JPS6197376A - Water-soluble polyester sizing agent - Google Patents

Abstract

PURPOSE:To provide the title sizing agent for production of sized yarn exhibiting excellent bundling power, adhesive strength and scouring property without causing coming-off of the sizing agent, prepared by polycondensation of dicarboxylic acid and diol in the presence of an ester of a specified compd. and a phosphoric acid compd. CONSTITUTION:The sizing agent is prepared by esterifying and polycondensing at least one aliphatic, alicyclic or aromatic dicarboxylic acid (e.g. isophthalic acid), at least one diol (e.g. ethylene glycol) and, when necessary, a dicrboxylic acid (derivative) having an SO3M group (where M is H or metal ion) in an aromatic nucleus of a diol (derivative) in the presence of 10 wt. % ester of at least one phosphoric acid compd. selected from among phosphoric, phospho rous, pyrophosphoric and polyphosphoric acids and a phosphoric acid compd. of formula of I or II (where n is 2-6; m is 2-10) (e.g. ethylene glycol ester of phosphorous acid).

Description

DETAILED DESCRIPTION OF THE INVENTION (Applications of J♀Gate 1.) KinoRsu 1 relates to a water-soluble polyester sizing agent used in the production of sizing yarn.More specifically, the present invention relates to When weaving yarns such as filament yarns, processed yarns, twisted yarns, and spun yarns are glued together to give cohesive strength, the type of loom to be used, such as shirttle loom, non-shirttle loom, iso, water jet loom, etc. The present invention relates to a water-soluble polyester paste that can be woven in any type of scouring process and facilitates scouring work after weaving.

[Conventional technology]

It is a common technical practice to glue textile threads during weaving. The main purpose of tIvI attachment is to impart cohesiveness to the yarn during the weaving process.1 Usually, polymeric materials such as starch, polyvinyl alcohol, polyacrylate, alone or in combination, are applied to the yarn to form a glue after the weaving operation. I am doing the extraction. However, when these materials are used, the sizing is not sufficient due to the binding and adhesive strength of the threads, and there is also a lot of glue that comes off during weaving, especially when using Tetoron or polyester filament threads in synthetic fibers or processed threads. In this case, this tendency is noticeable.

On the other hand, water-soluble polyester sizing agents are already known, such as those shown in U.S. Pat. In this case, sizing has the advantage that the binding and adhesive strength of the threads is sufficient and there is little amount of glue coming off, but there is a problem that special scouring is required. In recent years, weaving using water jet looms has become widespread, and in the scouring of polyacrylate sizing agents, which are the mainstream sizing agent, as described in RTRI, there is a tendency that the higher the pH, the better the desizing properties, and caustic soda is generally used. The scouring process was also simple and quick. On the other hand, conventional water-soluble polyester sizing agents have the property of coagulating in an aqueous solution of caustic soda, and therefore cannot be scoured. Currently, jl'+Germany is being performed. Due to the difficulty of such a scouring process, water-soluble polyester glue has a good contact force with polyester filament yarn, has less adhesive residue, and can be woven with a lower adhesion rate than polyacrylate glue. The advantages of this technology were not taken advantage of, and its actual use was limited to a small number of people.

[Problem that the invention seeks to solve]

As shown in item L, polyacrylate glue and other commonly used glue have good scouring properties, but sizing has insufficient thread cohesion and adhesion, and there is also a lot of glue that comes off during weaving. There was a problem. On the other hand, conventionally known water-soluble polyester sizing agents have the problem that, while they produce less glue during weaving and have good yarn binding and adhesive strength when sizing, they have extremely poor scouring properties.

The present invention aims to solve the above-mentioned problems of the prior art and to provide a water-soluble polyester sizing agent that has good cohesive strength and adhesive strength, and has excellent scouring properties.

