JP2003321651A - Hydrogenated rosin and production thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenated polymeric rosin that has a variety of excellent properties, e.g. color tone, heating stability, weather resistance and the like and scarcely inhibits the polymerization of acrylic monomers. <P>SOLUTION: In the method of producing hydrogenated rosin, at least one of polymeric rosin selected from the group consisting of polymeric rosins and esters thereof is hydrogenated or the polymeric rosin is hydrogenated and esterified with alcohol. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrogenated rosin compound, more specifically, a hydrogenated rosin compound which is light-colored, has excellent odor and heat stability, and weather resistance and does not hinder the polymerization of acrylic monomers. And a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polymerized rosin and its derivative, polymerized rosin ester, are used as tackifiers for adhesives, modifiers for rubbers and various plastics, resins for traffic paints, sizing agents for papermaking, It is used in various applications as a raw material for emulsifiers for synthetic rubber, resins for inks, resins for paints, solders, etc.

However, in general, these polymerized rosin compounds are colored yellow or yellowish brown in appearance, and are not satisfactory in stability such as heating stability and weather resistance. A light-colored, odorless, and stable polymerized rosin compound has been demanded because it can significantly improve the product value of the final product.

When a polymerized rosin compound coexists during the polymerization of the acrylic monomer, the polymerized rosin compound inhibits the polymerization of the acrylic monomer and an acrylic polymer having a sufficient molecular weight can be obtained. There wasn't.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention is to further improve various properties such as color tone, odor and stability of a conventionally known polymerized rosin compound and to polymerize an acrylic monomer. It is an object of the present invention to provide a polymerized rosin compound that hardly causes polymerization inhibition when it is carried out.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that the polymerized rosin compound is hydrogenated or the polymerized rosin is hydrogenated and then esterified. It was found that the hydrogenated rosin-based compound obtained by the above is light-colored, odorless, and excellent in various properties such as stability upon heating, and that it does not inhibit polymerization during preparation of the acrylic polymer. Has been completed.

That is, according to the present invention, (1) at least one polymerized rosin compound selected from the group consisting of polymerized rosin and its ester is hydrogenated, or (2) the polymerized rosin is hydrogenated and then with an alcohol. Provided is a hydrogenated rosin compound obtained by an esterification reaction.

Further, the method for producing a hydrogenated polymerized rosin compound of the present invention comprises at least one polymerized rosin compound selected from the group consisting of polymerized rosin and its ester,
It is characterized in that the hydrogenation reaction is carried out in the presence of a hydrogenation catalyst.

The method for producing a hydrogenated polymerized rosin compound of the present invention is characterized in that the polymerized rosin is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst and then to an esterification reaction with an alcohol.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrogenated rosin compound of the present invention is obtained by subjecting a polymerized rosin compound as a raw material to a hydrogenation reaction at least once, or after subjecting a polymerized rosin to a hydrogenation reaction at least once. It is a compound obtained by an esterification reaction with alcohol.

As the polymerized rosin compound as a raw material,
The polymerized rosin and the polymerized rosin ester obtained by esterifying the polymerized rosin are applicable.

The polymerized rosin is an unpurified rosin such as gum rosin, wood rosin or tall oil rosin, which is mainly composed of a resin acid such as abietic acid, parastolic acid, neoabietic acid, pimaric acid, isopimaric acid, dehydroabietic acid, or Distilled from these unpurified rosins,
It is obtained by polymerizing purified rosin from which low-boiling components and unsaponifiables that cause odor by operations such as recrystallization and extraction are polymerized, and, for example, these rosin compounds are boron trifluoride or its complex, chloride. It can be obtained by cationic polymerization in the presence of a catalyst such as aluminum, tin chloride, titanium chloride, sulfuric acid and phosphoric acid.

The polymerized rosin obtained from the purified rosin has a hue, odor,
It is more preferable in terms of heat resistance.

These polymerized rosins contain a polymerized rosin component in an amount of 10% or more. Polymerized rosin component is GPC (gel permeation chromatography)
Can be measured by "Polypale resin" (trade name) containing about 30% of a polymerized rosin component, "Daimalex resin" (trade name) containing about 65% of a polymerized rosin component are commercially available from Hercules.

