JPH11335654A - Tackifying resin and adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tackifying resin capable of imparting an excellent adhesive force and having excellent weather resistance by using a rosin substance containing tetrahydroabietic acid in a specific amount and/or its esterification product. SOLUTION: This tackifying resin comprises (A) a rosin substance containing tetrahydroabietic acid in an amount of >=50 wt.%, preferably >=80 wt.%, and/or a rosin ester derived from the component A. The component A is obtained, for example, by hydrogenating a rosin of raw material, such as gum rosin, in the presence of a hydrogenation catalyst under pressurization using hydrogen with heating until the tetrahydroabietic acid content of the hydrogenated rosin reaches >=50%. In order to improve the color tone of the component A, it is preferable to carry out a distillation purification treatment after the hydrogenation treatment. The component B is obtained by esterifying the component A with a polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a tackifier resin and a pressure-sensitive adhesive composition. The tackifier resin of the present invention can be used in any form of a solvent type or an emulsion type, and the pressure-sensitive adhesive composition containing the tackifier resin of the present invention is labeled as a solvent type pressure-sensitive adhesive composition or an aqueous pressure-sensitive adhesive composition. , Sheets, tapes and the like.

[0002]

2. Description of the Related Art Due to its convenience, adhesives are currently applied to many adhesive products such as labels, sheets and tapes. As the applications of the pressure-sensitive adhesive have expanded, the performance required of the pressure-sensitive adhesive has also become higher. As such required performance, adhesion to a polyolefin base material such as polypropylene and polyethylene has been emphasized.

In general, the adhesion to a polyolefin substrate is improved by blending a tackifying resin such as rosin or rosin ester with an acrylic or rubber-based pressure-sensitive adhesive.

However, pressure-sensitive adhesive compositions containing rosin or rosin ester are generally resistant to light (weather resistance).
Is significantly inferior, and contrary to the adhesive properties such as adhesive strength, the weather resistance decreases as the amount of rosin or rosin ester added increases. The use of a generally known hydrogenated rosin or hydrogenated rosin ester as a tackifier resin can improve weather resistance to some extent but cannot be said to be sufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a tackifying resin capable of imparting excellent adhesive strength and excellent weather resistance, and a pressure-sensitive adhesive composition obtained by blending the tackifying resin. The purpose is to provide.

[0006]

Means for Solving the Problems In view of the above-mentioned problems of the pressure-sensitive adhesive composition obtained by mixing a tackifier resin with an existing acrylic or rubber-based base resin, the present inventors have conducted intensive studies. As a result, they have found that among the rosin substances, those containing tetrahydroabietic acid in a specific amount or more can solve the above-mentioned problems as the tackifier resin, and have completed the present invention.

That is, the present invention relates to a tackifying resin comprising a rosin substance (A) containing 50% by weight or more of tetrahydroabietic acid and / or a rosin ester (B) derived from the rosin substance (A); A resin emulsion obtained by emulsifying a rosin substance (A) containing 50% by weight or more of abietic acid and / or a rosin ester (B) derived from the rosin substance (A) in the presence of an emulsifier; A solvent-based pressure-sensitive adhesive composition containing the acrylic polymer or rubber-based elastomer and the tackifying resin; an acrylic polymer emulsion or a rubber-based latex; and the tackifying resin emulsion. The present invention relates to a water-based pressure-sensitive adhesive composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The tackifying resin of the present invention is a rosin substance (A) containing 50% by weight or more of tetrahydroabietic acid and / or a rosin ester (B) derived from the rosin substance (A). is there. Preferably, the content of tetrahydroabietic acid is at least 60% by weight, more preferably at least 80% by weight. The higher the content of tetrahydroabietic acid in the rosin substance (A), the better. When the content of tetrahydroabietic acid is 50
If the amount is less than 10% by weight, the weather resistance of the resulting pressure-sensitive adhesive composition is not sufficient.

The rosin substance (A) containing 50% by weight or more of tetrahydroabietic acid is not particularly limited as long as it contains 50% by weight or more of tetrahydroabietic acid. For example, the rosin substance (A) can be obtained by subjecting a raw rosin to a hydrogenation treatment described below. In addition, as raw material rosin, gum rosin, wood rosin, tall oil rosin and the like can be mentioned.

[0010] The term "hydrotreating" means that a raw rosin is heated and reacted under hydrogen pressure in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include various known catalysts such as supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; and iodides such as iodine and iron iodide. The amount of the catalyst used is usually about 0.01 to 5% by weight, preferably 0.1 to 5% by weight, based on rosin.
The reaction temperature is about 100 to 300 ° C., preferably the lower limit is 150 ° C. and the upper limit is 290 ° C., and the hydrogen pressure is usually from normal pressure to 200 kg / cm in a sealed container.
It is performed under the condition of about ² and preferably about 50 kg / cm ^{2 at the} lower limit. The hydrogenation treatment is performed by appropriately combining these conditions so that the content of tetrahydroabietic acid in the obtained hydrogenated rosin is 50% by weight or more.

