JPS58141208A - Water-dispersible copolyester - Google Patents

Abstract

PURPOSE:The titled copolyester having moderate flexibility at normal temperature, prepared by copolymerizing a specified amount of two polyethylene glycols with a polyester prepared by polycondensing a dicarboxylic acid with a glycol. CONSTITUTION:In the production of a copolyester by reacting a dicarboxylic acid (or its esterifiable derivative) with a glycol and an esterifiable alkali metal sulfonate compound (e.g., sulfoterephthalic acid); 5-20mol%, based on the total glycol components, compound of formulaI, wherein n is 2-20, and/or compound of formula II, wherein n is 11-13, are copolymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a copolyester that has appropriate flexibility at room temperature and is water dispersible.

In the production of woven fabrics, fibers are used as multifilament yarns.
When used in ID form, it is preferable to treat the weaver with a sizing agent to bond the filaments prior to weaving.

Since the sizing agent needs to be removed after weaving to eliminate uneven dyeing, it is preferable to use a sizing agent that can be easily removed from the yarn by washing. Various water-dispersible polyesters have been proposed as yarn sizing agents for this purpose.

Such water-dispersible polyesters include (1) polyesters copolymerized with diethylene glycol having a glycol component of 20 moles or more and a sulfonic acid metal salt compound having an ester-forming bifunctional group (for example, 1 [Komei 47-408
73 Publication)■ 20~ of glycol component in polyester
A copolymer of 80% by weight of polyethylene glycol and a sulfonic acid metal salt compound having an ester-forming bifunctional group (e.g., JP-A-5O-1218341)
etc. are known.

However, the above copolymerized polyester (①) has a large amount of diethylene glycol (20 moles or more), so it has poor heat resistance,
It has the disadvantage of poor weather resistance, and when it is made into an aqueous dispersion, it becomes cloudy and has poor transparency.

On the other hand, for the copolyester (2), adding a large amount of high molecular weight polyethylene glycol (20 to 80% by weight) does not increase the intrinsic viscosity of the copolyester, which makes it difficult to develop flexibility and heat resistance. , weather resistance also deteriorates.

The inventors of the present invention have made extensive studies to eliminate such drawbacks, and have discovered a water-dispersible copolyester of TI L that has excellent overall physical properties as a sizing agent, and have arrived at the present invention.

That is, the present invention provides a polyester comprising at least one dicarboxylic acid or an ester-forming derivative thereof, and a glycol and an ester-forming sulfone-alkali metal salt compound, in which S7 or less is added to the total glycol component constituting the polyester. Formula H+ocH less than 20 molti
aci9゜OH (in the formula, n Id is an integer of 2 or more and 10 or less) and/or 611% or more and less than 20% by weight of the compound) 1 (-QC5c-su, #01i (in the formula, n' is 11 or more) This invention relates to a water-dispersible copolymerized polyester formed by copolymerizing a compound represented by the formula (an integer of 13 or less).

The dicarboxylic acid component used in the present invention is aliphatic.

It may be an alicyclic or aromatic acid. For example, oxalic acid, malonic acid, dimethylmalonic acid, and succinic acid.

Geltar*, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylgeltaric acid, azelain #I+L3-cyclopentanedicarbone 91. 1
．． 2-cyclohexanedicarboxylic acid.

1.3-Cyclohexanedicarboxylic acid 119114-Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthal II, g, s-dimethylterefur@a
Examples include 1e4-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 215-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, siphenin*, diglycolic acid, thiodiglopionic acid, and ester-forming derivatives thereof. Even if these are used on a two-month basis, they do not work at all.

Examples of the glycol include ethylene glycol, 1.2-propanediol, 1.3-propanediol, and 1.4-butanediol.

2.4-Dimethyl-2ethylhexane 1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-
1,3-propanediol, 1,6-hexanediol, 1,8-octanediol.

l,10-decanediol, 2,2.4-)limeter-1,6-hexanediol, 1,2-cyclohexanediol, 1.2-7 clohexa/dimetatool,
1,3-cyclohexane dimetatool, 1,4-cyclohexane dimetatool, 2,2,4,4-tetramethyl-1,3-cyclobuta/diol, P-ginrylene glycol, etc. are used. Among these, ethylene glyfur, 1,3-prono-diol, 1,4-7'tanediol, l,4-cyclohexane dimetatool, etc. are preferred.
L<, these 42S or more may be used.

Examples of the ester-forming sulfonic acid alkali IJ metal salt compound include sulfoterephthalic acid, 1I-klufoisophthalic acid, and 4-sulfophthalic acid.

4-Sulfonaphthalene-2,7-dicarbo/III sulfo-P-xylylene glycol, 2-sulfo-1,4-
Alkali metal salts such as bis(hydroxyethoxy)pe/zene and their ester-forming derivatives are preferred. The amount of the ester-forming sulfonic acid alkali metal salt compound to be used is not particularly determined, but it is preferably 0.1 mole or more relative to the dicarboxylic acid component.

The polyethylene glycol used in the present invention consists of two polyethylene glycol groups having different molecular weights.