Further, as the polymerized rosin, α, β-unsaturated carboxylic acid having 2 to 10 carbon atoms is also added to the above polymerized rosin.
It is also possible to use a species or a mixture of two or more species. More specifically, one of α, β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and itaconic acid, or α, β-unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid. There may be mentioned one or two or more species added.

Further, as the polymerized rosin compound as a raw material, phenol, cresol, bisphenol A, p
It is obtained by reacting phenols such as -tert-butylphenol, p-amylphenol, octylphenol, nonylphenol, dodecylphenol with formalin in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. Polymerized rosin obtained by addition reaction of resol type phenolic resin with polymerized rosin, or the above phenols in the presence of Lewis acid catalyst such as boron trifluoride or its complex, aluminum chloride, tin chloride, titanium chloride, sulfuric acid and phosphoric acid. You may use what was added to.

Examples of the polymerized rosin ester include compounds obtained by esterifying the above-mentioned polymerized rosin and the alcohol described below. Examples of the alcohol include aliphatic monohydric or polyhydric alcohols having 1 to 20 carbon atoms, for example, methanol, ethanol, isopropyl alcohol, isoamyl alcohol, n-hexyl alcohol, 2-ethylhexyl alcohol, n-.
Monohydric alcohols such as octyl alcohol, dodecyl alcohol, lauryl alcohol, stearyl alcohol, dihydroabietyl alcohol; dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol; glycerin, trimethylolethane, trimethylolpropane, etc. 3 Polyhydric alcohols: tetrahydric alcohols such as pentaerythritol and diglycerin can be mentioned.

In the esterification reaction, an esterification catalyst is not always necessary, but for the purpose of shortening the reaction time, for example, an acid catalyst such as acetic acid or paratoluenesulfonic acid, lithium hydroxide, sodium hydroxide, hydroxylation or the like. Alkali metal hydroxides such as potassium, alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide,
Metal oxides such as calcium oxide, magnesium oxide, zinc oxide, lead oxide and tin oxide can also be used. Further, phenols such as phenol, cresol, bisphenol A, p-tert-butylphenol, p-amylphenol, octylphenol, nonylphenol and dodecylphenol are esterified in the presence of an acid catalyst such as sulfuric acid, paratoluenesulfonic acid or alkylbenzenesulfonic acid. A polymerized rosin ester obtained by the chemical reaction may be used.

The hydrogenated polymerized rosin compound according to the present invention is obtained by hydrogenating the above-mentioned polymerized rosin compound. The hydrogenation reaction may be performed under conventional conditions by a conventionally known method. For example, a polymerized rosin compound is a hydrogenation catalyst and optionally n-pentane, n-hexane, cyclohexane, an aliphatic or alicyclic saturated hydrocarbon organic solvent such as decalin, α-pinene, β-pinene, dipentene, It can be carried out by heating in a closed container in the presence of a natural hydrocarbon organic solvent such as limonene or an aromatic hydrocarbon organic solvent such as toluene, xylene, alkylbenzene or dialkylbenzene.

The hydrogen pressure during the hydrogenation reaction is 1 MPa to 2
It is 5 MPa, preferably 5 MPa to 20 MPa. When the hydrogen pressure is less than 1 MPa, the hydrogenation reaction is insufficient and a hydrogenated rosin compound having excellent hue, odor and heat resistance cannot be obtained. Further, if the pressure is 25 MPa or more, strict equipment is required for safety, which is not preferable.

The reaction temperature in the hydrogenation reaction is 100 to 3
The temperature is 00 ° C, preferably 150 to 280 ° C. 100 ° C
If the amount is less than the above, the hydrogenation reaction is insufficient, and a hydrogenated rosin compound excellent in hue, odor and heat resistance cannot be obtained. Further, if the temperature is 300 ° C. or higher, the decomposition of the polymerized rosin compound proceeds, which is not preferable.

