JPH0610256B2 - Method for producing alkali-soluble polyester resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyester resin which can be easily dissolved in alkaline water.

[Prior Art] The presence of a large amount of carboxyl groups in the polyester resin makes it possible to make the polyester resin water-soluble. If the application to the fields of fiber glue, paper processing, paints, adhesives, etc. is expanded, Attempts at tightening have been studied for a long time.

For example, a method for introducing a carboxyl group may be a method of using a polyfunctional carboxylic acid having three or more functional groups as a condensed acid component during the production of a polyester resin, or a method of graft-polymerizing a polymerizable unsaturated carboxylic acid on the polyester resin.

[Problems to be Solved by the Invention] However, in the former method, there is a risk of thickening and gelation at the time of condensation, so the amount of carboxyl groups introduced is naturally limited, and in the latter method, carboxyl groups are unevenly distributed. Since it is introduced, the purpose of water solubilization cannot be fully achieved. That is, in this method, even if the solubility of the polyester resin reaches a considerable level, only a resin having a slow dissolution rate in water (alkaline water) can be obtained.

Such a drawback becomes a problem in practical use of the resin. For example, when it is used as a fiber sizing agent, it takes a long time for desizing after sizing as well as when preparing a sizing liquid. Improving the dissolution rate has become a serious issue in the development of water-soluble polyester resins.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that “a polyester resin containing an aromatic dicarboxylic acid as an acid component is reacted with halogenoacetic acid, a benzene ring The present invention has been completed by finding that the object can be achieved when the carboxyl group is introduced into the side chain of the benzene ring in the resin by dehydrohalogenation with hydrogen.

In the present invention, it is considered that a resin having a very fast dissolution rate in alkaline water can be produced because the carboxyl group is introduced in a non-localized manner in the benzene ring in the main chain of the polyester resin and in a large amount. ing.

Therefore, when such a resin is used as a fibrous sizing agent (for water jet loom etc.), it can be expected to have an even better de-sizing property and at the same time have a performance that is no different from the conventional sizing agent for fibers in terms of tie strength. Since it also has both properties, it can be used as a sizing agent of extremely high practical value.

The polyester resin of the present invention can be obtained by condensing the polyhydric alcohol component with any acid component as long as the aromatic dicarboxylic acid is an essential component in all or part of the acid component. Such acid components include terephthalic acid,
Isophthalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,3-cyclopentadicarboxylic acid, 1,2-
Cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
2,5-norbornane dicarboxylic acid, 1,4-naphthalic acid, diphenic acid, 4,4′-oxybenzoic acid, diglycolic acid, thiodipropion, 2,5-naphthalenedicarboxylic acid and the like can be mentioned.

These may be acid anhydrides, esters, chlorides and the like, and include, for example, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl terephthalate and diphenyl terephthalate.

In addition to the above, trivalent or higher polycarboxylic acids such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, 4-methylcyclohexene
1,2,3 tricarboxylic acid anhydride, trimesic acid and the like can also be used. The proportion of the aromatic dicarboxylic acid in all the acid components is 20 mol% to 100 mol%, preferably 50 mol% to 100 mol%.

Further, as the polyhydric alcohol, ethylene glycol, diethylene glycol, pyropyrene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3- Propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,
3-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 3-
Methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, Two
4,4-Tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, 4,4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'- Dihydroxybiphenol, o
-, M- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4'-isopropylidenebis (2,6-dichlorophenol), 2,5-naphthalenediol and p-xylenediol. .

In addition to the above, trihydric or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol can be used in a small amount. is there.

In addition to the above acid component and polyhydric alcohol component, a sulfonate group can be introduced into the resin by a generally known method. Typical examples of the condensing component used in this case include 5-sodiosphoisophthalic acid and 5-potassium sorboisophthalic acid, but the condensing component is not limited to these.

No special operation is required to produce a polyester resin by condensing the acid component and the polyhydric alcohol component,
Any conventionally known method may be used, but a typical example is to charge a reactor with a polyhydric alcohol component in an amount of 1.0 to 2.0 times the acid component together with a catalyst and raise the temperature to 140 to 280 ° C. Then, dehydration condensation is performed. As the catalyst used in this case, zinc acetate, zinc chloride, stannous lauryl, dibutyltin oxide, etc. are used, and these are usually added in an amount of 0.05 to 0.15 part by weight based on the dicarboxylic acid. A solvent is not particularly required, but if necessary, an inert solvent such as methyl acetate, benzene, acetone, xylene, toluene may be used. The polyester resin has a molecular weight of 3,000 to 30,
000 is suitable.

In the present invention, the above polyester resin is reacted with halogenoacetic acid to cause hydrogenation of the benzene ring and dehydrohalogenation.

Monochloroacetic acid is preferably used as the halogenoacetic acid, but monobromoacetic acid or the like can also be used. Of course, it is not necessarily limited to these.

The monohalogenoacetic acid is used in a proportion of 0.5 to 1.0 mol with respect to 1 mol of the aromatic dicarboxylic acid in the polyester resin.

There is no particular limitation in carrying out the above reaction, and the reaction is carried out without solvent or in an organic solvent. Xylene, toluene, etc. are used as the solvent. Examples of the catalyst include ferric dioxide and potassium bromide, and the reaction temperature is 150 to 2
A reaction time of 50 ° C. and 2 to 25 hours is suitable.

