JPH03277675A - Manufacture of colorless rosin compound - Google Patents

Abstract

PURPOSE:To obtain a rosin compound improved in color, odor, and stability as compared with rosins hitherto known at a relatively low cost by hydrogenating a merely purified rosin compound used as raw material and adding a specified organophosphorus compound thereto. CONSTITUTION:A purified rosin compound as raw material, comprising a purified rosin or a purified rosin ester is hydrogenated, and an organophosphorus compound is added to this reaction system to prepare a colorless rosin compound. Examples of the organophosphorus compound include various compounds shown by the formula (R-O-)3-P (wherein R groups may be the same or different and each stands for at least one of 1-12C alkyl, phenyl, alkylphenyl having 1-12C alkyl, and dialkylphenyl having two 1-12C alkyl groups). The amount of the organophosphorus compound to be added is about 0.01-1.0wt.% based on the purified rosin compound as raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a rosin compound that is colorless, odorless, and has excellent heat stability.

(Prior art) Rosin and its derivative, rosin ester, have been used as tackifiers for adhesives, modifiers for rubber and various plastics, resins for traffic paint, sizing agents for paper manufacturing, and synthetic rubber. It is used for various purposes as a raw material for emulsifiers, ink resins, paint resins, etc. However, in the rosin industry, colorless and highly stable rosin compounds can significantly improve the product value of final products.
Generally, rosin compounds have a yellow or yellowish brown appearance, and are unsatisfactory in terms of odor, heat stability, weather resistance (hereinafter referred to as stability), etc.

Therefore, in order to solve the above-mentioned drawbacks of the rosin-based compounds, the stability has been improved to some extent by hydrogenating unrefined rosin and disproportionated rosin, which is obtained by disproportionating unrefined rosin to improve its thermal stability. Although reprints have been made using hydrogenated rosin, or esterified products using disproportionated rosin or hydrogenated rosin, both are insufficient in terms of color tone, stability, etc.

Special Publication No. 45-33771 and Special Publication No. 49-20
Publication No. 599 describes a method of disproportionating rosin or a rosin-based compound using a specific organic sulfur compound, but both the disproportionated rosin and the disproportionated rosin-based compound obtained by this method have a poor color tone. , odor, and stability.

JP-A No. 55-9605 discloses a method for producing rosin ester with excellent stability, which involves purifying disproportionated rosin to remove high molecular weight substances and unsaponifiable substances contained in the raw material rosin. , a method for esterifying the obtained purified disproportionated rosin and alcohol is described.

However, although the rosin ester obtained by this method has relatively good stability compared to conventional rosin esters, it is colored in the esterification process and does not have satisfactory stability against heat coloring. However, there is room for improvement.

Furthermore, JP-A-59-230072 discloses a method for producing a light-colored and stable rosin ester, in which distilled purified rosin is produced in the coexistence of a specific organic sulfur compound that has both disproportionation ability and lightening ability. Although a method of esterification with alcohol has been described, the rosin ester obtained by this method is still insufficient in terms of color tone and stability.
Moreover, there is a problem in that there is a strong sulfur odor during heating due to the organic sulfur compound.

As described above, none of the conventional rosins and rosin esters can simultaneously satisfy all of the properties of color tone, odor, and stability.Therefore, there has been a strong desire for a rosin that is colorless and has good stability.

Therefore, the present applicant has already filed a patent application (Japanese Unexamined Patent Application Publication No. 63-118) for an invention related to a colorless rosin compound that meets the above requirements.
86783 and JP-A No. 64-85265), these inventions use purified disproportionated rosin or purified disproportionated rosin ester as raw material rosin compounds, and further process these raw material rosin compounds. Since it involves hydrogenation, it has the disadvantage of increasing the cost of the product.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present inventors have developed a novel rosin that provides, at a relatively low cost, a rosin that has further improved the color tone, odor, and stability properties of conventionally known rosins. The aim was to develop a manufacturing method.

(Means for Solving the Problems) In view of the above-mentioned problems, the present inventors conducted intensive studies and found that using a simple purified rosin compound as a raw material and subjecting it to a hydrogenation reaction, a specific oxidation preventive By adding the agent, the above-mentioned problems can be solved and (1) the appearance that meets the object of the present invention is almost colorless, and in addition, there is no odor when heated.
It has been discovered that a rosin compound with excellent properties such as stability can be obtained at a relatively low cost. The present invention was completed based on this new knowledge.

That is, the present invention provides a colorless rosin, which is prepared by hydrogenating a raw material purified rosin compound, which is purified rosin or purified rosin ester, and then adding an organic phosphorus compound to the reaction system. Relates to a method for producing a series compound.

