JPS5922919A - Rosin-based polyester resin and its manufacture - Google Patents

Abstract

PURPOSE:To obtain titled novel resin of extremely high purity and monodisperse molecular weight distribution, with its rosin groups regularly located in the side chain, by carrying out a reaction on heating between a dicarboxylic acid derivative and a rosin glycidyl ester. CONSTITUTION:The objective resin having structural unit of formula I [A is a divalent group of formula II, III, IV (R1 is H or methyl), V, VI (n is 2-8), VII(R2 is 8-18C alkyl or alkenyl), etc.; B is rosin residue], with a softening point of 50-190 deg.C, a glass transition point of 30-170 deg.C, and a number average molecular weight of 2,000-30,000, can be obtained by carrying out a reaction on heating between (A) a dicarboxylic acid derivative (or its anhydride) and (B) a rosin glycidyl ester, in the presence, if required, of (C) an organic amine. EFFECT:Having excellent dryability, blocking resistance, workability, etc., also capable of giving films of high strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel rosin-based polyester resin and a method for producing the same. More specifically, the present invention relates to a novel rosin thread-like polyester resin in which rosin groups are regularly arranged in molecular side chains, and a method for producing the same.

Conventionally, polyester resins using rosin have been known as polymeric materials that have many uses as binders and improving materials for paints, printing inks, adhesives, powders, road marking materials, and the like.

For example, so-called ester gum which is an esterified product of rosin and a polyhydric alcohol, an esterified product of maleated rosin or fumarized rosin and a polyhydric alcohol, or a rosin-modified alkyd made of rosin, drying vegetable oil, polycarboxylic acid and polyhydric alcohol. Examples include resin.

Esterified products modified with ester gum or maleic acid can be obtained by selecting the degree of modification of the polyhydric alcohol or maleic acid used, etc. The softening point of the resin, compatibility with other resins, solubility in various organic solvents, etc. These resins are mainly used as adhesion tackifiers, paint modifiers, etc. On the other hand, rosin-modified alkyd resins can be used to control the solubility of the resin in organic solvents and the coating film. Because of its excellent hardness and drying properties, it is widely used as a binder for paints and printing inks.

These conventionally known rosin polyester resins usually have a wide molecular weight distribution, and it is difficult to produce a product with a uniform molecular weight.

In particular, the rosin-modified alkyd resin has a highly condensed high molecular weight component, a relatively low molecular weight component,
Furthermore, it was confirmed that a considerable amount of unreacted raw materials were present.
Further, the resin usually does not have regular structural units and is composed of a condensate having an extremely random arrangement.

The present inventors conducted extensive research with the aim of developing a new rosin-based polyester that is completely different from the conventional rosin-based polyester resins, and finally completed the present invention.

In other words, the present invention is a novel linear polyester in which rosin groups are regularly introduced into the molecular side chains of the resin, which contains almost no unreacted raw materials in the resulting resin, and has an extremely high purity and monodisperse molecular weight distribution. At least one selected from the group consisting of the general formula: (wherein R represents a hydrogen atom or a methyl group, n represents an integer of 2 to 8, and R2 represents an alkyl or alkenyl group having 8 to 18 carbon atoms) It has a structural unit represented by one type of divalent group (B represents a rosin residue), and has a softening point of 50 to 190°C, a glass transition point of 30 to 170°C, and a number average molecular weight of 2.000.
50,000, in which polyester groups are regularly arranged in the molecular side chains.

The rosin polyester resin of the present invention can be obtained, for example, by heating and reacting a dicarboxylic acid derivative or its anhydride with a rosin glycidyl ester in the presence or absence of an organic amine.

The rosin used in the present invention includes gum rosin,
Also included are natural rosins such as wood rosin and tall oil rosin, hydrogenated rosins obtained by modifying these rosins, and disproportionated rosins. Naturally, abietic acid, dehydroabietic acid/dihydroabietic acid, pimaric acid, isopimaric acid, etc., which are not active ingredients of rosin, can also be mentioned.

The dicarboxylic acids used in the present invention include orthophthalic acid, isophthalic acid, terephthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid,
Methyltetrahydrophthalic acid, hexahydrophthalic acid,
Methylhexahydrophthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, sebacic acid,
Alkenylsuccinic acid having 8 to 18 carbon atoms, 8 to 1 carbon atoms
Mention may be made of eight alkyl succinic acids and their corresponding acid anhydrides.