In order to improve the color tone of the rosin substance (A), purification can be performed before or after the hydrogenation treatment. Preferably, purification treatment is performed after hydrogenation treatment. Here, the purification treatment means removing high-molecular-weight substances that are considered to have been generated from the peroxide contained in the raw material rosin and unsaponifiable substances originally contained in the raw material rosin. More specifically, operations such as distillation, recrystallization, and extraction may be performed, and purification by distillation is preferable industrially. In the case of distillation, the temperature is usually appropriately selected from the range of 200 to 300 ° C. and the pressure of 1 to 10 mmHg in consideration of the distillation time. In the case of recrystallization, for example, the raw material rosin or hydrogenated rosin is dissolved in a good solvent, then the solvent is distilled off to form a concentrated solution, and a poor solvent is added to this solution. Good solvents include ketones such as benzene, toluene, xylene, chloroform, lower alcohol, and acetone;
Examples of acetates such as ethyl acetate include n-hexane, n-heptane, cyclohexane, and the like as poor solvents.
Isooctane and the like. Further, in the case of extraction, the raw material rosin or hydrogenated rosin is converted into an aqueous alkali solution using alkaline water, and the insoluble unsaponifiable product is extracted with an organic solvent, and then the aqueous layer is neutralized.

Further, in order to improve the color tone of the rosin substance (A), there is a method of further performing a dehydrogenation treatment or a hydrogenation treatment. Ordinary conditions can be adopted for the dehydrogenation treatment. For example, a rosin substance (A) is subjected to an initial hydrogen pressure of less than 10 kg / cm ² , preferably 5 kg in a closed vessel in the presence of a dehydrogenation catalyst.
The reaction is performed in a range of less than kg / cm ² , a reaction temperature of about 100 to 300 ° C., preferably a lower limit of 200 ° C. and an upper limit of 280 ° C. Since it is a dehydrogenation reaction, hydrogen is substantially unnecessary,
The initial hydrogen pressure is less than 10 kg / cm ² with the intention of utilizing the generated hydrogen for peroxide reduction, and the pressure may be adjusted by the self-pressure of the generated hydrogen or by slightly supplying hydrogen from outside. . As the dehydrogenation catalyst, various known catalysts can be used without any particular limitation. Palladium-based, rhodium-based, and platinum-based catalysts can be preferably exemplified. The amount of the catalyst used is usually 0.1 to the rosin substance (A).
About 01 to 5% by weight, preferably 0.05% by weight,
The upper limit is 3% by weight.

The rosin esterified product (B) derived from the rosin substance (A) is obtained by esterifying the rosin substance (A). In order to improve the color tone of the rosin esterified product (B), the rosin substance (A) may be subjected to a dehydrogenation treatment during or after the esterification reaction.

In the esterification reaction, ordinary rosin ester conditions for causing an esterification reaction between a rosin and a polyhydric alcohol can be employed as they are. For example, the reaction is carried out by heating the rosin substance (A) and the polyhydric alcohol to about 150 to 300 ° C. under an atmospheric pressure under an inert gas stream to remove water produced by the reaction outside the system. The charging ratio of the rosin substance (A) and the polyhydric alcohol is not particularly limited, but is usually about 1.1 to 1.5 times the amount of a hydroxyl group equivalent to the carboxyl group equivalent of the rosin substance (A). It is better to use polyhydric alcohols.

Examples of polyhydric alcohols include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; and tetrahydric alcohols such as pentaerythritol and diglycerin. Hydric alcohol; hexahydric alcohol such as dipentaerythritol. In addition,
In the reaction, an esterification catalyst is not necessarily required, but in order to shorten the reaction time, for example, an acid catalyst such as acetic acid and paratoluenesulfonic acid, an alkali metal hydroxide such as lithium hydroxide, and calcium hydroxide. Alkaline earth metal hydroxides and metal oxides such as calcium oxide and magnesium oxide can also be used.

When the dehydrogenation treatment is performed after the esterification reaction, the dehydrogenation may be performed under the same conditions as described above. When the dehydrogenation treatment is carried out during the esterification reaction, a predetermined amount of the rosin substance (A) and the polyhydric alcohol are charged under a stream of nitrogen gas, and the reaction is carried out in the presence of the above-mentioned dehydrogenation catalyst, usually under atmospheric pressure. The reaction is performed by heating to about 150 to 300 ° C. to remove the reaction water outside the system.