The present invention has an organic phosphorus compound that has various functions such as reduction, antioxidant, and color prevention in the reaction system after the hydrogenation reaction of the raw material purified rosin compound. The present invention relates to a new manufacturing method that can provide rosin compounds with excellent odor and stability, and the rosin compounds obtained by this method are derived from the various performances of conventional rosin compounds. This is completely inconceivable based on the stereotypes that have been formed. That is, according to the present invention, a nearly colorless rosin can be obtained, which dispels the conventional stereotype that rosin compounds have a yellow or tan appearance. Furthermore, the rosin compound retains the characteristics of conventional rosin compounds, that is, wide compatibility with various polymers.

By the way, the causes of coloring of rosin compounds are 1. The presence of high molecular weight substances and unsaponifiable substances contained in the raw material rosin; 2. This is thought to be due to the presence of resin acids with high oxygen absorption properties such as abietic acid having a conjugated double bond among the resin acids.

Therefore, the present invention was completed by focusing on the elimination of the above-mentioned causes.1 In the present invention, (1) the raw material purified rosin-based compound, which is purified rosin or purified rosin ester, is used as the raw material; (2) the purified rosin-based compound is used as the raw material; It is essential to subject the rosin compound to a hydrogenation reaction, and (1) to add an organic phosphorus compound that functions as an antioxidant to the reaction system after the hydrogenation reaction.

Therefore, by simply hydrogenating a purified rosin compound, or by simply hydrogenating a rosin compound and then refining it, it is impossible to obtain a rosin compound having the excellent properties that are the object of the present invention.

The purified rosin compound that is the starting material of the present invention includes:
This applies to purified rosin or purified rosin ester. Among these, purified rosin is gum rosin whose main component is resin acids such as abietic acid, ballast phosphoric acid, neoabietic acid, bimaric acid, isobimaric acid, and dehydroabietic acid.
It is obtained by refining unrefined rosin such as wood rosin and tall oil rosin.

In the present invention, purified rosin ester, which is another starting material, can be easily obtained by using the purified rosin and esterifying it with the following alcohols. Alcohols used here include 2 monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, and lauryl alcohol; dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol; glycerin trihydric alcohols such as , trimethylolethane, and trimethylolpropane; and tetrahydric alcohols such as pentaerythritol and diglycerin. Note that an esterification catalyst is not necessarily required for the reaction, but to shorten the reaction time, for example, an acid catalyst such as acetic acid or paratoluenesulfonic acid, an alkali metal hydroxide such as lithium hydroxide, calcium hydroxide, etc. Alkaline earth metal hydroxides, metal oxides such as calcium oxide, magnesium oxide, etc. can also be used.

In the present invention, as mentioned above, it is essential that the raw material rosin compound is a specific purified product; however, in this specification, purification refers to unsaponifiables contained in the unpurified raw material rosin compound. It also means removing high molecular weight substances that are thought to have arisen from peroxides. Specifically, distillation and recrystallization.

It is sufficient to carry out operations such as extraction, and purification by distillation is preferred industrially.When using distillation, the temperature is usually 200~200℃.
The temperature is appropriately selected from a range of 300° C. and a pressure of 1 to 105 ml/g in consideration of the distillation time. In the case of recrystallization, it can be carried out, for example, by dissolving unpurified rosin in a good solvent, then distilling off the good solvent to obtain a concentrated solution, and adding a poor solvent to this solution. Good solvents include benzene, toluene, xylene, chloroform, lower alcohols, ketones such as acetone, lower alkyl acetates such as ethyl acetate, and poor solvents include n-hexane,
Examples include n-hebutane, cyclohexane, isooctane, and the like. Furthermore, the purification can be carried out by using alkaline water to convert the unpurified raw material rosin compound into an alkaline aqueous solution, extracting insoluble unsaponifiable substances with an organic solvent, and then neutralizing the aqueous layer to obtain the raw material purified rosin compound. .

In the present invention, it is necessary to subject the raw material purified rosin compound obtained as described above to a hydrogenation reaction. The hydrogenation reaction may be carried out under normal conditions, for example, the purified rosin compound is mixed with a hydrogenation catalyst and, if necessary, an aliphatic or alicyclic saturated hydrocarbon organic solvent such as n-pentane, n-hexane, or cyclohexane. It can be carried out by heating at 100 to 300°C, preferably 200 to 280°C, at an initial hydrogen pressure of 50 to 200 kg/cm in a closed container in the presence of a hydrogenation catalyst. For example, metal powders such as palladium carbon, rhodium carbon, nickel, and platinum can be used.The amount of the catalyst to be used is 0.01 to 5 heavy H based on the purified rosin compound.
z, preferably (1,1~:l!I%).

In the present invention, after obtaining the hydride of the raw material purified rosin compound via the hydrogenation step, one element,
It is necessary to add an organic phosphorus compound having various functions such as antioxidant and color prevention, and only by this addition can the object of the present invention be obtained.