The rosin glycidyl ester used in the present invention can be prepared by heating and reacting rosin with an alkaline substance such as epihalohydrin and all organic amines.

The organic amines used in the present invention are preferably tertiary amines or onium salts thereof, and specific examples of the tertiary amines include trimethylamine, dimethylbenzylamine, methyldibenzylamine, tribenzylamine, and dimethylaniline. , dimethylcyclohexylamine, methyldicyclohexylamine, tripropylamine, tributylamine, N-phenylmorpholine, N-
Examples include methylpiperidine and pyridine. Specific examples of onium salts of tertiary amines include tetramethylammonium chloride, tetramethylammonium bromide, hensyltriethylammonium chloride, allyltriethylammonium bromide, tetrabutylammonium chloride, methylsilioctylammonium chloride, and trimethylamine. Examples include hydrochloride, triethylamine hydrochloride, and pyridine hydrochloride.

In the present invention, the reaction proceeds stoichiometrically, so the molar ratio of the dicarboxylic acids and rosin glycidyl ester used is preferably 1:1, but usually 1.5:1.
It is also possible to set it within the range of 1.0 to 1.0:1.5.

In the present invention, it is not always necessary to use organic asnes, but depending on the type of dicarboxylic acids used, they may be used to shorten the reaction time. It is preferably within the range of 0.01 to 5% by weight, or 0.05 to 1% by weight.

In addition, in the present invention, the novel rosin-based linear polyester resin of the present invention can be used in a high yield regardless of the presence or absence of a solvent during the reaction, but the water produced during the reaction can be smoothly distilled out of the system. It is also possible to use a solvent as the refluxing solvent. The solvent to be used is determined in consideration of azeotropic properties with the produced water, non-reactivity with rosin glycidyl esters, dicarboxylic acids, etc., and specific examples include toluene and xylene. If a solvent is used during the reaction, it can be distilled off under reduced pressure to recover the solid content.

In the present invention, the reaction temperature and reaction time are appropriately determined in consideration of the yield of the product, but when an acid anhydride is used as the dicarboxylic acid, the reaction temperature is 100 to 2.
50°C1 preferably 130-180°0, 150-300°C1 preferably 1 when dicarboxylic acid is used
The temperature is preferably 80 to 260°C, and in any case the reaction time is preferably 0.5 to 10 hours, preferably 1 to 8 hours. The end point of the reaction in the present invention can be easily determined by appropriately measuring the acid value of the resin produced or by gel permeation chromatography.

The novel rosin-based linear polyester resins of the present invention can be obtained at high yields, and these resins can be used as binders for paints, printing inks, adhesives, flooring materials, road marking materials, etc. It is suitably used for applications such as and improving agents.

When the rosin thread polyester resin obtained by the present invention is used for such purposes, it usually has film strength, drying properties, blocking resistance, solubility in organic solvents, compatibility with other resins, and handling operations due to melting. Therefore, based on this reason, the softening point is 50 to 19.
It is preferable that the glass transition point is 30 to 170°C, the number average molecular weight is 20, and DO to 30.000.

That is, if the softening point is less than 50°C, the film strength, drying property and blocking resistance will be poor, and if it exceeds 190°C, the solubility, compatibility and workability will be poor. If the glass transition point is less than 60°C, the film strength, drying property and blocking resistance will be poor, and if it exceeds 170°C, the solubility, compatibility and workability will be poor. If the number average molecular weight is less than 2,000, the film strength will be poor due to the low molecular weight, and if it exceeds 30,000, the compatibility with other resins and workability will be poor.

There are no particular restrictions on the molecular weight distribution, but from the viewpoint of solubility in organic solvents and compatibility with other types of resins, it is usually 5.
．． 0 J:, those below J are preferred.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 [Manufacture of high-purity dehydroabietic acid] After converting the disproportionated rosin into a monoethanolamine salt, it was recrystallized several times using a 1:1 mixed solvent of water and ethanol, and the salt was eliminated with hydrochloric acid. White needle-like crystals of dehydroabietic acid were obtained. The melting point of this substance is 178°C, the acid value is 18
2.3, and high-speed liquid lithography (hereinafter referred to as H
As a result of the measurement by LQ), the chart changed to have a single sharp peak. The results of elemental analysis showed the following values. Moreover, the yield was 96.5%.・Elemental analysis value”
20H28o2 Theoretical value (%): a79.95 H9,39 Actual value (%)
): 080.21 H9,43 Reference Examples 2 to 4 The constants of the raw materials used, disproportionated rosin, gum rosin, and hydrogenated rosin (referred to as Reference Examples 2 to 4 in this order) are shown below.

