JPS59147013A - Novel urethanized polyester resin and binder for water jet room consisting thereof - Google Patents

Abstract

PURPOSE:A novel urethanized polyester resin useful as a binder for water jet room, having specific properties, improved water resistance and binder eliminating properties, obtained by reacting a polyester polyol with a polyisocyanate at a specified temperature. CONSTITUTION:A dicarboxylic acid (e.g., malonic acid, etc.) is condensed with an alkylene glycol (e.g., ethylene glyocol, etc.) and a polycarboxylic acid (e.g., trimellitic acid, etc. to give a polyester polyol, which is reacted with a polyisocyanate (e.g., 2,4-tolylene diisocyanate, etc.) at 50-130 deg.C, to give the desired urethanized polyester resin having a ratio of ester bond/ester bond+urethane bond based on molar ratio of 0.70-0.95 and 30-100KOHmg/g acid value. The urethanized polyester resin is dissolved in an alkali water and blended with any processing agent for fabric, softening agent, plasticizer, etc., to give a binder for water jet room.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel rethanized polyester resin, and provides a resin particularly useful as a sizing agent for quarter jet looms.

Recently, quarter-jet weaving machines, which produce textiles by flying the warp threads with a jet of water instead of the shuttle used in conventional weaving machines, have been able to operate at high speeds and significantly improve weaving efficiency. There are high expectations for these reasons.

Since this method uses a large amount of water, the warp sizing agent that is compatible with this weaving machine is different from conventional warp sizing agents! It is newly required that the glue film after gluing and drying has sufficient water resistance, and it is also necessary to have sufficient desizing properties for post-processing such as dyeing after weaving. A sizing agent for quarter jet looms must be able to fully satisfy the contradictory properties of water resistance and desizing properties.

The most typical sizing agent is an acrylic ester-acrylic acid copolymer sizing agent, but its binding power to hydrophobic fibers such as polyester fibers is unsatisfactory, and efficient sizing is difficult. The reality is that this is not possible.

However, as a result of extensive research, the present inventors have found that a flexinized polyester resin is obtained by reacting a polyester polyol containing a carboxyl group with a polyisocyanate at a temperature of 50 to 130°C, and that 0.95, CB) Acid value is 50-100 KOH21v/yte,s
The present inventors discovered that a new L/X polyester resin is useful as a sizing agent for quarter jet looms and completed the present invention.

The resin of the present invention is a novel compound not only for its uses but also for the resin itself, which has not been described in any literature.

The resin is produced by converting a carboxyl group-containing polyester polyol with a polyisocyanate. The raw material carboxyl group-containing polyester polyol is, for example, dicarboxylic acid, alkylene glycol and 6
The most common method is to condense a polycarboxylic acid with a higher valence. The acid value of the polyester polyol varies depending on the acid value of the final product, but it is usually 40 to 150.
'KOH1+v/y range concavity. Further, the polyol must have at least two hydroxyl groups in the molecule. Although it is advantageous for the hydroxyl group to be present at the end of the molecule in terms of preventing gelation during resin production, there is no problem in having the hydroxyl group present in the molecule as long as condensation reactions are taken into account.

Examples of dicarboxylic acids are oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, geltaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylgeltaric acid, azelaic acid, cepacic acid, fumaric acid, maleic acid. , itaconic acid, 1,6-cyclopencune dicarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 1,6-cyclopenkunedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, fucuric acid, terephthalic acid, iso7thalic acid, 2°5-norbornanedicarboxylic acid, 1,4-sugar Examples include 7curic acid, siphenic acid, 4,4'-oxybenzoic acid, diglycolic acid, thiodipropion, and 2,5-7taledicarboxylic acid.

These may be acid anhydrides, esters, talolides, etc., such as dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-7taledicarboxylate, dimethyl iso7thalate, dimethyl terephthalate, and diphenyl tereptalate. including.