The final resin has a molecular weight of 5,000 to 20,000 and an acid value of 1.
Practical ones of 100 to 300 KOHmg / g.

The thus obtained alkali-soluble polyester resin can be applied to various fields such as sizing agents for fibers, paints, adhesives, and molded products, and is used by being dissolved in aqueous ammonia, aqueous sodium hydroxide, aqueous sodium carbonate, etc. However, the effect of the present invention can be most exerted in the use as a paste.

In the preparation of the paste solution, the above resin is neutralized directly or if necessary with a polyester resin neutralized with alkaline water or the like, and then diluted or dissolved in water. Starch, PVA,
A PVA derivative, an acrylic paste, an oil agent, and other auxiliary agents may be used in combination, if necessary. in this case,
The concentration of the paste solution is in the range of 5 to 30% by weight in view of the accumulation of bubbles in the paste solution and the appropriate amount of the paste adhered to the fibers, and the viscosity is 5 to 20 cp at the concentration of 10% by weight (20 ° C).
It is appropriate to adjust it so that it is in the range of about s.

Since the sizing agent can exert excellent effects as described above, it is advantageously applied to a wide range of general spun yarns and filaments regardless of whether natural fibers or synthetic fibers or sizing methods are used.

[Operation] Since the alkali-soluble polyester resin obtained in the present invention has an improved dissolution rate in alkaline water, the desizing can be efficiently performed especially when used as a sizing agent for fibers.

[Example] Next, the method of the present invention will be described more specifically with reference to Examples.

Example 1 2 equipped with a stirrer, rectification column, nitrogen inlet tube, vacuum device
Glass lining reactor with 1 mol of isophthalic acid, 1.0 mol of ethylene glycol, and 0.
5 mol and 0.05 part of dibutyl oxide and 0.05 part of antimony trioxide were charged, esterified at 180 to 230 ° C., and then condensed under vacuum of 0.1 to 1.0 mmHg to give a molecular weight of 20,000, Acid value 1KOHmg / g, hydroxyl value 6K
A OH mg / g polyester resin was produced.

Next, in the same reaction can as above, 100 parts of polyester resin,
0.28 part of monochloroacetic acid was introduced, 0.2 part of ferric dioxide and 0.8 part of potassium bromide were further added, and the reaction was carried out at 210 ° C. for 8 hours.

The obtained alkali-soluble polyester resin has a molecular weight of 1
It was 8,000 and oxidized 128 KOHmg / g.

Various physical properties of the resin were measured. The results are shown in the table.

Examples 2 to 3 Instead of the polyester resin used in Example 1, terephthalic acid / isophthalic acid / ethylene glycol / neopentyl glycol = 0.5 / 0.5 / 1.0 / 0.5 (molar ratio) was used. Based on polyester resin (Example 2) and polyester resin (Example 3) composed of isophthalic acid / adipic acid / ethylene glycol / diethylene glycol = 0.8 / 0.2 / 0.8 / 0.7 (molar ratio), respectively. As a polymer, the same reaction as in the same example was performed. The results are shown in the table.

As a control example, an experiment was carried out when acrylic acid was graft-polymerized to the base polymer of Example 1. The results are also shown in the table.

The measurement of various physical properties is as follows.

(1) Solubility in alkaline water The time until dissolution was measured so that the concentration was 20% in ammonia water equivalent to the acid value of the alkali-soluble polyester resin.

(2) Evaluation of sizing agent <Preparation of sizing solution> A 10% aqueous solution was prepared by dissolving the sizing agent in water containing ammonia in an amount equal to the carboxyl group equivalent in the polyester resin. This was used as a sizing agent for water jet loom.

<Gluing conditions> Raw yarn; Polyester yarn (50d / 24 filaments) Gluing conditions; Isizer Warping Slasher Ro Gluing temperature 20 ° C C Gluing speed 100m / min D Drying speed chamber 120 ° Cylinder 90 ° C <Physical property measurement> Adhesion rate 2-3 g of glued yarn is put into 100 times amount of 0.5% sodium carbonate aqueous solution, desizing is performed 3 times at 90 ° C., washed with water, dried and weighed. The weight difference between the glued yarn and the desizing yarn is measured. I asked.

Squeeze ratio It was calculated by dividing the amount of adhesion (%) by the adhesive density (%) and multiplying by 100.

Tying force test Using Matsui Purifier TM type tie force tester, weight 100g,
The average number of times of friction until the yarn was broken at an angle of 145 ° (10 mm) was measured.

Desizing rate Put 2-3 g of sizing thread in 100 times amount of water, and 80-85 ℃
Desizing was performed for 10 seconds and 20 seconds, washed with water, dried and weighed. The desizing amount was determined from the weight difference between the desizing yarn and the desizing yarn, and the ratio to the adhesion amount was shown.

[Effect of the Invention] Since the carboxyl group is delocalized and introduced into the alkali-soluble polyester resin obtained in the present invention, the dissolution rate in alkaline water is remarkably improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09J 167/02 JFU 8933-4J D06M 15/507 D21H 17/53 (56) References JP 62 -1725 (JP, A)

Claims (2)

[Claims] 1. A polyester resin containing an aromatic dicarboxylic acid as an acid component, wherein a halogenoacetic acid is reacted to dehydrohalogenate hydrogen on a benzene ring to introduce a carboxyl group into the resin. Method for producing alkali-soluble polyester resin. 2. The method according to claim 1, wherein monochloroacetic acid is used as the halogenoacetic acid.