As the hydrogenation reaction catalyst, various known catalysts can be used without particular limitation. Examples include supported catalysts in which palladium, rhodium, platinum, etc. are supported on carbon or alumina, metal powders such as nickel and platinum, iodides such as iodine and iron iodide, and the like. In order to obtain a hydrogenated rosin-based compound having excellent color tone and stability when heated, palladium-based, rhodium-based, platinum-based, nickel-based catalysts are preferable, and specifically, palladium carbon, rhodium carbon, platinum It is preferable to use carbon or stabilized nickel. The amount of the catalyst used is 0.01 to 10% by weight, preferably 0.5 to 5% by weight, based on the polymerized rosin compound.

The hydrogenated rosin compound of the present invention is obtained by subjecting the polymerized rosin to a hydrogenation reaction at least once,
It can also be obtained by an esterification reaction with alcohol.
As the polymerized rosin in this case, the polymerized rosin exemplified above is similarly used. The method of hydrogenation reaction is also the same as above.

The alcohol used for esterification is
Similar to the alcohol used for the above-mentioned polymerized rosin ester, for example, methanol, ethanol, isopropyl alcohol, isoamyl alcohol, n-hexyl alcohol, 2-ethylhexyl alcohol, n-octyl alcohol, dodecyl alcohol, lauryl alcohol,
Monohydric alcohols such as stearyl alcohol and dihydroabietyl alcohol; Dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol; Trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane; pentaerythritol, diglycerin, etc. 4 tetrahydric alcohols.

The esterification reaction can also be carried out in the same manner as in the preparation of the above polymerized rosin ester. That is, an esterification catalyst is not always necessary, but in order to shorten the reaction time, for example, an acid catalyst such as acetic acid or p-toluenesulfonic acid, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide. It is also possible to use alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and metal oxides such as calcium oxide, magnesium oxide, zinc oxide, lead oxide and tin oxide. Further, phenols such as phenol, cresol, bisphenol A, p-tert-butylphenol, p-amylphenol, octylphenol, nonylphenol and dodecylphenol are esterified in the presence of an acid catalyst such as sulfuric acid, paratoluenesulfonic acid or alkylbenzenesulfonic acid. A chemical reaction may be carried out.

The hydrogenated rosin compound of the present invention includes
If necessary, the heating stability can be further improved by adding an antioxidant such as a phenol compound or an organic phosphorous acid compound. Specific examples of the phenol compound include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, and 2.
4-dimethyl-6-t-butylphenol, 4,4'-
Examples thereof include hindered phenol compounds such as butylidene bis (3-methyl-6-t-butylphenol) and tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.
Further, as organic phosphorous acid, triphenol phosphite, tricresyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4-butylidene-bis (3-methyl-6-t-) is used.
Butylphenyl-di-trinyl) 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-
Examples thereof include 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene and the like.

The hydrogenated rosin compound of the present invention has an extremely light appearance, is odorless, and is excellent in various properties such as heating stability and weather resistance. In addition, it retains the characteristic of being a conventional polymerized rosin compound, that is, has a wide compatibility with various polymers. Further, even when the hydrogenated rosin compound of the present invention is coexisted in the acrylic monomer to polymerize, an acrylic polymer having a sufficient molecular weight can be obtained with almost no inhibition of polymerization. Therefore,
Of the hydrogenated rosin-based compounds of the present invention, non-esterified products are modifiers for soap-based detergent compositions, tackifiers for pressure-sensitive adhesives or hot-melt adhesives, and modified rubbers and various plastics. It can be suitably used as a material, a raw material for traffic paint, a modifier for ink / paint, and a resin for solder. In addition, esters of hydrogenated rosin compounds are tackifiers for pressure sensitive adhesives or hot melt adhesives, modifiers for rubbers and various plastics, raw materials for traffic paints, chewing gum base materials, inks and paints. Can be suitably used as a modifier, a pigment coating agent, a resin for soldering, etc., and can improve the commercial value of the final product in these applications. Further, the alkali metal salt of the hydrogenated rosin compound of the present invention can be suitably used as a synthetic rubber and an emulsifier for emulsion polymerization.

[0028]

EXAMPLES The method of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The hydrogenated rosin compound in each example was measured by the following method.