The rosin substance (A) containing 50% by weight or more of tetrahydroabietic acid thus obtained and / or
Alternatively, the rosin esterified compound (B) can further improve the color stability by adding an organic phosphorus compound. Examples of the organic phosphorus compound include triphenyl phosphite, tricresyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-
t-butylphenyl-di-tridecyl) phosphite,
Cyclic neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, 9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-
(Butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
-Oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene and the like. The amount of the organic phosphorus compound to be used is 1% by weight or less, preferably 0.5% by weight or less, based on the rosin substance (A) and / or the rosin esterified product (B).

The tackifying resin comprising the rosin substance (A) and / or the rosin esterified product (B) is
It can also be used as a tackifying resin emulsion which is emulsified in the presence of an emulsifier to form a resin emulsion.

The emulsifier used for emulsification includes α
-Anionic emulsifiers such as olefin sulfonate, alkyl sulfate, alkyl phenyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, half-ester salt of sulfosuccinic acid of polyoxyethylene aralkyl phenyl ether, rosin soap, polyoxyethylene alkyl phenyl ether, etc. Can be exemplified. The amount of the emulsifier used is not particularly limited, but is usually about 1 to 10 parts by weight, preferably 1 part by weight as a solid content, based on 100 parts by weight of the rosin substance (A) and / or the rosin esterified product (B). The upper limit is 5 parts by weight. If the amount exceeds 10 parts by weight, the water resistance of the water-based pressure-sensitive adhesive composition tends to decrease. If the amount is less than 1 part by weight, the stability of the resin emulsion during emulsification tends to deteriorate.

As a method of emulsifying the rosin substance (A) and / or the rosin esterified product (B), for example,
A method of dissolving a rosin substance (A) and / or a rosin esterified product (B) in a solvent such as benzene or toluene, adding the emulsifier and soft water, emulsifying using a high-pressure emulsifier, and then removing the solvent under reduced pressure. , Rosin substance (A)
And / or a small amount of a solvent such as benzene or toluene is mixed so that the softening point of the rosin esterified product (B) is about 90 ° C. or less, then an emulsifier is kneaded, and hot water is gradually added to the mixture. After the emulsion is obtained by phase emulsification, the solvent is removed under reduced pressure or used as it is, or the temperature is raised to the softening point of the rosin substance (A) and / or the rosin esterified product (B) or higher in an autoclave. A method in which an emulsifier is kneaded, hot water is gradually added, and phase inversion emulsification is carried out to emulsify the emulsion can be used. In the present invention, any method can be employed.

The solvent-based pressure-sensitive adhesive composition of the present invention is obtained by mixing an acrylic polymer or a rubber-based elastomer with a tackifying resin comprising the rosin substance (A) and / or the rosin esterified product (B). It is.

As the acrylic polymer, those generally used for various acrylic pressure-sensitive adhesives can be used. There is no particular limitation on the composition, and various known acrylic acid esters and / or methacrylic acid esters ｛
A homopolymer or a copolymer mainly composed of (meth) acrylate and abbreviation (a) can be used as it is. Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2
-Ethylhexyl and the like. Further, (meth) acrylic acid, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N
-Methylol (meth) acrylamide or the like may be used in combination.
Further, if desired, other copolymerizable monomers such as vinyl acetate and styrene may be used in combination to such an extent that the adhesive properties of the (meth) acrylate polymer are not impaired. The glass transition temperature of the acrylic polymer containing (meth) acrylic acid ester as a main component is not particularly limited, but is usually -70 to 0 ° C, preferably -60 to -10 ° C.
It is good to be in the range of. When the glass transition temperature is too high, the tack tends to decrease, and when the glass transition temperature is too low, the adhesiveness tends to decrease.

The amount of the tackifying resin composed of the rosin substance (A) and / or the rosin esterified product (B) relative to the acrylic polymer is 100
2 to 4 parts of tackifier resin based on parts by weight (solid content)
It is preferable to use it in a range of about 0 parts by weight (solid content conversion amount). In particular, the lower limit is preferably 5 parts by weight and the upper limit is preferably 20 parts by weight. If the amount of the tackifying resin is less than 2 parts by weight, it is difficult to impart sufficient adhesive strength. If the amount exceeds 40 parts by weight, not only the adhesive strength decreases but also the adhesive becomes hard and the tack becomes poor. It is not preferable because it decreases.

The acrylic pressure-sensitive adhesive composition uses a crosslinking agent such as a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, or an epoxy resin in addition to the acrylic polymer and the tackifying resin, and has a cohesive strength and heat resistance. Can be improved.