One is the formula H+oC so CH1+! lOH [n ij in the formula
an integer of 2 or more and 10 or less], such as diethylene glycol.

Triethylene glycol, tetraethylene glycol, and pentaethylene glycol are used.

The other one is polyethylene glycol represented by 2H+0CHaC%-)n#011 (in the formula, n' is an integer of 11 or less): 13J or less. These may be used alone or in combination, or two groups may be used simultaneously. The amount of polyethylene glycol added is 2H+QC based on the total glycol components constituting the polyester.
The low molecular weight polyethylene glycol represented by 5C% snOH [in the formula, n is an integer from 2 to 1zlOJu] is 5 moles or more and less than 20 moles, The high molecular weight polyethylene glycol represented by the integer from 11 to 13 is 5 times Jt- or more x.

1 position or less is required. Anything outside this range has the above-mentioned drawbacks. For example, 2H+ in polyester
If 1 of the compound represented by OCH,Cpeng90H [in the formula, n is an integer of 2 or more and 10 or less] is 20 mol or more per 1 c of the total glycol component, heat resistance, weather resistance and transparency will deteriorate. , H+0CR- [in the formula, n is an integer of 11 or more and 13 or less] in an amount of 20% by weight or more, the heat resistance, weatherability, and flexibility deteriorate. In addition, formula I (
-oCH,C1%-)IlOR [where Dvh is an integer of 2 or more and 10 or less] containing less than 5 moles of low molecular weight polyethylene glycol, and a dye of the formula a-eo
cicH! -+, n' in the 1oHc formula is an integer from 11 to 13] 5 weight of polyethylene glycol -
If it is less than that, the solubility will be poor and the object of the present invention will not be achieved.

To produce the water-dispersible copolyester of the present invention,
Any general method such as a polymerization method using transesterification or a direct polymerization method can be applied as is.

For example, (1) heating a predetermined amount of dicarboxylic acid alkyl ester, glycol, and sulfonic acid alkali metal salt dialkyl ester in the presence of a transesterification catalyst, and performing a transesterification reaction while distilling off the methanol produced;
Next, a polymerization catalyst, a stabilizer, and a predetermined amount of polyethylene glycol are added, and then ethylene glycol is distilled off under high temperature and high vacuum to perform polycondensation.

■Dicarboxylic acid, glycol, and ester-forming sulfonic acid alkali metal salt compound are heated without a catalyst or in the presence of an esterification catalyst, and the water produced is distilled off at normal pressure or under pressure to form Nisdel, and then polyethylene glycol is The method of polycondensation using 5 parts by weight is most commonly employed.

It is better to add sulfonic acid alkali metal salt dialkyl ester, ester-forming sulfo/II alkali gold I14 base compound, and polyethylene glycol before transesterification or esterification, but they can also be added after transesterification or esterification. good.

In addition, these compounds may be separated using glycol liquid, flakes, or powder.

The copolymerized polyester 1J obtained as described above has excellent adhesive properties, and is also comprehensively superior in terms of heat resistance, weather resistance, solubility, transparency, and flexibility.

The present invention will now be described in detail with reference to examples.

Example 1 82.5 parts of dimethyl terephthalate, 23 parts of Is-sodium dimethyl sulfonate. Wings, ethylene glycol 57
．． Part a, 8.0 parts of diethylene glycol, 0.0 parts of zinc acetate.
After mixing 13 parts and carrying out a transesterification reaction while distilling methanol off at 140 to 200°C, 0.079 parts of trimethyl phosphate and 0.087 parts of antimony trioxide were added.
9.8 parts, polyethylene glycol with an average molecular weight of 600
1 part and polymerized with 26 parts ℃ I O 82 Hg, 35℃
A polymer with an intrinsic viscosity of 0.46 was obtained, which was calculated from the viscosity determined by 1111 in an ornochlorophenol solution.

5 parts of this polymer was added to 95 parts of water at room temperature, stirred for 30 minutes under boiling at 100°C, and the solution was kept at room temperature for 3 hours. As a result, the solution was colorless and transparent, had no turbidity at all, and had good water dispersibility.

Furthermore, the cloth containing this aqueous dispersion had good adhesiveness and flexibility.

Thermal stability was also good as shown in Table 1, and nine polymers were obtained which were excellent overall.

Example 2゜49.5 parts of dimethyl kephthalate, 3.4 parts of 1f dimethyl 5-sodium sulfonate, 50 parts of ethylene glycol
．． 2 parts and 0.079 parts of zinc acetate, 140-20
After carrying out the transesterification reaction while distilling off methanol at 0°C, 59 parts of trimethyl phosphate O, O, 0.087 parts of antimony trioxide, and 9.4 parts of polyethylene glycol with an average molecular weight of 1i600 were added and the mixture was heated at 250°C.
．． Intrinsic viscosity 0.4 calculated from 6111 with ornochlorophenol solution at 35°C and Kujo degree.
7 poly! I got -.

The water dispersibility, adhesion, and flexibility of this polymer were investigated in the same manner as in Example 1, and good results were obtained in all cases. In addition, the thermal stability was excellent (very good and excellent overall).No other polymers were obtained.