[Technical means for solving the problem] The present inventors
As part of various research, we are developing esters of phosphoric acid, phosphorous acid, etc. with ethylene glycol, diethylene glycol, etc. for the purpose of imparting water solubility to monopolycondensates during polycondensation after esterification in the manufacturing process of water-soluble polyester resins. When the compound is added, the resulting polycondensate not only becomes water-soluble as originally intended, but also provides good scouring properties without impairing performance such as adhesive strength, which is the original characteristic of water-soluble polyester resin. As a result of further intensive research, we discovered that it imparts properties and enables continuous scouring with caustic soda.

The present invention has now been completed.

That is, in the water-soluble polyester paste according to the present invention, when producing a water-soluble polyester resin by esterifying at least one dicarboxylic acid and at least one diol and performing single polycondensation, phosphoric acid, at least one phosphoric acid compound selected from the group consisting of pyrophosphoric acid, polyphosphoric acid, and phosphoric acid, and - general formula HO(CH2)n-OH (wherein n is an integer from 2 to 6), or general formula
)1(OCR2CH2)m-OH (where m is 2-1
It is made of a water-soluble polyester 4#l fat prepared by adding 10% by weight or less of an esterified compound of the compound represented by (which is an integer of 0) based on the total amount of monomers.

Moreover, the second water-soluble polyester glue according to the present invention is
At least 20% to 90% of the water-soluble polyester resin as described above, a fatty acid having 14 to 28 carbon atoms, an alcohol wax of 1 to 41 degrees, an oxidized wax, and a natural wax with a melting point of 50 to 100°C. 1 type melting point 5
Wax emulsion 80 made by emulsifying wax at 0 to 100°C with a nonionic activator and/or anionic activator
-10mJit%.

The dicarboxylic acid component for producing the water-soluble polyester resin in the present invention is an aliphatic acid component.

(A ring or aromatic acid can be used. Examples of such dicarboxylic acids are sulfuric acid, malo/acid, dimethylmalonic acid, succinic acid, curtaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2.2
-dimethylgeltallohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid. 2.

These are 5-flubornanedicarboxylic acid, 1,4-naphthalic acid, siphenin #1, diglycol, thiodipropionic acid, and 2,5-naphthalenedicarboxylic acid.
Note that the dicarboxylic acid component in the present invention includes S anhydrides, esters, acid chlorides, and the like corresponding to the above-mentioned acids.

Moreover, as a diol component in the present invention.

Aliphatic, cycloaliphatic or aromatic diols can be used. Examples of these diols are ethylene glycol,
Propylene glycol, 1,3-propanediol, 2
．． 4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-diol, 3-propanediol,
2-Ethyl-2-butyl-1.

3-propanediol, 2-ethyl-2-ynbutyl-1.3-propanediol, 1.3-butanediol 1.4-butanediol, 1.5-pentan/ol, 1.8-hexanediol, 2. , 2.4 −)
riftyl-1,6-hexanediol, ■. 2-cyclohexane dimetatool, l,3-cyclohexane, methanol, 1.4-cyclohexane dimetatool, 2,
2. , 4,4,-tetramethyl-1,3-cyclobuta 7
Nool, 4.4'-thiodiphenol, 4.4'-methylenenonphenol, 4.4'-(2-/lupornylidene)diphenol, 4,4'-dihydroxybiphenol o-, m-, p-dihydroxy benzene 7, 4
．． 4'-isopropylidene diphenol, 4.4'-impropylidene bis(2.6-dichlorophenol)
,, 2.5-naphthalenediol, p-xylenodiol, diethylene glycol, triethylene 7 glycol, tetraethylene glycol, and the like.

In the production of the water-soluble polyester resin in the present invention, cycarpo7 containing one SO3M group (wherein M is hydrogen or a metal ion) bonded to an aromatic nucleus is used to make the polycondensate produced water-soluble. Diols (including derivatives thereof) or diols (including derivatives thereof) and other difunctional monomers may be used in combination. An example of such an aromatic nucleus is Hensen. Includes naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl and methylenodiphenyl. The metal ion of the above sulfonate base is.
Na, K, Mg, Ca, Cu,
and Fe.