Here are the organic phosphorus compounds.

General formula +1): (R-0-), -P (wherein R is the same or different, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms) and a dialkylphenyl group having two alkyl groups having 1 to 12 carbon atoms.

Specific examples thereof include triphenyl phosphite,
Tricresyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,
4-Butylidene-bis(3-methyl-6-L-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetrayl bis(octadecyl phosphite) Tris(nonylphenyl) phosphite, Tris(dinonylphenyl) Phosphite, 9.10-dihydro-9-oxa-IO-phosphaphenanthrene-1
O-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-
9-Oxa-■-phosphaphenanthrene-1O-oxide,! 0-decyloxy9.1O-dihydro-9-
Examples include oxa-1O-phosphaphenanthrene.

Among the above, when considering lightening effect, stabilizing effect, and cost, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl ) Various phosphite compounds such as phosphite are preferred.

The amount of the organic phosphorus compound to be used is 0.1 to 1.0% by weight of the raw material purified rosin compound. Preferably 0. O1
~0.5 ftIt%. 0. If it is less than 1), the effect of adding the organic phosphorus compound will be insufficient, and if it exceeds 1,01!1%, MJ will be used in excess.
Without i, it becomes uneconomical.

The method of adding the organic phosphorus compound is not particularly limited as long as it is added to the reaction system after the hydrogenation reaction is completed, but it is usually added as soon as possible after returning to normal pressure after the hydrogenation reaction is completed. It is preferable to add the organic phosphorus compound in an oxygen-free atmosphere.Also, there are no particular restrictions on the temperature of the reaction system when adding the organic phosphorus compound, but it may be below the decomposition temperature of the organic phosphorus compound. Baku1 Usually 250℃
The following shall apply. In addition, when an organic phosphorus compound is present during the hydrogenation reaction, it is not preferable because it tends to inhibit the progress of the hydrogenation reaction or lower the color tone of the obtained rosin compound.

The final target rosin compound obtained by the method of the present invention has an almost colorless appearance and has excellent performance such as odor, stability, and compatibility when heated. be. Therefore, among the final target rosin compounds, non-esterified products can not only be suitably used as modifiers for soap-based cleaning compositions, but also alkali metal salts of the rosin can be used as emulsifiers for synthetic rubber and emulsion polymerization. It can be used suitably. In addition, esterified products of rosin compounds, which are the final products, are used as tackifier rubbers for pressure-sensitive adhesives or hot melt adhesives, as modifiers for various plastics, as raw materials for traffic paints, as base materials for chewing gum, and as inks. - Can be suitably used as a paint modifier, pigment coating agent, solder flux, etc., and improves the commercial value of the final product in these applications.

In addition, the present invention can be carried out using the raw material purified rosin compounds (purified disproportionated rosin, purified disproportionated rosin ester) in the inventions described in JP-A-63-186783 and JP-A-64-85265. Although it is possible to apply this method, the cost is high as mentioned above.

(Examples) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 0) Purified acid value 171, softening point (measured by the ring and ball method specified in JIS 5902, the same applies hereinafter) 74°C 1 color Gardner 6 unrefined Chinese gum rosin was heated for 3s-1g under a nitrogen seal.
Distilled under reduced pressure, acid value 180.4, softening point 80°0
℃, color tone Gardner 4 main distillate was used as purified rosin.

Note that the distillation conditions are as follows.

[Margin 1 below (2) Hydrogenation 200 g of purified rosin obtained in +1 above and 5% palladium on carbon (water content 50%) 1. Og l
! 2. After charging into a shaking autoclave and removing oxygen in the system, pressurize the system with hydrogen to 50 g/cs".
The temperature was raised to 0'C, and a hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a rosin compound with a # value of 175, a softening point of 82°C, and a color tone of Gardner 2.

(3) Addition of organic phosphorus compound To 100 g of the rosin compound of (2) above, add 0.1 g of an organic phosphorus compound (triphenyl phosphite),
After stirring at approximately 200°C for 30 minutes, the inside of the system was cooled to room temperature and the acid value was 175. Softening point: 82℃, color tone: 100
A final rosin compound was obtained.

Examples 2 to 3 In Example 1 (3), the types of organic phosphorus compounds were changed to tris(nonyl phenyl) phosphite and diphenylisodecyl phosphite, and the amount used was 0.2 g each. The final rosin compound was obtained in the same manner as above. Example 2 has an acid value of 176.
, a softening point of 81"C, and a color tone of Hazen 120. The material of Example 3 had an acid value of 175, a softening point of 80.degree. C., and a color tone of Hazen 120.