The Gardner color number conforms to JIS K5400.

The acid value was in accordance with JIS K5400.

Softening point This was based on the ring and ball method described in JIS K2871.

Heating stability 10 g of the sample was placed in a test tube having an inner diameter of 1.5 cm and a height of 15 cm, and the sample was left still in a circulating air dryer at 180 ° C. without a lid,
By changing the number of Gardner colors at the initial stage, after 6 hours, and after 24 hours, changes in color tone with time were observed.

Weather resistance : 2.0 g of resin having a uniform grain size of 60 to 100 mesh was placed in an ointment can having an inner diameter of 5.6 cm and a height of 1 cm. The change in weight increase (oxygen absorption amount) and color tone (Gardner color number) after irradiation for 15 hours was observed.
The color tone is evaluated by using a 50% xylene solution.

Degree of Polymerization of Polymerized Rosin A tetrahydrofuran solution having a resin concentration of 0.2% is used for Shod.
ex KF-802.5 (1), KF-802 (1
GPC column (all made by Showa Denko) and KF-801 (two) GPC (Waters 2690:
It was analyzed by Nippon Waters Co., Ltd.). Refractive index detector (W
aters410: manufactured by Nippon Waters Co., Ltd.) was used. Mobile phase flow rate: 0.8 ml / min, measurement temperature: 40 ° C.
The degree of polymerization was calculated by the following formula. Polymerization degree = A / (A + B) × 100 (%) A: Area strength of polymerized rosin component B: Area strength of unpolymerized rosin component

Hydrogenation rate of polymerized rosin A tetrahydrofuran solution having a resin concentration of 0.2% was used for Shod.
ex KF-802.5 (1), KF-802 (1
GPC column (all made by Showa Denko KK) and KF-801 (two) GPC column (Waters269)
0: made by Nippon Waters Co., Ltd.) to separate rosin acid and polymerized rosin, and photodiode array detector (Waters)
996: manufactured by Nippon Waters Co., Ltd.). Mobile phase flow rate: 0.8 ml / min, measurement temperature: 40 ° C. The hydrogenation rate was calculated by calculating the area strength reduction rate of the polymerized rosin component using the following formula. Hydrogenation rate = (A−B) / A A: Area intensity of the polymerized rosin component at 260 nm at the material B: Area intensity of the polymerized rosin component of hydride at 260 nm The polymerized rosin ester undergoes alkali hydrolysis to polymerize. The area intensity at 260 nm of the rosin component was measured to measure the hydrogenation rate.

Polymerization with acrylic acid 75 parts of butyl acrylate, 23 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid and 10 parts of a polymerized rosin compound as a sample, 60 parts of ethyl acetate and 30 parts of toluene were stirred with a stirrer. After being charged in a reactor equipped with a cooling pipe and a nitrogen introducing pipe, the temperature was raised to 70 ° C. under a nitrogen stream. Then azobisisobutyronitrile 0.
1 part was added and the temperature was kept at the same temperature for 10 hours to complete the polymerization reaction. At the same temperature, unreacted acrylic monomers, ethyl acetate and toluene were distilled off under reduced pressure, the amount of acrylic polymer produced in the reactor was measured, and the polymerization rate was calculated. The weight average molecular weight of the obtained acrylic polymer was measured by GPC (gel permeation chromatography) under the following conditions. The polymerization rate of the acrylic polymer without adding the polymerized rosin compound was 100%, and the weight average molecular weight was 300,000.

Measurement of weight average molecular weight of acrylic polymer A tetrahydrofuran solution having a resin concentration of 0.2% was subjected to Ultr.
a StagelPlus MX 10 ⁶ Å (1
Book), Ultra Styagel PlusMX 1
0 ⁵ Å (1) column (all manufactured by Nippon Waters Co., Ltd.)
Was analyzed by GPC (Waters 2690: manufactured by Nippon Waters Co., Ltd.). Refractive index detector (Water)
s410: manufactured by Nippon Waters Co., Ltd.) was used. The molecular weight is a weight average molecular weight and shows a polystyrene conversion value. Mobile phase flow rate: 1.0 ml / min. Measurement temperature: 4
0 ° C.