As the rubber-based elastomer, a styrene / butadiene copolymer (hereinafter, referred to as SBR), a natural rubber (hereinafter, referred to as NR), or the like can be used.

The rosin substance (A) and / or rosin esterified compound (B) with respect to a rubber elastomer
The amount of the tackifier resin used is from about 10 to 150 parts by weight (solids equivalent) of the tackifier resin based on 100 parts by weight (solids equivalent) of the rubber-based elastomer. Is preferred. In particular, the lower limit is preferably 25 parts by weight and the upper limit is preferably 100 parts by weight. When the compounding amount of the tackifier resin is less than 10 parts by weight, it is difficult to impart sufficient adhesive strength. When the compounding amount exceeds 150 parts by weight, not only the adhesive force decreases but also the adhesive becomes hard and the tack becomes poor. Tends to decrease.

The solvent-based pressure-sensitive adhesive composition may optionally contain a thickener, a filler, an antioxidant, a film-forming aid, an ultraviolet absorber and the like. Further, various known tackifier resins can be used in combination as long as the performance of the tackifier resin of the present invention is not impaired.

The water-based pressure-sensitive adhesive composition of the present invention is obtained by mixing an emulsion of an acrylic polymer or a rubber-based latex with an emulsion of a tackifying resin comprising the rosin substance (A) and / or the rosin esterified product (B). It is.

As the acrylic polymer emulsion,
Emulsions generally used for various acrylic pressure-sensitive adhesives can be used. The acrylic polymer emulsion is usually obtained by emulsion polymerization of an acrylic ester and / or a methacrylic ester. As the emulsion polymerization method, various methods such as a batch charge polymerization method, a monomer sequential addition polymerization method, an emulsion monomer sequential addition polymerization method, and a seed polymerization method can be employed.

The acrylate and methacrylate (hereinafter referred to as (meth) acrylate) monomers used include methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. Esters, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like. One of these may be used alone, or two or more may be mixed. Used. Further, in order to impart stability to the obtained emulsion, a part of the (meth) acrylic acid ester can be used in a small amount instead of (meth) acrylic acid. Further, if desired, a copolymerizable monomer such as vinyl acetate, styrene, or the like can be used in combination without impairing the adhesive properties of the (meth) acrylate polymer. The glass transition temperature of these (meth) acrylate-based polymers is generally about -70 to 0 ° C, preferably -60 to -10 ° C. If the temperature exceeds 0 ° C., the tack is undesirably reduced. Further, as an emulsifier used for the acrylic polymer emulsion, an anionic emulsifier, a partially saponified polyvinyl alcohol, or the like can be used, and its amount is usually 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic polymer emulsion. It is about.

For the acrylic polymer emulsion,
The amount of the emulsion of the tackifier resin composed of the rosin substance (A) and / or the rosin esterified product (B) is as follows. ~ 4
It is preferable to use it in a range of about 0 parts by weight (solid content conversion amount). In particular, the lower limit is preferably 5 parts by weight and the upper limit is preferably 20 parts by weight. If the amount of the tackifying resin emulsion is less than 2 parts by weight, it is difficult to impart sufficient adhesive strength. If the amount exceeds 40 parts by weight, not only the adhesive strength is reduced but also the adhesive becomes hard and the tackiness becomes high. Is also undesirably reduced.

As the rubber latex, styrene / butadiene copolymer latex (hereinafter, referred to as SBR latex), natural rubber latex (hereinafter, referred to as NR latex) and the like can be used. SBR latex refers to SBR latex and / or carboxy-modified S
BR latex, which is usually commercially available for adhesives can be used. In particular, in consideration of rubber elasticity, low-temperature physical properties, and the like, the bonding ratio of styrene / butadiene is preferably about 25/75 to 45/55 by weight. The gel fraction (toluene-insoluble matter weight%) is 35 to 65%.
Are preferred. Further, as the NR latex, either a depolymerized one or a non-depolymerized one can be used. One type of rubber latex such as SBR latex or NR latex may be used, or two or more types may be used by mixing at an arbitrary ratio.

The above-mentioned rosin substance (A) and / or rosin esterified product (B) with respect to rubber-based latex
The amount of the emulsion of the tackifying resin emulsion consisting of the tackifying resin emulsion is 10 to 150 parts by weight per 100 parts by weight (solid content) of the rubber-based latex.
It is preferable to use the composition in a range of about parts by weight (solid content equivalent). In particular, the lower limit is preferably 25 parts by weight and the upper limit is preferably 100 parts by weight. If the amount of the tackifying resin emulsion is less than 10 parts by weight, it is difficult to impart sufficient adhesive strength. If the amount exceeds 150 parts by weight, not only the adhesive strength is reduced but also the adhesive becomes hard, and the tackiness increases. Also tend to decrease.