Disproportionated rosin: acid value 162, softening point 79°C1 purity 87
% Ronsis R (manufactured by Arayo Kagaku Kogyo ■) Gum rosin: acid value 169, softening point 75°C1 purity 91%
, gum rosin hydrogenated rosin with color tone WW: acid value 165, softening point 74°C1 purity 89
% (manufactured by Arayo Kagaku Kogyo ■) Reference Example 5 [Production of high-purity dehydroabietic acid glycidyl ester] High-purity dehydro produced in Reference Example 1 was placed in a 300 m 1 colben equipped with a stirring device and a reflux condenser. 50 g of abietic acid, 1009 g of epichlorohydrin) and 0.059 g of benzyltrimethylammonium chloride were charged and dissolved under stirring, then heated to 80°C and reacted at the same temperature for 4 hours. Furthermore, 8 g of granular sodium hydroxide was added in portions, and the reaction was carried out at 100°C for 2 hours with stirring. After the precipitated common salt was evaporated, unreacted epichlorohydrin in the furnace liquid was distilled off using a rotary evaporator, and 2 ml of the solution was further removed to completely remove volatile components at 120°C. The obtained colorless and transparent oil was confirmed to be highly pure dehydroabietic acid glycidyl ester from the following measurement results. This product had an acid value o1 and an epoxy equivalent of 372 (theoretical value 357), and the HOL was a monodisperse peak.

Engineering R spec) A/(am)-1725,1260,
920,82ONMR spectrum: (δ value, ppm)
:Solvent 0DO131,2 (12H), 2.6 (2H
), 3 (IH), 4 (2I (), 7 (5H) Reference example 6
~8 Disproportionated rosin glycidyl ester, gum rosin glycidyl ester, and hydrogenated rosin glycidyl ester (referred to as Reference Examples 6 to 8 in this order) were synthesized in the same manner as in Reference Example 5. Various measurement results are shown below.

Disproportionated rosin glycidyl ester: acid value 0, epoxy equivalent weight 435.4 HLO: two BQR spectra based on each glycidyl ester of dehydroabietic acid and dihydroabietic acid: almost the same as Reference Example 5 NMR spectrum: Reference Example 5 Gum rosin glycidyl ester: acid value 0, epoxy equivalent 422.3 nLcz imitation 1i branch dehydroabietic acid glycidyl ester and several peaks R spectrum based on glycidyl esters such as abietic acid and palustric acid, which are the main components. : Almost the same as Reference Example 5 NMR spectrum: Reference Except exception, 3.5.75p
yn hydrogenated rosin glycidyl ester: acid value 0, epoxy equivalent 42 HLC: two peaks based on the dehydroabietic acid glycidyl ester of (li[ and the main component dihydroabietic acid glycidyl ester) R spectrum: almost the same as Reference Example 5 Spectrum: Reference Reference Exception: 3p Example 1 High purity dehydroabietic acid glycidyl ester obtained in Reference Example 5 35.8.I (Oj mol) and anhydrous 14.8. (0.1 mol) of phthalic acid was charged and reacted at 160°C for 6 hours under a nitrogen stream.
The reaction was carried out at °C for 1 hour to obtain a colorless and transparent resin. The yield was 98.3%.

Various measurement results are shown below.

Acid value 8.5, hydroxyl value 13.6, number average molecular weight 4266
, Molecular weight distribution 1.63, Softening point (鵠) 120°C1 Glass transition point ('%) 82°C Engineering R spectrum 71720c
m-1 NMR spectrum (δ value, ppm): Solvent ODO! 3,
.

1.2.4, 5 (4H), 5.5 (IH), 7.0 (
3H), 7, 5 (4H) GPO: Monodisperse peak elemental analysis value: (03□H3606)n Theoretical value (%): a75.78 H7,19 actual value)
: (174,01H7,10 The regularity of the molecular structure was clarified by the following selective amine decomposition method.