Production Example 1 [Preparation of purified polymerized rosin (1)] Unpurified Chinese gum rosin (Gardner color number 6, acid value 17)
(0, softening point: 76 ° C.) was distilled under a nitrogen blanket at 400 Pa, and a main distillate having a Gardner color number of 2, an acid value of 180 and a softening point of 80 ° C. was used as a purified rosin. The distillation conditions are as shown in Table 1 below.

[Table 1] 500 g of the obtained purified rosin and 500 g of dehydrated toluene were placed in a three-necked flask and dissolved, and anhydrous aluminum chloride 2
5 g was added, and the mixture was reacted at 50 to 55 ° C for 2 hours. Next, the reaction mixture was transferred to a separating funnel, a 5% hydrochloric acid aqueous solution was added, and the mixture was shaken well. The upper layer was separated and washed with dilute aqueous sodium hydroxide solution and then with water. Then, vacuum distillation was carried out to obtain 450 g of purified polymerized rosin (1) having a Gardner color number of 3, a softening point of 95 ° C., an acid value of 165 and a polymerization degree of 30%.

Preparation Example 2 [Preparation of purified polymerized rosin (2)] 500 g of the purified rosin obtained in Preparation Example 1 and 500 g of dehydrated toluene were placed in a three-necked flask and dissolved, and 50 g of anhydrous aluminum chloride was added to the mixture to give 50-55. The reaction was conducted at 8 ° C for 8 hours. Next, the reaction mixture was transferred to a separating funnel, a 5% hydrochloric acid aqueous solution was added, and the mixture was shaken well. The upper layer was separated and washed with dilute aqueous sodium hydroxide solution and then with water. Then vacuum distillation is performed,
460 g of purified polymerized rosin (2) having a Gardner color number of 4, a softening point of 135 ° C., an acid value of 150, and a polymerization degree of 65% was obtained.

Example 1 Polypeel resin (trade name, manufactured by Hercules Co., Ltd .: degree of polymerization 30%, Gardner color number 6, acid value 163, softening point 95)
C.) 100 g, cyclohexane 100 g and 5% palladium carbon 3 g were charged in a shaking autoclave,
After removing oxygen in the system, the system was pressurized to 15 MPa with hydrogen and heated to 200 ° C., and hydrogenation reaction was carried out at the same temperature for 4 hours to obtain an acid value of 158, a softening point of 95 ° C., and a Gardner color number of 1. 98 g of hydrogenated rosin was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin. In addition, in the GPC analysis when measuring the hydrogenation rate, 260% of the polypeel resin before the hydrogenation reaction was used.
The chromatogram and area intensity at nm are shown in FIG. 1, and the chromatogram and area intensity at 260 nm of the obtained hydrogenated rosin are shown in FIG. 2, respectively.

Comparative Example 1 Table 2 shows the evaluation results of the heat resistance, weather resistance and polymerizability of the polypale resin.

Example 2 An acid value of 16 was obtained in the same manner as in Example 1 except that 100 g of the purified polymerized rosin (1) obtained in Production Example 1 was used.
4, 98 g of hydrogenated rosin having a softening point of 95 ° C. and a Gardner color number of 1 was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin.

Comparative Example 2 Table 2 shows the evaluation results of the heating stability, weather resistance and polymerizability of the purified polymerized rosin (1) obtained in Production Example 1.

Example 3 Daimalex resin (trade name, manufactured by Hercules Company:
Hydrogen having an acid value of 145, a softening point of 140 ° C. and a Gardner color of 2 is prepared in the same manner as in Example 1, except that 100 g of a polymerization degree of 65%, a Gardner color of 6, an acid value of 145, and a softening point of 140 ° C.) are used. 100 g of chemically polymerized rosin was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin.

Comparative Example 3 Table 2 shows the evaluation results of the heating stability, weather resistance and polymerizability of the Dimalex resin.