The water-based pressure-sensitive adhesive composition may contain an antifoaming agent, a thickener, a filler, an antioxidant, a water-proofing agent, a film-forming aid, and the like, if necessary.

[0035]

According to the present invention, it is possible to provide a tackifier resin which can impart excellent adhesive strength and also has excellent weather resistance, and a pressure-sensitive adhesive composition obtained by blending the tackifier resin.

[0036]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, all parts and percentages are by weight unless otherwise specified.

Production Example 1 (Production of Acrylic Polymer) In a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen inlet pipe, 57 parts of ethyl acetate, 33 parts of toluene, 97 parts of butyl acrylate and 97 parts of acrylic acid After the parts were charged, the temperature was raised under a nitrogen stream until the temperature in the system reached about 75 ° C. Then, 0.5 part of azobisisobutyronitrile and 10 parts of ethyl acetate were previously dropped from the dropping funnel into the system in about 3 hours, and the temperature was kept at the same temperature for 5 hours to complete the polymerization reaction. Thus, an acrylic polymer having a solid content of 49.6% and a viscosity (23 ° C.) of 11,000 cps was obtained.

Production Example 2 (Production of acrylic polymer) Production Example 1 was the same as Production Example 1 except that the mixing ratio of the acrylic monomer was changed to 73 parts of butyl acrylate, 25 parts of 2-ethylhexyl acrylate, and 2 parts of acrylic acid. Exactly the same as above, solid content 49.4%, viscosity (23 ° C) 8000 cps
Was obtained.

Production Example 3 (Production of Acrylic Polymer Emulsion) (1) 43.90 parts of butyl acrylate and 1.36 parts of acrylic acid (2) 0.23 part of catalyst (potassium persulfate), pH adjuster 0.11 part of heavy sodium and 9.04 parts of water In a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen inlet tube, water 4 was added under a nitrogen gas stream at 70 ° C.
4.46 parts and 0.90 of an anionic emulsifier (trade name: Hytenol S, solid content: 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
After dissolving the mixture, 1/10 of the total of the above (1) and (2) was added under stirring, and the mixture was added at 70 ° C. under a nitrogen gas stream.
Preliminary reaction was performed for 0 minutes, and then (1) and (2)
Was added dropwise over 2 hours to carry out dropwise polymerization. After dropping all of (1) and (2), the reaction was completed for 1 hour at 70 ° C., cooled to room temperature,
It was taken out while performing a 00 mesh wire mesh filtration to obtain an acrylic polymer emulsion having a solid content of 45.7%.

Production Example 4 (Production of Acrylic Polymer Emulsion) The blending ratio (1) of the acrylic monomer in Production Example 3 was 33.0 parts of butyl acrylate, 11.3 parts of 2-ethylhexyl acrylate, and 0.1 part of acrylic acid. Production Example 3 except that 9 parts were used
In the same manner as above, an emulsion of an acrylic polymer having a solid content of 46.1% was obtained.

Example 1 (Production of tackifying resin) (1) Hydrogenation treatment An acid value of 171 and a softening point of 76 were added to a 3-liter autoclave.
C., 1000 g of unpurified Chinese gum rosin having a color tone of Gardner Color 6 and 5 g of 5% palladium carbon (water content: 50%) as a hydrogenation catalyst, oxygen in the system was removed, and then the system was hydrogenated with hydrogen at 100 kg / cm. ^After pressurizing to ² , the mixture was heated to 260 ° C. with stirring and hydrogenated at the same temperature for 3 hours to obtain a hydrogenated rosin having an acid value of 167, a softening point of 74 ° C. and a color tone Gardner Color 4.

(2) Esterification reaction 500 g of the hydrogenated rosin obtained in the above (1) was placed in a 1-liter four-necked flask, heated to 180 ° C. under a nitrogen stream, and melted and stirred at 200 ° C. at 200 ° C. After adding 55 g, the temperature was raised to 280 ° C., and an esterification reaction was carried out at the same temperature for 12 hours. The acid value was 3.1, the hydroxyl value was 12.2, and the softening point was 9
A hydrogenated rosin ester having a color tone of Gardner Color 4 at 5 ° C. was obtained.

Example 2 (Production of tackifying resin) 500 g of the hydrogenated rosin obtained in Example (1) was placed in a 1-liter four-necked flask, and heated at 180 ° C under a nitrogen stream.
After adding 60 g of pentaerythritol at 200 ° C. under melting and stirring, the temperature was raised to 280 ° C., and an esterification reaction was carried out at the same temperature for 12 hours to obtain an acid value of 7.8 and a hydroxyl value of 21,
A hydrogenated rosin ester having a softening point of 103 ° C. and a color tone Gardner Color 4 was obtained.