Furthermore, in order to make the resulting polycondensate water-soluble, it can be neutralized with at least one alkali metal hydroxide, aqueous ammonia, or alkanolamine. Alkali metal hydroxides used as such neutralizing agents include hydrium hydroxide, sodium hydroxide, potassium hydroxide, etc., and alkanolamines include mono-, di-, and triethanolamine, and mono-hydroxide.

Di,tripropaturamine, amine methylpropanediol, aminomethylpropanediol, aminoethylpropanodiol, morpholine, etc. are used.

The wax emulsion (oil agent) used in the second water-soluble polyester glue according to Hikari 1 includes carnauba wax, carnauba wax, beeswax, white wax, and montan wax as natural waxes.

Bran wax, etc., and synthetic waxes such as oxidized polyethylene wax, oxidized wax, and wax obtained by esterification of sorbitan, pentaerythritol, glycerin, ethylene glycol, and fatty acids with carbon fi 14 to 28 are used as raw materials, and these are used as ordinary nonionic waxes. It is a wax emulsion made by using an activator and/or an anion activator. In the above, a small amount of low-melting point animal and vegetable oil or mineral oil can be used in combination, but since the glue film is largely plasticized, if too much is used in combination, the performance of the glue will deteriorate.

[For production]

Polyester resin is a linear polymer.
With water-soluble polyester resin as a glue!
In order to give the resin 1 toughness as a child actor to increase the adhesion strength, the α button was made long and the 1. It tended to be difficult to refine the materials.

On the other hand, in the water-soluble polyester resin of the present invention, at least one phosphoric acid compound selected from the group consisting of phosphoric acid, birophosphoric acid, polyphosphoric acid, and phosphorous acid and the general formula HO(CH2) are used in the manufacturing process. n-OH (wherein n is an integer from 2 to 6) or general formula H
(OCH2C)f2)m-OH (in the formula, 5m is an integer from 2 to 1o) esterified product (hereinafter simply referred to as the specified phosphoric acid ester) is added, and a linear polymer However, because the phosphoric acid component creates a cross-linked structure, the resin itself is sufficiently strong despite the low degree of polymerization of the linear portion. Furthermore, during scouring with caustic soda, the phosphoric acid component and the straight chain crosslinking part are cut, so the polymer easily decomposes, or in addition, the straight chain part itself has a low degree of polymerization, so it is in a state where it is more easily decomposed. Therefore, it is thought that the water-soluble polyester sizing agent of the present invention made of the resin can be continuously scoured with caustic soda. Furthermore, as mentioned above, conventional water-soluble polyester pastes tend to coagulate in caustic soda aqueous solutions due to the salting-out effect; Due to the action of acid esters, caustic soda easily dissolves in the main solution.

In addition, V-formation of the water-soluble polyester resin in the present invention
In addition to the above-mentioned effects, the addition of a certain phosphoric acid ester in step [step] also has the effect of improving the melt thermal stability of the polymer, accelerating hydrolysis, and reducing other side effects of the esterification catalyst. In addition, the blend f of this predetermined phosphoric acid ester is 10% or less based on the total amount of monomers, and especially in the case of polycondensation T under reduced pressure, it is 0.5 to 2%.
is the appropriate value, and in the case of polycondensation at normal pressure, 5 to 10% H,+% is 'Ii'. If it exceeds 10% and 7.1%, gelling and sizing of the resin will cause problems such as bronking of the yarn. In addition, if phosphoric acid, birophosphoric acid, polyphosphoric acid, or phosphorous acid is simply used as an additive instead of the specified phosphoric acid ester described in j.
This is inconvenient because the polycondensation reactivity deteriorates and time is consumed in the small assembly, and furthermore, problems such as discoloration of the tree 111i occur. In addition, there is no special limitation regarding +111 when adding the above-mentioned specified phosphoric acid ester as long as it exhibits the desired effect as described above, but if the specified phosphoric acid ester is mixed during transesterification, transesterification may be slightly inhibited. Since there is a possibility that

In the second water-soluble polyester sizing agent according to the present invention, a predetermined wax emulsion is used in combination with the water-soluble polyester resin as described above, and the scouring property is further improved and smoothness is imparted to the thread during sizing. As a result, the friction between the yarn and the system is slightly reduced and the binding force is also improved.