Example 4 An acid value of 15 was obtained in the same manner as in Example 1 except that 100 g of the purified polymerized rosin (2) obtained in Production Example 2 was used.
4, 99 g of hydrogenated rosin having a softening point of 135 ° C. and a Gardner color number of 2 was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin.

Comparative Example 4 Table 2 shows the evaluation results of the heat stability, weather resistance and polymerizability of the purified polymerized rosin (2) obtained in Production Example 2.

Example 5 Polygale resin (500 g) was placed in a four-necked flask, heated to 210 ° C. under a nitrogen blanket, and 25 g of acrylic acid was added dropwise over 4 hours while stirring at the same temperature. 520 g of acrylic acid addition-polymerized rosin having a valence of 190 and a softening point of 105 ° C. was obtained. 100 g of the resulting acrylic acid addition-polymerized rosin, 100 g of xylene, and 5 g of 5% palladium carbon were charged into a shaking autoclave,
After removing oxygen in the system, the system was pressurized to 15 MPa with hydrogen and heated up to 250 ° C., and hydrogenation reaction was carried out at the same temperature for 4 hours to obtain an acid value of 190, a softening point of 105 ° C., and a Gardner color number of 1. 100 g of hydrogenated rosin polymerized with acrylic acid was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained acrylic acid-hydrogenated rosin.

Comparative Example 5 Table 2 shows the evaluation results of the heating stability, weather resistance and polymerizability of the acrylic acid addition-polymerized rosin obtained in Example 5.

Example 6 An acrylic resin having a Gardner color number of 3, an acid value of 196 and a softening point of 105 ° C. was prepared in the same manner as in Example 5 except that 500 g of the purified polymerized rosin (1) obtained in Production Example 1 was used. 519 g of acid addition-polymerized rosin was obtained, and 100 g of this acrylic acid addition-polymerized rosin was used to perform the same procedure as in Example 5.
Obtained was 99 g of an acrylic acid-hydrogenated hydrogenated rosin having an acid value of 195, a softening point of 105 ° C. and a Gardner color number of 1. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained acrylic acid-hydrogenated rosin.

Comparative Example 6 Table 2 shows the evaluation results of the heating stability, weather resistance and polymerizability of the acrylic acid addition-polymerized rosin obtained in Example 6.

Example 7 500 g of polypeel resin was placed in a four-necked flask, heated to 180 ° C. under a nitrogen blanket, and dissolved under stirring to 200
After adding 60 g of pentaerythritol at ℃, 280
The temperature was raised to 0 ° C., and the esterification reaction was carried out at the same temperature for 12 hours to obtain 510 g of a polymerized rosin ester having an acid value of 15, a softening point of 120 ° C. and a Gardner color number of 6. The polymerized rosin ester is hydrogenated in the same manner as in Example 1,
99 g of a hydrogenated rosin ester having an acid value of 15, a softening point of 125 ° C. and a Gardner color number of 2 was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin ester.

Comparative Example 7 Heat stability of the polymerized rosin ester obtained in Example 7,
Table 2 shows the evaluation results of weather resistance and polymerizability.

Example 8 A polymerized rosin having an acid value of 16, a softening point of 125 ° C. and a Gardner color number of 3 was prepared in the same manner as in Example 7 except that 500 g of the purified polymerized rosin (1) obtained in Production Example 1 was used. 502 g of SRL was obtained, and 100 g of the obtained polymerized rosin ester was used in the same manner as in Example 7 to obtain 100 g of hydrogenated polymerized rosin S having an acid value of 15, a softening point of 125 ° C. and a Gardner color number of 2. Table 2 shows the evaluation results of the heat stability, weather resistance and polymerizability of the obtained hydrogenated rosin ester.

Example 9 Hydrogenated Polymerized Rosin 50 Obtained by the Same Method as in Example 1
Transfer 0 g to a four-necked flask and place under a nitrogen blanket for 180 g.
The temperature was raised to ℃, and glycerin 60 was added at 200 ℃ with dissolution and stirring.
After adding g, the temperature was raised to 270 ° C and the temperature was raised to 12
The esterification reaction is carried out for a time to obtain an acid value of 15 and a softening point of 105.
℃, Gardner color number 2 hydrogenated polymerized rosin ester 50
5 g was obtained. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin ester.

