JPH0115626B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new urethanized polyester resin, and provides a resin particularly useful as a sizing agent for water jet rooms. Recently, it has been discovered that waterjet-type fabrics, which produce fabrics by flying the warp threads with a jet of water instead of the shuttle in conventional weaving machines, are capable of high-speed operation and have significantly improved weaving efficiency. It is expected that this will lead to improved performance. Since this method uses a large amount of water, there is a new requirement for a warp sizing agent that is compatible with this weaving machine to have sufficient water resistance for the glue film after sizing and drying, unlike conventional warp sizing agents. At the same time, it is also necessary to have sufficient desizing properties for post-processing such as dyeing after weaving, and sizing agents for water jet looms must have the contradictory properties of water resistance and desizing properties. It must be completely satisfactory. 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, making efficient sizing difficult. The reality is that it is not possible. However, as a result of intensive research, the present inventors found that
It is a urethanized polyester resin obtained by reacting a polyester polyol containing a carboxyl group and a polyisocyanate at a temperature of 50 to 130°C, and the (A) ester bond/ester bond + urethane bond in the resin is 0.07 on a molar basis. 〜0.95, (B) A novel urethanized polyester resin having an acid value of 30 to 100 KOHmg/g was found to be useful as a sizing agent for water jet rooms, and the present invention was completed. 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 urethanizing a polyester polyol containing a carboxyl group with a polyisocyanate. The most common method for producing a carboxyl group-containing polyester polyol as a raw material is to condense a dicarboxylic acid, an alkylene glycol, and a trivalent or higher-valent polycarboxylic acid. Depending on the acid number of the final product, the acid number of the polyester polyol varies considerably, but is usually selected from the range of 40 to 150 KOH mg/g. 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. The number average molecular weight of the polyester polyol is preferably 300 to 1,500. Examples of dicarboxylic acids are oxalic 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-cyclopentanedicarboxylic acid, 1,2-
Cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 2,5-norbornanedicarboxylic acid,
1,4-naphthalic acid, diphenic acid, 4,4'-
Examples include oxybenzoic acid, diglycolic acid, thiodipropion, and 2,5-naphthalene dicarboxylic acid. These may be acid anhydrides, esters, chlorides, etc., and include, for example, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl isophthalate, dimethyl terephthalate, and diphenyl terephthalate. Examples of alkylene glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene 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, 2.
2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1.
3-Cyclohexane dimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4.
4'-thiodiphenol, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol,
o-, m- and p-dihydroxybenzene, 4.
Examples include 4'-isopropylidene diphenol, 4,4'-isopropylidene bis(2,6-dichlorophenol), 2,5-naphthalene diol and p-xylene diol. Examples of trivalent or higher (poly)carboxylic acids or their anhydrides include trimellitic acid, trimellitic anhydride,
Examples include pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3 tricarboxylic anhydride, and trimesic acid. These may be used alone or in combination of two or more. The method for obtaining the polyester polyol of the present invention is as follows. The dicarboxylic acid component, alkylene glycol component, and polycarboxylic acid, or other components as necessary, such as pentaerythritol, glycerin, trimethylolpropane,
It is obtained by esterifying a polyalcohol such as trimethylolethane at a temperature of 170 to 280°C in the presence of an esterification catalyst such as dibutyltin oxide or antimony trioxide. The polyester polyol described above is then reacted with a polyisocyanate. The urethanization reaction is carried out by dissolving a 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 dilaurate. The carboxyl groups in the polyester polyol must remain in the molecule.
For this purpose, it is necessary to carry out the above reaction at a temperature of 50 to 130°C and to control the reaction so that the hydroxyl groups of the polyester polyol and the polyisocyanate react selectively to form urethane bonds. The urethanized polyester resin obtained by this operation has (A) an ester bond/ester bond + urethane bond in a molar ratio of 0.70 to 0.95, preferably 0.80 to 0.90 (B)
Acid value is 30~100KOHmg/g, preferably 40~
Must satisfy the requirement of 80KOHmg/g. If the value of (A) is less than 0.70, a glue with sufficient binding power cannot be obtained, while if it is more than 0.95, there is a risk of gelation during resin production, and even if a resin is obtained, it will not be soluble in alkaline water. However, the aqueous solution is unstable and cannot be used as a sizing agent. or,