Example 3 (Production of tackifying resin) (1) Hydrogenation treatment An acid value of 171 and a softening point of 76 were added to a 3-liter autoclave.
C., 1000 g of crude Chinese gum rosin of color tone Gardner Color 6 and 7 g of 5% palladium carbon (water content: 50%) as a hydrogenation catalyst were added, and after oxygen in the system was removed, the system was hydrogenated at 100 kg / cm. ^After pressurizing to ² , the mixture was heated to 260 ° C. with stirring and hydrogenated at the same temperature for 3 hours to obtain hydrogenated rosin having an acid value of 170, a softening point of 76 ° C. and a color tone Gardner Color 4.

(2) Purification treatment The hydrogenated rosin obtained in the above (1) was treated for 3 m in a nitrogen stream.
Distillation under reduced pressure of mHg, acid value 175, softening point 85 ° C,
The main fraction shown in Table 1 having the constant number of the color tone Gardner 1 was defined as purified hydrogenated rosin.

[0046]

[Table 1]

(3) Esterification reaction 500 g of the purified hydrogenated rosin obtained in the above (2) was placed in a 1-liter flask, heated to 180 ° C. under a nitrogen stream, and melted with stirring at 200 ° C. to 60 g of glycerin. Was added, and the mixture was heated to 280 ° C., and an esterification reaction was carried out at the same temperature for 12 hours. The acid value was 5, the hydroxyl value was 15.2, and the softening point was 97.
A purified hydrogenated rosin ester having a color tone of Gardner Color 2 was obtained.

(4) Dehydrogenation treatment The purified hydrogenated rosin ester 200 obtained in the above (3)
g and 1 g of 5% palladium carbon were charged into a 1-liter immersion autoclave, oxygen in the system was removed, and the system was pressurized to 0.5 kg / cm ² with hydrogen to 270 g.
C. and dehydrogenated at the same temperature for 3 hours. Hydrogenated rosin ester having an acid value of 5.5, a hydroxyl value of 15.5, a softening point of 97.degree. C. and a color tone of Hazen color 1 or less (Hazen color 100). I got

Example 4 (Production of Tackifying Resin) (1) Hydrogenation Example 1 (1) was the same as Example 1 (1) except that the amount of 5% palladium carbon used as the hydrogenation catalyst was changed to 8 g. The hydrogenation was carried out in the same manner as in (1) to obtain a hydrogenated rosin having an acid value of 170, a softening point of 79 ° C. and a color tone of Gardner Color 4.

(2) Esterification reaction Esterification was carried out in the same manner as in Example 1 (2), except that the hydrogenated rosin in Example 1 (2) was replaced with that obtained in Example 4 (1). The reaction was carried out to obtain a hydrogenated rosin ester having an acid value of 18.9, a hydroxyl value of 17.5, a softening point of 96 ° C, and a color tone Gardner Color 6.

Example 5 (Production of tackifier resin) (1) Hydrogenation treatment Example 1 (1) was repeated except that the amount of 5% palladium carbon used in the hydrogenation catalyst was changed to 10 g in Example 1 (1). )
The same hydrogenation as above was performed, acid value 172, softening point 82 ° C,
A hydrogenated rosin of color tone Gardner Color 5 was obtained.

(2) Esterification reaction The same esterification as in Example 1 (2) except that the hydrogenated rosin in Example 1 (2) was replaced with the one obtained in Example 5 (1). The reaction was carried out to obtain an acid value of 18 and a hydroxyl value of 1
5.1 A hydrogenated rosin ester having a softening point of 97 ° C. and a color tone Gardner Color 6 was obtained.

Comparative Example 1 (Production of Tackifying Resin) 500 g of unpurified Chinese gum rosin having an acid value of 171 and a softening point of 76 ° C. and a color tone Gardner Color 6 was placed in a 1-liter flask and heated to 180 ° C. under a nitrogen stream. After adding 55 g of glycerin at 200 ° C. with melt stirring, the temperature was raised to 280 ° C., and an esterification reaction was carried out at the same temperature for 12 hours, acid value 8.5, hydroxyl value 12.5, softening point 90 ° C. A rosin ester of color tone Gardner Color 6 was obtained.

Comparative Example 2 (Production of Tackifying Resin) (1) Disproportionation Treatment Unrefined Chinese gum rosin having an acid value of 171 and a softening point of 76 ° C. and a color tone of Gardner Color 6 was used as a catalyst in 1000 g of palladium-containing carbon (hereinafter referred to as carbon). 0.3 g of a 5% palladium carbon) (water content: 50%) was added, and a disproportionation reaction was carried out while stirring at 280 ° C. for 4 hours in a nitrogen stream.
A disproportionated rosin having an acid value of 170, a softening point of 78 ° C. and a color tone of Gardner Color 6 was obtained.