[Examples 1 to 12 and Comparative Examples 1 to 2] As described above, water-soluble polyester resin water of the present invention mt-A-F, comparative water-soluble polyester resin water RJH, and wax emulsion/PNQ were prepared, respectively. These water-soluble polyester resin aqueous solutions A-F of the present invention and comparative water-soluble polyester 4! Table 1 shows the test results of the solubility of each glue film in the Caseintar aqueous solution for the L fat aqueous solution H.

In addition, the above water-soluble polyester resin aqueous solution A-
Each sizing agent of F and comparative water-soluble polyester resin aqueous solution H (
Examples 1 to 6 and Comparative Example 1), and each glue formed by mixing a portion of the water-soluble polyester resin aqueous solution A-F of the present invention, a comparative water-soluble polyester resin aqueous solution H, and the above wax emulsion P-Q. (Examples 7-12 and Comparative Example 2), their sizing agents were 125 denier.

Table 2-1 and Table 2-2 show the test results for thread-system friction and sizing properties for the threads, and further scouring of the sizing agent. The test results of Song are shown in Table 3.

9 Polyester-A'126.1'g (0.65 mol) of methyl terephthalate.

29.9 g (0.18 mol) of isophthalic acid, 14.2 g (0.07 mol) of sepati/acid, 28.8 g (0.07 mol) of dimethyl sodium 5-sulfoisophthalate.
A mixture of 124 g of ethylene glycol and an esterification catalyst was stirred in a flask under a carbon dioxide atmosphere and heated to 250° C. over about 4 hours to carry out transesterification. After cooling, 2.0 g of ethylene glycol ester of phosphorous acid was added, and the pressure was reduced to 3 to 8 mmHg.
A hard polyester resin with a melting point of 110°C was obtained by polymerizing at 240-250°C for about 30 minutes.Then, the polyester resin was dissolved in water to make a 25% aqueous solution, and a transparent liquid was obtained. This is used as the water-soluble polyester resin aqueous solution A of the present invention.

-Polyester 1 "'"B-.

Dimethyl terephthalic acid 77.8g (0.4 mol)
Isophthalic acid? 4.7g (0.45 mol), amber chuan 11.8g (0.1 mol), dimethyl sodium 5-sulfoisophthalate 14.8g (0.05 mol)
A mixture of 124 g of ethylene glycol and an esterification catalyst was stirred in a flask under a carbon dioxide atmosphere and heated to 250° C. over about 4 hours, resulting in transesterification. After cooling, add 4.0 g of diethylene glycol ester of polyphosphoric acid and reduce the pressure to 3 to 8 m*.
A hard polyester resin with a melting point of 100°C was obtained by polymerizing Hg at 240-250°C for about 30 minutes.Then, the polyester resin was dissolved in water to make a 25% aqueous solution, and a transparent liquid was obtained. This is used as A: Invention water-soluble polyester resin aqueous solution B.

r-polyester tree-'JC's... 3g (o, 5 mol) of terephthalic acid, 4L8 of isophthalic acid
g (0.3 mol), adipic acid 14.6 g (
0.1 mol), dimethyl sodium 5-sulfoisophthalate 29.8 g (0.1 mol), ethylene glycol 93 g,! , 45 g of 4-butanediol to which an esterification catalyst was added was heated to 250°C over about 4 hours while stirring in a carbon dioxide atmosphere in a flask.
Transesterification was performed. After cooling, add 8.0 g of diethylene glycol ester from the liquor.

A hard polyester resin with a melting point of 110°C was obtained by combining Kanto at a reduced pressure of 3 to 8 feet Hg at 240 to 250°C for about 30 minutes.Then, the polyester resin was dissolved in water to make a 25% aqueous solution, and a transparent solution was obtained. A liquid was obtained. This is used as the water-soluble polyester resin aqueous solution C of the present invention.