Example 4 500 g of purified rosin obtained in Example 1 (1) was added to 4 lε volumes.
The temperature was raised to 180°C under a nitrogen seal, and 60g of glycerin was added at 200°C while dissolving and stirring. 7,5. A purified rosin ester with a softening point of 90° C. and a color of Gardner 5 was obtained. 200 g of the purified rosin ester and 51 palladium carbon (water content 50
%) was charged into a 1β shaking autoclave, and after removing oxygen in the system, it was heated to 1 (lOKg/
The pressure was increased to 275℃ and the temperature was increased to 275℃.

A hydrogenation reaction was carried out at the same temperature for 3 hours, and the a number was 12.5.
A rosin compound with a softening point of 86° C. and a color of Gardner 2 was obtained. The rosin compound! After adding 0.1 g of triphenyl phosphite to 0.0 g and stirring at about 200°C for 30 minutes, the system was cooled to room temperature, and the a value was 12.5° and the softening point was 8.
A final rosin compound with a color tone of Hazen 80 was obtained at 6°C.

Examples 5 to 6 Same as Example 4, except that the type of organic phosphorus compound was changed to tris(nonyl phenyl) phosphite and diphenylisodecyl phosphite, and the amount used was 0.2 g each. The final rosin compound was obtained. The acid value of Example 5 was 12.3. The softening point was 85.5° C., and the color tone was Hazen 100. The acid value of Example 6 was 12. ! , softening point 85℃, color tone Hazen! It was oo.

Comparative example 1 The rosin compounds obtained in Examples 1) and 2) were used.

As mentioned above, immediately after the completion of the hydrogenation reaction, this product has an acid value of 1
75. The softening point was 82° C. and the color tone was Gardner 2, but when it was left at room temperature for 30 days, it changed to an acid value of 175, a softening point of 82° C., and a color tone of Gardner 4.

Comparative Example 2 Rosin Compound 10 obtained in Comparative Example 1 after standing for 30 days
0 g of xylene i and 0.2 g of triphenyl phosphite were added to 0 g under a nitrogen atmosphere, stirred and dissolved, and then removed from xylene to obtain a final rosin compound with an acid value of 175, a softening point of 82°C, and a color of Gardner 4. Obtained.

Comparative Example 3 The rosin compound obtained in Example 4 before addition of triphenyl phosphite was used. As mentioned above, immediately after the hydrogenation reaction, the acid value of this product is high! 2.5, softening point 86℃1
The color was Gardner 3, but when it was left at room temperature for 30 days, the color changed to Gardner 3 with an acid value I of 2.5 and a softening point of 86°C.

Comparative Example 4 Rosin compound 10 obtained in Comparative Example 3 after standing for 30 days
100 g of xylene and 0.2 g of triphenyl phosphite were added to 0 g under a nitrogen atmosphere, stirred and dissolved, and then dexylene was removed to obtain a final rosin compound with an acid value of 12.5, a softening point of 86°C, and a color tone of Gardner 3. Obtained.

Examples 1 to 6 and Comparative Examples 1 to 4 (However, Comparative Example 1
In cases 3 and 3, those before being left at room temperature were used. ) was evaluated as follows.

(Heating stability) Samples were placed in a test tube with an inner diameter of 1.5 cm and a height of 15 cm.
g was placed in a circulating air dryer at 200° C. without a lid, and changes in color tone (Gardner) over time were observed.

The results are shown in Table 1.

(Weather resistance) 60~! Put 2.0 g of resin adjusted to the particle size of OO mesh into an ointment can with an inner diameter of 5.6 cm and a height of 10 cm, and add a 400 W mercury lamp (manufactured by Toshiba Corporation, model: H40DF) to 40 cm.
Weight increase (oxygen absorption amount) and color tone (Gardner) changes were observed when irradiated for 15 hours from a distance of m. still,
The color tone was evaluated using a 50% xylene solution. The result is the first
Shown in the table.

Table 1 [Blank below: Effects of the invention] The present invention provides a rosin-based compound with significantly improved performance such as color tone, odor, and stability compared to conventionally known rosin-based compounds at a relatively low cost. A lingering effect is produced.

Arakawa Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. It is characterized by being prepared by hydrogenating a raw material purified rosin compound, which is purified rosin or purified rosin ester, and then adding an organic phosphorus compound to the reaction system. A method for producing a colorless rosin compound. 2. The method for producing a colorless rosin compound according to claim 1, wherein the organic phosphorus compound is represented by the following general formula (1). General formula (1): (R-O-)_3-P (wherein R is the same or different, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 12 carbon atoms) Indicates at least one type selected from the group consisting of a phenyl group and a dialkylphenyl group having two alkyl groups having 1 to 12 carbon atoms.) 3. The amount of organic phosphorus compound added is 0 to the raw material purified rosin compound. 3. The method for producing a colorless rosin compound according to claim 1 or 2, wherein the amount is .01 to 1.0% by weight.