(2) Esterification reaction 500 g of the disproportionated rosin obtained in the above (1) was placed in a 1 liter flask, and heated to 180 ° C. under a nitrogen stream.
After adding 55 g of glycerin at 200 ° C. under melt stirring,
The temperature was raised to 280 ° C., and an esterification reaction was carried out at the same temperature for 12 hours to obtain a disproportionated rosin ester having an acid value of 7, a hydroxyl value of 13.8, a softening point of 93 ° C. and a color tone Gardner Color 6.

Comparative Example 3 (Production of tackifying resin) (1) Hydrogenation treatment An acid value of 171 and a softening point of 76 were added to a 3-liter autoclave.
C., 1000 g of unrefined Chinese gum rosin with color tone Gardner Color 6 and 2 g of 5% palladium carbon (water content: 50%) as a hydrogenation catalyst, oxygen in the system was removed, and then the system was hydrogenated with 100 kg / cm. ^After pressurizing to ² , the mixture was heated to 260 ° C. with stirring and hydrogenated at the same temperature for 3 hours to obtain hydrogenated rosin having an acid value of 170, a softening point of 75 ° C. and a color tone Gardner Color 4.

(2) Esterification reaction 500 g of the hydrogenated rosin obtained in the above (1) was placed in a 1-liter flask, and heated to 180 ° C. under a nitrogen stream.
After adding 55 g of glycerin at 200 ° C. under melt stirring,
The temperature was raised to 280 ° C., and an esterification reaction was performed at the same temperature for 12 hours to obtain a hydrogenated rosin ester having an acid value of 6.5, a hydroxyl value of 16, a softening point of 96 ° C. and a color tone Gardner Color 5.

Table 2 shows the content (%) of tetrahydroabietic acid ester in various rosin esters finally obtained in the above Examples and Comparative Examples. The content of the tetrahydroabietic acid ester contained in various rosin esters was determined by hydrolyzing each rosin ester, and measuring the hydrolyzate by gas chromatography analysis in accordance with ASTM D3008-82.

[0059]

[Table 2]

Example 6 (Production of Tackifying Resin Emulsion) After dissolving 100 parts of the hydrogenated rosin ester obtained in Example 1 (2) in 35 parts of toluene at 100 ° C. for about 1 hour,
After cooling to 0 ° C., 5 parts of an anionic emulsifier (sodium dodecylbenzenesulfonate) in terms of solid content and water 1
60 parts were added, and the mixture was vigorously stirred at 75 ° C. for 1 hour to perform preliminary emulsification. The obtained pre-emulsion was emulsified under a high pressure of 200 kg / cm ² by a high-pressure emulsifier (manton gauulin) to obtain an emulsion. Next, 200 parts of the emulsion was charged into a vacuum distillation apparatus, and vacuum distillation was performed at 50 ° C. and 100 mmHg for 6 hours to obtain a tackifier resin emulsion having a solid content of 50%.

Examples 7 to 10 and Comparative Examples 4 to 6 (Production of Tackifying Resin Emulsion) In Example 6, the hydrogenated rosin ester obtained in Example 1 (2) was changed to the rosin ester shown in Table 3. except,
A tackifier resin emulsion having a solid content of 50% was obtained in the same manner as in Example 6.

[0062]

[Table 3]

Example 11 100 parts (in terms of solid content) of the acrylic polymer obtained in Production Example 1 and 10 parts of the tackifier resin (rosin ester) obtained in Example 1 (2) were thoroughly kneaded, and then kneaded. 1.6 parts of a polyisocyanate compound (trade name: "Coronate L", manufactured by Nippon Polyurethane Co., Ltd.) was added as a crosslinking agent to obtain a crosslinked acrylic pressure-sensitive adhesive composition. The obtained acrylic pressure-sensitive adhesive composition was applied to a 38 μm-thick polyester film with a dry film thickness of 25 using a dice type applicator.
The sample was applied so as to have a thickness of about μm, and then the solvent in the adhesive composition was removed to prepare a sample tape, and various tests were performed by the performance evaluation method described later.

Examples 12 to 20, Comparative Examples 7 to 12 (Preparation of Acrylic Adhesive Composition) In Example 11, the type of acrylic polymer or the type of tackifying resin was changed as shown in Table 4. Otherwise in the same manner as in Example 11, a crosslinked acrylic pressure-sensitive adhesive composition was obtained. Further, a sample tape was prepared in the same manner as in Example 11, and various tests were performed by a performance evaluation method described later.