Example 3 Terephthalic dimethyl 82. Part s, dimethyl 5-sodium sulfonate it! 11.2 parts of ethylene glycol S, 7.4 parts of ethylene glycol S, 11.0 parts of diethylene glycol K, and 0.13 parts of zinc acetate were mixed, 140-2:;G.

After carrying out the transesterification reaction while distilling off methanol at ℃, trimethylphos 7a)0. Oes Department, 31
0.146 parts of hyacinnamon was added and polymerized to obtain a polymer having an intrinsic viscosity of 0.47 calculated from the viscosity measured with an orne chlorophenol solution at s11°C.

Results of investigating water dispersibility, adhesion, 1-softness, and thermal stability of this polymer using the same method as in Example 1.

Comparative Examples 1 to 4 Comparative Examples 1 to 4 As in Example 1.2, the amount of added calories of polyethylene glycol or diethylene glycol was adjusted according to the IK1 table composition. Transesterification and polycondensation reactions were carried out in the same manner as in Examples 2 and 3 with the following changes: Poly! - Tube generated.

This produced polymer was evaluated in the same manner as in Example 1. As shown in Table 1, when polyethylene glycol or diethylene glycol is used as a hydroxide, water dispersibility deteriorates when the amount added is reduced. In addition, when the amount of polyethylene glycol is increased, the thermal stability deteriorates, and the inherent viscosity of the polymer does not decrease by -1, resulting in poor flexibility.When the amount of diethylene glycol is increased, the thermal stability and water dispersibility are deteriorated.

Remarks l) Dimethyl terephthalate 2) Dimethyl isophthalate 3) Dimethyl 5-sodium sulfoisophthalate 4) Ethylene glycol 5) Diethylene glycol 6) Polyethylene glycol (average molecular weight = 600) 7) From the viscosity measured in orthochlorophenol solution at 116°C Calculated intrinsic viscosity b) Hue before and after drying when the polymer was dried for 6 hours (
Yellowness) Change A: Very small change in hue B: Small change in hue C: Large change in hue g) Evaluation of water dispersibility ■: Colorless and transparent 0: Cloudy but uniformly dispersed Q: Solid remains 1O) 7. Evaluation 1: Adhesive very well 2: Adhesive well 3: Introspective of adhesion.

Patent applicant: Teijin Limited 1. - Procedural amendment, dated February 7, 1980, +F Office Director's Palace 1, Indication of case Patent application No. 1987-22786 2, Title of invention: water-dispersible copolymerized polyester 3 Relationship with the company case making the amendment Patent Applicant 1-11 Minamihonmachi, Higashi-ku, Osaka (300) Teijin Limited Representative Tomoo Tokusue 5 [Detailed Description of the Invention aq+ column /7) (1) of the specification subject to amendment
) Specification, page 4, line 16, ``1,4-naphthalene dicarboxylic acid 1 is deleted.

(-Same, 6th true, 12th line, 13th-14th lines.

Page 7, lines 1 to 8, line 4, lines 7 to 8, line 6, line 11,
Page 8, lines 2-3, line S, lines 17-18, page 9, line 4, line #19, page 11, lines 8-i1, 12
Page, lines 1S to 1@, lines 1Sjj, lines 2 to 3, line 5, and line 8 of 111, ``Polyethylene glycol 1'' is corrected to ``polyoxyethylene glycol.''

(3) Same, page 6, line 16, page 10, line #14.

page 12, line 2 1m 16 lines, 1llk1s) [,11
In lines 7 and 8, and in the first sji[, 謔ding line, diethylene glycol 1 is corrected to be "dioxyethylene glycol."

(4) Same, page 6, line 11, "triethylene dalycol" is corrected to "trioxyethylene glycol".

, (5) Same, #I6 True $lK Correct [tetraethylene glycol J in lines 17-11 to [tetraoxyethylene glycol J].

(611til, 6th jj% line z8 [pentaethylene glycol 1 1 pentaoxyethylene glycol 1
I am corrected.

(7) Same, 9th true, 7th to 8th lines of "sulfonic acid alkali metal salt dialkyl ester and 1 are deleted.

(8) Same, stripe 1oli, th: + line, Mstl, ms line.

and 812 True, [sulfone dimethyl] in the first line is corrected as [sulfoinphthalate dimethyl J.

(9) Same, t sm, line 3 [diethylene glycol j
[Correct as dioxyethylene glycol 1.

that's all

Claims (1)

[Claims] At least one dicarboxylic acid or Nisdell-forming derivative thereof and a glycol and an ester-forming sulfur, 17r
Ik alkaline metal salt compound - Formula H + OC 1% CI% of 5 mol or more and less than 20 mol based on the total glycol components constituting the polyester in Tokarana 6 polyester
Compounds represented by 1+nOH (in the formula, n is a II number of 2 or more and 1O or less) and/or all 11 or more and less than 20 weight - of the formula H (-OCR, CH, -), OH (in the formula, n is 11
A water-dispersible monomer polyester obtained by copolymerizing a compound represented by the following and a number of 13 or less.