Examples of alkylene glycols include ethylene glycol, diethylene glycol, globylene glycol, cyclopylene glycol, 1.propanediol, 2.
4-dimethyl-2-ethylhexane-1-ro-diol, 2,2-dimethatV-1,6-propanediol (neopentyl glycol), 2-ethyl-2-zotiroot 6-propanediol, J, 2 -=thi...-2-isobutylatero-bu...andiol, 1,6-butanediol, 1,4-butanediol, 1,5-pencunediol, 1,6-hexanediol, 2,2・4-to! J
Methyl-1,6-hexanediol, 1,2-cyclohexanedimetatool, 1.ro-cyclohexanedimethanol, 1,4-cyclohexanedimetatool, 2.2.
4,4-Tetramethyl-1,6-cyclobutanediol, 4,4'-thiodi7eth/-ol, 4,4'-methylenedi7eth/-ol, 4,4'-(2-norbornylidene)diphenol , 4,4'-dihydroxybiphenol, 0-
, m- and p-dihydroxybenzene, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene bis(2,6-dichlorophenol), 2,5-su7
Mention may be made of tale diol and p-xylene diol.

Examples of (poly)carboxylic acids having a valence of 6 or more or their anhydrides include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1
, 2,5-tricarboxylic acid anhydride, trimesic acid, and the like. These may be used alone or in combination of two or more.

The method for obtaining the zero-start polyester polyol is as follows. The dicarboxylic acid component, alkylene glycol component, and polycarboxylic acid, or other components as necessary, such as boria such as pentaerythritol, chrycerin, trimethylolpropane, and trimethylolethane.
) Recol is obtained by hair stylation reaction at a temperature of 170 to 280'C in the presence of an esterification catalyst such as digtyltin oxide or antimony trioxide.

The polyester polyol described above is then reacted with a polyisocyanate. The phretanization reaction is carried out by dissolving the polyester polyol in a solvent such as acetone or ethyl acetate, and adding polyisocyanate dropwise in the presence of a catalyst such as di-n-butyltin dilacrate. The carboxyl groups in the polyester polyol must remain in the molecule.

For this purpose, it is necessary to perform the above reaction at a temperature of 50 to 160 DEG C. and to control the reaction so that the hydroxyl groups of the polyester polyol and the polyisocyanate react selectively to form flexic bonds.

The flexinized polyel ratio obtained by such operation is 0.70 to 0.95, preferably 0.80 to 0.90)
Acid value is 60-100 KOHT9/y preferably 40-100
The requirement of 80KOH■/y must be satisfied.

If the value of (5) is less than 0.70, a glue with sufficient binding power cannot be obtained, while if it is more than 95, there is a risk of gelation during resin production, or even if a resin is obtained, Since it is insoluble in alkaline water or the aqueous solution is unstable, it is impossible to use it as a sizing agent. Also, the value of (B) is 50 KOH
If it is less than 1/y, it is extremely difficult to prepare an aqueous solution, while if it is more than 100 KOH7Ni151', the glue tends to block, causing problems in its handling.

In order to satisfy the above conditions, in the phretanization reaction of polyester polyol, the ratio of polyisocyanate to polyol is 0.8: 1.0 to 1.5.
: It may be used at a ratio of 1.0 (molar ratio).

Examples of the polyisocyanate include 2.4-) lylene diisocyanate, 2.6-) lylene diisocyanate, 2,
4 and 2.6-) lylene diincyanate mixture, 4.
4'-diphenylmethane diisocyanate, m-7 enylene diisocyanate, xylylene diisocyanate,
Tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,
4-cyclohexylylene diisocyanate, 4,4'-dicyclohexylylene diisocyanate, O, 6'-dimethyl-4,4'-biphenylene diisocyanate, 6,
6'-dimethoxy-4,4'-biphenylene diisocyanate, 6,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-s7tale diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, etc. are used.

Crude tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate or carbodiimide-modified 4
, 4'-diphenylmethane diisocyanate may also be used.

The above polyisocyanates may be used alone or as a mixture of two or more.

When preparing a paste for a quarter jet loom using the above-mentioned urethanized polyester resin, it is necessary to dissolve it in alkaline water such as aqueous ammonia. The solid content concentration of the sap is suitably about 5 to 15% by weight in consideration of workability and the like. Any fiber processing agent, softener, plasticizer, fiber auxiliary agent, etc. may be used in combination with the liquid.

The sizing agent for quarter-jet looms of the present invention is widely used in quarter-jet looms regardless of the type of sizing yarn, such as hydrophobicity, synthetic fiber, natural fiber, filament yarn, or spun yarn. It is extremely suitable as a weaving sizing agent during weaving.

Above, we have mainly described the case where the resin of the present invention is used as a sizing agent for quarter-jet looms, but the resin can also be used for other purposes such as adhesives, binders, paints, coatings, fiber treatment agents, molded products, etc. Useful.

Next, the present invention will be explained in more detail by giving examples.