[0065]

[Table 4]

Example 21 (Preparation of water-based acrylic pressure-sensitive adhesive composition) Acrylic polymer emulsion 10 obtained in Production Example 3
0 parts (in terms of solids) and 10 parts (in terms of solids) of the tackifying resin emulsion obtained in Example 6 were mixed with Primal AS as an acrylic thickener.
0.5 parts of E-60 (manufactured by Nippon Acrylic Co., Ltd.)
Was added and the mixture was thickened with aqueous ammonia to obtain an aqueous acrylic pressure-sensitive adhesive composition. The obtained aqueous acrylic pressure-sensitive adhesive composition was applied to a 38 μm-thick polyester film using a dice-type applicator so that the dry film thickness became about 25 μm, and then water in the adhesive composition was removed. A sample tape was prepared in this manner, and various tests were performed by a performance evaluation method described later.

Examples 22 to 30 and Comparative Examples 13 to 18 (Preparation of Aqueous Acrylic Pressure-Sensitive Adhesive Composition) In Example 21, the types of acrylic polymer emulsions or the types of tackifier resin emulsions are shown in Table 5. A water-based acrylic pressure-sensitive adhesive composition was obtained in the same manner as in Example 21 except for the above. Further, a sample tape was prepared in the same manner as in Example 21, and various tests were performed by a performance evaluation method described later.

[0068]

[Table 5]

(Performance Test) After the sample tape was left to mature for one week, the adhesive properties were evaluated by the following test methods. The evaluation results are shown in Table 6 or Table 7.

(1) Adhesiveness A sample tape (25 mm wide × 150 mm long) was attached to a polypropylene plate, and was adhered at 20 ° C. according to PSTC-1.
180 ° peeling was performed at a peeling speed of 300 mm / min, and the adhesive force per 25 mm width at that time was measured.

(2) Tack Using a sample tape, the J.T.
The measurement was performed by the Dow method under the conditions of an inclination angle of 30 degrees and a measurement temperature of 20 ° C. The numbers in Table 5 indicate the ball numbers. Is shown.

(3) Cohesive force A sample tape (25 mm × 25 mm) was affixed to a stainless steel plate, and a load of 1 kg was applied at 40 ° C., and a shift (m
m) was measured.

(4) Weather Resistance Xenon light ノ ン irradiation energy: 765 W / cm ² (300 to 800 n) from a distance of 20 cm from the adhesive surface of the sample tape
m), illuminance: 150 Klx, spectral distribution: CIE No.
20 approx., Lamp used: 1.1 kW xenon lamp 照射 was irradiated for a certain period of time, and the change in tack value was evaluated. Tack is NS Probe Tack Tester ｛Probe: AA # 4
The measurement was carried out in a 20 ° C. atmosphere using 00 polishing, load: 100 g, dwell time: 1 second.

[0074]

[Table 6]

[0075]

[Table 7]

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Claims (8)

[Claims] 1. The method of claim 1 wherein the tetrahydroabietic acid is 50% by weight.
The rosin substance (A) contained above and / or the rosin esterified compound (B) derived from the rosin substance (A)
A tackifying resin comprising: 2. Tetrahydroabietic acid is 50% by weight.
The rosin substance (A) contained above and / or the rosin esterified compound (B) derived from the rosin substance (A)
And a resin emulsion obtained by emulsifying the resin in the presence of an emulsifier. 3. A solvent-based pressure-sensitive adhesive composition comprising an acrylic polymer or a rubber-based elastomer and the tackifier resin according to claim 1. 4. The solvent-type pressure-sensitive adhesive composition according to claim 3, wherein 2 to 40 parts by weight (in terms of solid content) of a tackifier resin is blended with respect to 100 parts by weight (in terms of solid content) of the acrylic polymer. . 5. The solvent-based pressure-sensitive adhesive composition according to claim 3, wherein 10 to 150 parts by weight (solid content) of the tackifier resin is blended with 100 parts by weight (solid content) of the rubber-based elastomer. 6. A water-based pressure-sensitive adhesive composition comprising an acrylic polymer emulsion or a rubber-based latex and the tackifier resin emulsion according to claim 2. 7. The aqueous pressure-sensitive adhesive composition according to claim 6, wherein 2 to 40 parts by weight (solid content) of the tackifier resin emulsion is blended with 100 parts by weight (solid content) of the acrylic polymer emulsion. Stuff. 8. A tackifier resin emulsion of 10 to 15 parts by weight per 100 parts by weight of rubber latex (in terms of solid content).
The water-based pressure-sensitive adhesive composition according to claim 6, wherein 0 part by weight (in terms of solid content) is blended.