/'I　　''゛Polyester °II' 斤°D tone.

Terephthalic acid58. l g (0.35 mol), Isophthal I! l183.0g (0.5 mol),
Dodeca7 2il @ 25.8 g (0.1 mol),
Dimethyl sodium 5-sulfoisophthalate 14.8
g (0.05 mol), ethylene glycol Il
A mixture of 236 g of 1,6-hexaneol and 236 g of 1,6-hexaneol was stirred in a flask under a 75% gas atmosphere and heated to 250°C over about 4 hours to carry out transesterification. I did this.

After filtration, ethylene glycol ester of phosphorous acid 5.0
g, and vacuum 3-8 ml IHg, 240-250°C.
A hard polyester resin with a melting point of 100° C. was obtained by polymerization for about 30 minutes, and then the polyester resin was dissolved in water to make a 25% aqueous solution, and a clear liquid was obtained. This is used as an aqueous solution of the water-soluble polyester resin of the present invention.

Un-Akebono r Polyester 'E's dimethyl terephthal fi? ? , fig (0.4 mol), dimethyl isophthalic m77.8 g (0.4 mol), adipine chuu 29.2 g (0.2 mol), ethylene glycol 124 g, ethylene glycol ester of pyrophosphoric acid 3
While stirring 0 g of esterification catalyst in a flask under a carbon dioxide atmosphere, it was heated to 250 g over about 4 hours.
Raise the temperature to ℃. Thereafter, excess ethylene glycol was discharged from the reaction system, and polymerization was carried out at 240 to 250°C for about 1 hour under normal pressure to obtain a hard polyester resin with a melting point of 100°C. continue.

When the polyester resin No. 7 was neutralized with 78 g of an aqueous solution of caustic soda diluted to 10% to make a 20% aqueous solution, a transparent liquid was obtained. This is used as the water-soluble polyester 8N fat aqueous solution E of the present invention.

Wood C Polyester F' Dimethyl terephthalic acid 58.2 g (0.3 mol)
, trimethylisophthalfi 77.8 g (0,4
mol), succinic acid 35.4 g (0.3 mol), ethylene glycol! A mixture of 24 g and 21 g of phosphorus-poor diethylene glycol ester added with an esterification catalyst is heated to 250° C. over about 4 hours while stirring in a carbon dioxide atmosphere in a flask. After that, excess ethylene glycol was discharged out of the reaction system, and the temperature was raised to 240-250°C.
Polymerization was carried out at normal pressure for about 1 hour to obtain a hard polyester resin with a melting point of 30°C. Next, the polyester resin was neutralized with 10 g of ammonia water (10%), and 2
When made into a 0% aqueous solution, a transparent liquid was obtained. This is used as an uninvented water-soluble polyester resin water-soluble i&F.

Polyester tree "JL" J Dimethyl terephthal M12G, 1g (0.85 mol)
.

29.9 g (0.18 mol) of isophthalic acid, 4.2 g (0.07 mol) of heptanoic acid I, 29.6 g (0.1 mol) of methyl sodium 5-sulfoisophthalate.
mole), a mixture of 124 g of ethylene glycol and an esterification catalyst; and 1 (Test method) Attachment 1t-HC%): Scouring loss; Measured according to 5.

Friction between yarn and system: 20℃, 65% using a yarn friction binding force tester
%RH and a load of 500 g/10 threads, observe the fluffing state due to friction between the threads and the system at five locations. Thread-system n
The rub is evaluated using the following symbols: ■ (no fuzz), 0 (almost no fuzz), Δ (little fuzz), and × (many fuzz).

Sizing properties: #M indicates the state of the glue after the thread is run for 5000 m in a water jet loom at a rotation speed of 400 times/min, a thread speed of 20 cm/min, and a running tension of 40 g. ! ! Sympathize. The adhesive removal property is evaluated using the following symbols: O (no glue removed), 10 (almost no glue removed), Δ (little glue removed), and × (many glue removed).