2 g of the obtained polyester resin was placed in a 100 ml eggplant-shaped flask, 20 ml of n-butylamine was added, and the mixture was refluxed for 1 hour. Then, n-butylamine was distilled off under reduced pressure using a rotary evaporator to obtain a white paste. Benzene was added to this and dissolved by heating, and then allowed to cool to room temperature to obtain white needle-like crystals. After heating and refluxing the crystals with 6N hydrochloric acid, the precipitated crystals were washed with water in a furnace and dried.
and I! by NMR! After conducting 11 tests, it was determined that it was phthalic acid.

Further, the furnace solution was dried to obtain a colorless and transparent oily substance. This was measured by NMR and partition chromatography and confirmed to be dehydroabietic acid monoglyceride. From the above results, only phthalic acid and dehydroabietic acid monoglyceride were detected as amine decomposition products of the resin, proving that the p-zine groups are regularly arranged in the molecular side chains in the molecular structure of the resin. .

Example 2 High purity dehydroabietic acid glycidyl ester 35.
8g (0.1 mol) and tetrahydro anhydride 7/1r
! ! 115.29 (0.1%)tt The reaction was carried out in the same manner as in Example 1 to obtain a colorless and transparent resin. Various measurement results are shown below.

Acid value 7.8, hydroxyl value 8.5, number average molecular weight 4320,
Molecular weight distribution 1.52, softening point 119°c1 glass transition point 80.5°0 HLO: Monodisperse peak error spectrum' 1720 cr+rl NMR spectrum (δ value, ppm): Solvent CDC/31.2.4
．． 2 (4H), 5.2 (IH), 5.5 (2H) Elemental analysis value "C31H4006'n Theoretical value (%): 07!1.20 H7,93 actual value (2)): 075.BOH8, D2 In the same manner as in Example 1, it was confirmed that the molecular structure had regularity.

EXAMPLES In Example 1, the molar ratios of the rosin glycol, diester, and dicarboxylic acids used were the same, and only their types were used in place of those shown in Table 1.

゛However, when the dicarboxylic acids used were anhydrides, the same reaction conditions as in Example 1 were adopted, but when an acid was used as in Example 7 or 8, a water separator was installed. The temperature was raised to 240 to 260°a in a reactor equipped with the same temperature, and the reaction was carried out at the same temperature for 6 hours while distilling off the produced water. In addition, when a high molecular weight resin is used as in Example 4, 0.1% of benzyl)limethylammonium chloride is added to the disproportionated rosin glycidyl ester as a catalyst and heated to 180°C.
The reaction was carried out for 6 hours.

Table 1 shows the measurement results of the acid value, hydroxyl value, number average molecular weight, molecular weight distribution, softening point, and glass transition point of various polyester resins. In addition, it was confirmed that all the resins obtained in Examples 6 to 10 had regular molecular structures.

Comparative Example Disproportionated rosin 50o9 (1 mol) and Glyquirin 929 (1 mol) were charged into a No. 11 full pen equipped with a stirring device, a reflux condenser, and a water separator, and 260 to 2
React at 80°0 for 5 hours, then phthalic anhydride 148
was added to the mixture and reacted at 26 oooa for 6 hours to complete the esterification reaction and yield 1 pale yellow resin. First check the various measurement results.
Shown in the table.

Regarding the regularity of the molecular structure, as a result of selective amine decomposition in the same manner as in Example 1, large amounts of monoglyceride, diglyceride, and triglyceride were observed in the disproportionated rosin, and it also contained a large amount of glycerin in addition to phthalic acid. It was found by gas chromatography measurement that Therefore, it was proved that this polyester resin, unlike the resin of Example 1, lacked regularity in its molecular structure.

Claims (1)

[Scope of Claims] 1 General formula: at least one divalent group selected from the group consisting of: an integer of 2 to 8, R2 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms; B indicates a rosin residue), and has a softening point of 50 to 190%,
Glass transition point is 60-170°0, number average molecular weight is 2.
A rosin-based polyester resin having rosin groups regularly arranged in molecular side chains, characterized in that the molecular side chains thereof have a molecular weight of 000 to 30,000. 2 General formula characterized by heating and reacting a dicarboxylic derivative or its anhydride with a rosin glycidyl ester in the presence or absence of organic amines: (wherein R is a hydrogen atom or a methyl group, n is an integer of 2 to 8, R2 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and B represents a rosin residue). It has the structural unit shown below and has a softening point of 50 to 190'C! , glass transition point is 30-170°C, number average molecular weight is 2.000
~50,0 (30) A method for producing a rosin-based polyester resin in which rosin groups are regularly arranged in molecular side chains.