Example 1 In a 21 flask equipped with a nitrogen blowing tube, a thermometer, a stirrer, and a distillation column, isophthalic acid 498y (6 mol), trimellitic anhydride 192y (1 mol), neopentyl glycol 312y (5 mol), diethylene glycol 212y (
2 mol) and 0.5 y of zinc acetate dihydrate were charged, and a polyester polyol was obtained by a conventional method at 190 to 230°C under nitrogen blowing.

The number average molecular weight measured by osmotic pressure method was 1100, acid value 51.6 KOH/f/, and hydroxyl value 103.0.

This polyester polyol 55J' (0.5 mol) was mixed with 600 ml of ethyl acetate! VC dissolved, dilacrynic acid di-n-
Butyltin o and sy were added, and inphorone diisocyanate + 119 (0.5 mol) was added dropwise at 50°C over 1 hour to carry out a phretanization reaction. After the reaction was completed over 24 hours at the boiling point of ethyl acetate, ethyl acetate was distilled off to produce phretanized polyef, 7': /L/ resin. The acid value was 45 KOH/y, the hydroxyl value was 0, and the number average molecular weight was 20,000 by osmotic pressure method. Furthermore, there were 120 ester bonds and 15 frethane bonds in the resin. The structure of the phretanized polyester resin was confirmed based on the following analytical data.

Precisely weigh this urethanized polyester resin 2y to 1/2N.
After dissolving in sodium hydroxide aqueous solution, boil for 2 hours and 1/2
Back titration with N-hydrochloric acid revealed that the amount of sodium hydroxide consumed was 27.25e. The acid value of the polyester resin is 0.006 diester bonds/y. Further, the nitrogen content determined by the kill pool method was 1.05% by weight, and the number of shiftletane bonds was 0.00075 pieces/y.

Next, 100 y of phretanized polyester resin was dissolved in 895 y of water containing 5 y of 28% aqueous ammonia to obtain a 10% aqueous solution. Table 1 shows the performance as a glue for quarter jet rooms.

Table 1 also shows the performance of a commercially available acrylic adhesive for quarter jet looms as Control Example 1.

Examples 2 to 4 Control Examples 2 to 5 The same experiment as in Example 1 was conducted except that the resin shown in the table was used in place of the phretanized polyester resin in Example 1.

The results are shown in Table 2.

Table 1 (Note) Original yarn; polyester yarn (50d/24 filament) sizing conditions; ■Sizer Warving slasher @ sizing temperature
45℃ θ Gluing speed 100 m/m1n O Drying speed Chicken bar 120"'C cylinder
90°C Adhesion Rate Sized yarn 2 to 3y was placed in 100 times the volume of 0.5% sodium carbonate aqueous solution, desizing was performed 6 times at 90°C, and after washing and drying, the weight was measured, and the sizing yarn and unsizing yarn were measured. It was determined by the weight difference.

Squeezing rate was determined by dividing the adhesion amount (%) by the gluing density (%) and multiplying the result by 100.

Conjugation force test Using Matsui Seiki TM type conjugation force test root, weight 10021
The average number of frictions until yarn breakage was measured at an angle of 145° (10su+). In addition, under normal conditions, 20℃, 65%R
Measurements were taken after immersion in water at 20° C. for 6 and 60 minutes when wet. The measurement was repeated 10 times and the average value is shown.

Desizing rate Sized yarns 2 to 6 y were placed in 100 times the volume of 0.5% sodium carbonate aqueous solution, desizing was carried out at 90°C for 50 minutes, and after washing and drying, the weight was measured and the difference between powdered yarn and desizing yarn was determined. The amount of glue removed was calculated from the difference in weight, and the ratio to the amount of adhesive was shown.

Table 2 of

Claims (1)

[Scope of Claims] 1. A phrethanized polyester resin obtained by reacting a polyester polyol containing a carboxyl group with a polyisocyanate at a temperature of 50 to 130°C, 0.70 to 0.95 in the resin, (B) Acid value! l O~100 KOHIIW/yf6
New rethanized polyester resin. It is a phretanized polyester resin obtained by reacting a polyester polyol containing two carboxyl groups and a polyisocyanate at a temperature of 50 to 130°C, and the resin has an acid value of 0, 70 to 0.95, (B) acid value 75f 30 to 100 KOHW/yTEARC L/p A glue for quarter jet looms whose main ingredient is Sy-converted polyester resin.