(The following is the margin of this page) Table 2-L Table 2-2 Note: The blending amount in the sizing agent composition column is shown in Toryobu Hikibu (Toryobu Hikibu).

1m i, l practice 1 (excluding tester 7) i, +r, circular in the center of Renshu/Tetron footer 3%
Apply glue and heat set after preliminary drying.
After scouring and field washing, dyeing is performed and dyeing spots are evaluated. Pre-drying at 130℃ for 1 minute, heat setting at 180℃
°C for 20 seconds, scouring bath composition is caustic soda 2.0g/l
, Sodium triplyphosphate 0.5g/l Score Roll 450 (Nonionic jIII paste made by Hana E Ishichichi) 20g/l
Text, scouring bath temperature is 35℃, hot water washing is 10 seconds at 60℃, water washing is 10 seconds at room temperature, and dyeing bath composition is Roguemi 7B 0.
．． The evaluation method of scouring property is carried out under each condition of 2g/cross.
This is done using the following symbols: (no glue remains), Δ (residual glue is 1·v), and × (clear glue remains).

(This is a blank page on the next page) As shown in the test results in Table 11, Table 2-1, Table 2-2, and Table 3, the water-soluble polyester resin aqueous solution A of the present invention
-F has a much higher solubility in the caustic soda aqueous solution than the comparative water-soluble polyester resin aqueous solution H, and the water-soluble polyester pastes according to Examples 1-12, especially the water-soluble polyester pastes according to Examples 7-12 containing wax emulsions. Compared to the water-soluble polyester pastes according to Comparative Examples 1 and 2, the water-soluble polyester paste has much better scouring properties, and also has good sizing properties in terms of yarn binding strength and sizing properties.

〔Effect of the invention〕

As described above, in the water-soluble polyester sizing agent of the present invention, a specified phosphate ester is added in the manufacturing process of the water-soluble polyester resin, and the sizing agent has good thread cohesion and adhesive strength, and there is little slip-off of the sizing agent. , excellent scouring properties 1
The M-kneading process can easily be made into one continuous scouring process.

In addition, the water-soluble polyester sizing agent containing a predetermined wax emulsion according to the present invention has further improved scouring properties compared to the above-mentioned sizing agent, and furthermore, the sizing agent has a 4.61 property of 11
- Since the fibers can be stretched, friction between the threads and the yarn system is reduced, and binding strength is improved.

that's all

Claims (2)

[Claims] (1) When producing a water-soluble polyester resin by esterifying and polycondensing at least one dicarboxylic acid and at least one diol, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, or phosphorous acid is used at the latest during the polycondensation. at least one phosphoric acid compound selected from the group consisting of the general formula HO-(CH_2)_n-OH (wherein n is an integer from 2 to 6), or the general formula H-(OCH_2CH_2)_m-OH (In the formula,
(m is an integer of 2 to 10) A water-soluble polyester glue made of a water-soluble polyester resin, in which 10% by weight or less of an esterified compound of the following formula is added based on the total amount of monomers. (2) When producing a water-soluble polyester resin by esterifying and polycondensing at least one dicarboxylic acid and at least one diol, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, or phosphorous acid is used at the latest during the polycondensation. at least one phosphoric acid compound selected from the group consisting of the general formula HO-(CH_2)_n-OH (wherein n is an integer from 2 to 6), or the general formula H-(OCH_2CH_2)_m-OH (In the formula,
m is an integer of 2 to 10) 20 to 90% by weight of a water-soluble polyester resin obtained by adding 10% by weight or less of an esterified product of the compound represented by the formula (m is an integer of 2 to 10) based on the total amount of monomers, and a fatty acid having 14 to 28 carbon atoms. 1~
At least one member selected from the group consisting of tetrahydric alcohol esters, oxidized polyethylene wax, oxidized wax, and natural waxes with a melting point of 50 to 100°C
Wax emulsion 80-10 made by emulsifying wax at 00°C with a nonionic activator and/or anionic activator
A water-soluble polyester glue made by mixing % by weight.