhesive composition/adhesive composition is formed. Conditions for heating or drying can be appropriately set according to the thickness of the adhesive layer/adhesive layer, etc., and the temperature is, for example, 10° C. to 120° C., and the time is, for example, 0.1 hour to 10 hours. The thickness (thickness after drying) of the adhesive layer/adhesive layer varies depending on the application, but is preferably 5 μm to 200 μm. [Example]

The following examples and comparative examples are given to describe the present invention in more detail, but the present invention is not limited to these examples. Unless otherwise specified, "part" and "%" in an Example are based on mass.

[Manufacture of rosin phenolic resin composition] Example 1 100.0 parts of gum rosin and 150.0 parts of phenol from China-made masson pine were put into a reaction vessel equipped with a stirring device, a condenser, a thermometer, and a nitrogen gas inlet pipe/water vapor inlet pipe, and the temperature was raised to 100°C, and 96% 2.1 parts of sulfuric acid were reacted for 4 hours under a nitrogen stream. Add 3.0 parts of hydrated lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 2 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 0.2 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 0.1 part of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 4 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 2.0 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 5 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 4.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 6 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of slaked lime, thioxanth-9-one (thioxanthone) (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.), 0.5 parts, 4,4'-thiobis(6-tertiary butyl-3-methanol) phenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co.) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 7 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 0.5 parts of anthrone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6" , Addivant Co.) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 8 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 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-tertiary butyl-3-methyl Phenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co.) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Example 9 In the same reaction vessel as in Example 1, 100.0 parts of gum rosin and 150.0 parts of phenol derived from slash pine produced in China were added, the temperature was raised to 100°C, 2.1 parts of 96% sulfuric acid were added, and the reaction was carried out under a nitrogen stream. 4 hours. Add 3.0 parts of hydrated lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese Yunnan pine, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Simao pine produced in China, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Brazilian Caribbean pine, the temperature was raised to 100° C., and 2.1 parts of 96% sulfuric acid was added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of hydrated lime, 0.5 parts of xanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6 ", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 1 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. After adding 3.0 parts of slaked lime and 0.1 part of 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co., Ltd.), decompression at 10kPa The temperature was lowered to 280° C. and reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 2 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of slaked lime, 0.5 parts of anthraquinone (manufactured by Kawasaki Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6" , Addivant Co.) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

Comparative example 3 In the same reaction vessel as in Example 1, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese pine masson, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. Add 3.0 parts of slaked lime, 0.5 parts of 9-xenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM- 6", manufactured by Addivant Corporation) 0.1 part, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and it was reacted 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 and 150.0 parts of phenol derived from slash pine produced in China were added, the temperature was raised to 100°C, 2.1 parts of 96% sulfuric acid were added, and the reaction was carried out under a nitrogen stream. 4 hours. After adding 3.0 parts of slaked lime and 0.1 part of 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co., Ltd.), decompression at 10kPa The temperature was lowered to 280° C. and 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Chinese Yunnan pine, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. After adding 3.0 parts of slaked lime and 0.1 part of 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co., Ltd.), decompression at 10kPa The temperature was lowered to 280° C. and 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Simao pine produced in China, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid were added, and it was reacted under a nitrogen stream for 4 Hour. After adding 3.0 parts of slaked lime and 0.1 part of 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co., Ltd.), decompression at 10kPa The temperature was lowered to 280° C. and 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, after adding 100.0 parts of gum rosin and 150.0 parts of phenol derived from Brazilian Caribbean pine, the temperature was raised to 100° C., and 2.1 parts of 96% sulfuric acid was added, and it was reacted under a nitrogen stream for 4 Hour. After adding 3.0 parts of slaked lime and 0.1 part of 4,4'-thiobis(6-tertiary butyl-3-methylphenol) (trade name "Lowinox TBM-6", manufactured by Addivant Co., Ltd.), decompression at 10kPa The temperature was lowered to 280° C. and reacted at the same temperature for 4 hours to obtain a rosin phenol resin composition.

(measurement of hue) The color tone (Gardner chroma) of the rosin phenol resin composition and the raw material natural rosin in Examples 1 to 12 and Comparative Examples 1 to 7 were measured in accordance with JIS K 0071-2. The results are shown in Table 1.

[Table 1] Rosin (A) Compound (C) Rosin phenolic resin composition Pine species Hue (Gardner Chroma) composition Usage amount ^※ (%) Hue (Gardner Chroma) Example 1 Masson pine from China 6+ Xanthone 0.5 5- Example 2 Xanthone 0.2 5+ Example 3 Xanthone 0.1 5+ Example 4 Xanthone 2.0 4-5 Example 5 Xanthone 4.5 4-5 Example 6 Thioxanth-9-one 0.5 5 Example 7 Anthrone 0.5 5+ Example 8 9(10H)-acridone 0.5 5-6 Example 9 Chinese slash pine 8 Xanthone 0.5 5 Example 10 Chinese Yunnan Pine 7 Xanthone 0.5 5 Example 11 Simao pine from China 7 Xanthone 0.5 5 Example 12 Brazilian Caribbean pine 9 Xanthone 0.5 6 Comparative example 1 Masson pine from China 6+ - - 6-7 Comparative example 2 Anthraquinone 0.5 7+ Comparative example 3 9-Termine 0.5 7 Comparative example 4 Chinese slash pine 8 - - 7 Comparative Example 5 Chinese Yunnan Pine 7 - - 7 Comparative example 6 Simao pine from China 7 - - 7 Comparative Example 7 Brazilian Caribbean pine 9 - - 7-8 Notes in Table 1 follow. * It is the value of the usage-amount (mass %) of the compound (C) with respect to 100% mass % of rosins (A) in each Example and a comparative example.

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Claims (10)

A rosin phenolic resin composition, which comprises: a rosin phenolic resin which 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. The rosin phenol resin composition according to claim 1, wherein the hue of the rosin phenol resin composition is 6 or less on the Gardner color scale. The rosin phenol resin composition according to claim 1 or 2, wherein the rosin (A) is a rosin derived from at least one pine species selected from the group consisting of slash pine, Nanyang pine, Caribbean pine, king pine, loblolly pine, Yunnan pine and Simao pine. The rosin phenol resin composition according to any one of claims 1 to 3, wherein the rosin (A) is a purified rosin. A method for producing a rosin phenol resin composition, comprising making rosin ( A) Steps of reacting with phenols (B). The method for producing a rosin phenol resin composition according to claim 5, wherein the compound (C) is used in an amount of 0.05% by mass to 5% by mass relative to 100% by mass of the rosin (A). The manufacture method of the rosin phenol resin composition as described in claim 5 or 6, wherein, the manufacture method comprises making rosin (A) and phenols (B) in the presence of compound (C) and phenol sulfides The steps of the reaction. A tackifying resin composition comprising the rosin phenol resin composition described in any one of claims 1-4. The tackifying resin composition according to claim 8, wherein the tackifying resin composition is an aqueous dispersion of the rosin phenol resin composition according to any one of claims 1-4. An adhesive composition/adhesive composition, wherein it comprises the tackifying resin composition described in claim 8 or 9, and a base polymer.