If the value of (B) is less than 30 KOH mg/g, it is extremely difficult to prepare an aqueous solution, while if it is more than 100 KOH mg/g, the adhesive tends to block, causing inconvenience in its handling. Further, the number average molecular weight of the urethanized polyester resin is preferably 3,000 to 20,000. In order to satisfy (A) and (B), in the urethanization reaction of polyester polyol, the ratio of polyisocyanate to polyol is 0.8:1.0 to 1.0.
It may be used at a ratio of 1.5:1.0 (molar ratio). Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4 and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, m-phenylene diisocyanate, Xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,
4-cyclohexylene diisocyanate, 4,
4′-dicyclohexylmethane diisocyanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-
4,4'-biphenylene diisocyanate, 1,5
-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, etc. are used. Crude products of tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate and modified products such as carbodiimide-modified 4,4'-diphenylmethane diisocyanate can also be used. The above polyisocyanates may be used alone or as a mixture of two or more. When preparing a glue for a water jet room 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 size solution 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 water jet looms of the present invention is widely used in water jet looms regardless of the type of sizing yarn, such as hydrophobic strength or weakness, synthetic fibers, natural fibers, filament yarns, or spun yarns. It is extremely suitable as a weaving paste when weaving using a loom. Above, we have mainly described the case where the resin of the present invention is used as a glue for water jet rooms.
It is useful for various applications such as paints, coatings, fiber treatment agents, and molded products. Next, the present invention will be explained in more detail by giving examples. Example 1 498 g (3 mol) of isophthalic acid was placed in two flasks equipped with a nitrogen blowing tube, thermometer, stirrer, and distillation column.
192 g (1 mole) of trimellitic anhydride, 312 g (3 moles) of neopentyl glycol, 212 g (2 moles) of diethylene glycol, and 0.5 g of zinc acetate dihydrate were charged, and a polyester polyol was obtained by a conventional method at 190 to 230 °C under nitrogen blowing. Ta. The number average molecular weight measured by osmotic pressure method is 1100, acid value 51.6KOHmg/g,
The hydroxyl value was 103.0. Dissolve 550 g (0.5 mol) of this polyester polyol in 600 g of ethyl acetate, add 0.3 g of di-n-butyltin dilaurate, and dissolve 111 g of isophorone diisocyanate at 50°C.
(0.5 mol) was added dropwise over 1 hour to carry out the urethanization reaction. After the reaction was completed over 24 hours at the boiling point of ethyl acetate, the ethyl acetate was distilled off to produce a urethanized polyester resin. Acid value 45KOHmg/
g, hydroxyl value 0, number average molecular weight by osmotic pressure method is
It was 20,000. Also, the ester bond in the resin is 120
There were 15 urethane bonds. The structure of the urethanized polyester resin was confirmed using the following analytical data. 2 g of this urethanized polyester resin was accurately weighed, dissolved in a 1/2N aqueous sodium hydroxide solution, boiled for 2 hours, and back titrated with 1/2N hydrochloric acid, and the amount of sodium hydroxide consumed was 27.2 cc. From the acid value of the polyester resin, the number of ester bonds is 0.006/
It is g. In addition, the nitrogen content determined by the Kirdahl method is 1.05% by weight, and the number of urethane bonds is
It was 0.00075 pieces/g. Next, add 100g of urethanized polyester resin to 28%
10% dissolved in 895g of water containing 5g of ammonia water
An aqueous solution of was obtained. Table 1 shows the performance as a glue for water jet rooms. Table 1 also shows the performance of a commercially available acrylic water jet room adhesive as Control Example 1. Examples 2 to 4 Comparative Examples 2 to 5 The same experiments as in Example 1 were conducted except that the urethanized polyester resin in Example 1 was replaced with the resin shown in the table. The results are shown in Table 2.

【table】

【table】

[Table] The number average molecular weights of the urethanized polyester resins are as follows. Example 2 (6200), Example 3 (4400) Example 4
(3700).

Claims (1)

[Claims] 1. dicarboxylic acid and alkylene glycol; and 3.
It is a urethanized polyester resin obtained by reacting the hydroxyl groups of a polyester polyol containing carboxyl groups and hydroxyl groups with polyisocyanate at a temperature of 50 to 130°C, which is obtained by condensing a polycarboxylic acid with a polycarboxylic acid having a higher value than the hydroxyl group. A sizing agent for a water jet room whose main ingredient is a urethanized polyester resin having (A) an ester bond/ester bond + urethane bond having a molar ratio of 0.70 to 0.95, and (B) an acid value of 30 to 100 KOHmg/g.