Comparative Example 9 500 g of polypell resin instead of hydrogenated rosin
An acid value of 1 was obtained by the same method as in Example 9 except that
5, 510 g of a polymerized rosin ester having a softening point of 105 ° C. and a Gardner color number of 6 was obtained. Table 2 shows the evaluation results of the heat stability, weather resistance and polymerizability of the obtained polymerized rosin ester.

Example 10 Hydrogenated polymerized rosin 50 obtained in the same manner as in Example 2
An esterification reaction was carried out in the same manner as in Example 9 except that 0 g was used to obtain 500 g of a hydrogenated rosin ester having an acid value of 15, a softening point of 105 ° C. and a Gardner color number of 2. Table 2 shows the evaluation results of the hydrogenation rate, heating stability, weather resistance, and polymerizability of the obtained hydrogenated rosin ester.

Comparative Example 10 Example 10 was repeated except that 500 g of the purified polymerized rosin (1) obtained in Production Example 1 was used in place of the hydrogenated polymerized rosin.
By the same method as described above, 500 g of a polymerized rosin ester having an acid value of 15, a softening point of 105 ° C. and a Gardner color number of 4 was obtained. Table 2 shows the evaluation results of the heat stability, weather resistance and polymerizability of the obtained polymerized rosin ester.

[0059]

[Table 2]

[0060]

EFFECTS OF THE INVENTION According to the present invention, various properties such as color tone, heat stability and weather resistance are remarkably improved as compared with conventionally known polymerized rosin compounds, and the polymerization of acrylic monomers is hardly inhibited. A hydrogenated rosin compound can be obtained.

[Brief description of drawings]

1] FIG. 1 is a graph showing 260 nm of GPC of the polyresin resin used in Example 1 when measuring the hydrogenation rate.
And the area intensity.

FIG. 2 is 260 nm in GPC when measuring the hydrogenation rate of the hydrogenated rosin obtained in Example 1.
And the area intensity.

Claims (12)

[Claims] 1. A method of hydrogenating at least one polymerized rosin compound selected from the group consisting of (1) polymerized rosin and its ester, or (2) hydrogenated polymerized rosin and then esterification reaction with alcohol. A hydrogenated rosin compound obtained by 2. The hydrogenated rosin compound according to claim 1, wherein the polymerized rosin is a purified polymerized rosin. 3. The hydrogenated polymerized rosin compound according to claim 1, wherein the polymerized rosin is a polymerized rosin to which an α, β-unsaturated carboxylic acid is added. 4. At least one polymerized rosin compound selected from the group consisting of polymerized rosin and its ester,
The method for producing a hydrogenated rosin compound according to claim 1, wherein the hydrogenation reaction is carried out in the presence of a hydrogenation catalyst. 5. The method for producing a hydrogenated rosin compound according to claim 4, wherein the polymerized rosin is a purified polymerized rosin. 6. The method for producing a hydrogenated rosin compound according to claim 4, wherein the polymerized rosin is a polymerized rosin to which an α, β-unsaturated carboxylic acid is added. 7. The method for producing a hydrogenated rosin compound according to claim 1, wherein the polymerized rosin is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst, and then subjected to an esterification reaction with an alcohol. 8. The hydrogenated rosin compound according to claim 7, wherein the polymerized rosin is a purified polymerized rosin. 9. The method for producing a hydrogenated rosin compound according to claim 7, wherein the polymerized rosin is a polymerized rosin to which an α, β-unsaturated carboxylic acid is added. 10. The hydrogen pressure during the hydrogenation reaction is 1 MPa to
The method for producing a hydrogenated rosin-based compound according to claim 4 or 7, which has a pressure of 25 Mpa. 11. The reaction temperature during the hydrogenation reaction is 100 to 100.
The method for producing a hydrogenated rosin-based compound according to claim 4 or 7, which is 300 ° C. 12. The method for producing a hydrogenated rosin-based compound according to claim 3, wherein the hydrogenation catalyst is a nickel-based, palladium-based, rhodium-based or platinum-based catalyst.