JPS61124686A - Size for hydrophobic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a polyester-based polyester [3
(Relating to a sizing agent for hydrophobic fibers whose main ingredient is fat.

[Prior art and its problems 1 Recently, auto-jet weaving machines, which manufacture textiles by flying the warp threads by jetting water instead of the shuttle used in conventional 'jA weaving, have been operating at high speed. This method is becoming more and more popular in general because it is possible to significantly improve weaving efficiency.

Since a large amount of water is used in this method, a textile glue suitable for this method is required to have sufficient water resistance for the glue film after drying, as well as sufficient water resistance for post-processing such as dyeing. It is also necessary to have good desizing properties, and a sizing agent for automatic wet rooms must be able to fully satisfy the contradictory properties of water resistance and desizing properties.

The most typical type of such glue is an acrylic ester-acrylic acid copolymer based glue, but its binding power is not satisfactory compared to polyester type 1, and efficient sizing is not possible. is the reality. In addition, in order to further improve weaving efficiency in the weaving industry, the above-mentioned automatic jet 5
! ! Although there is a trend toward further increasing the operating speed of m11, a glue having sufficient binding power to withstand such increased speeds has not yet been found. For this reason, the method of increasing the conjugation strength by increasing the 7° of glue to IILM# has been adopted, but of course this not only increases the amount of glue used, resulting in a large economic loss. In addition, with conventional adhesives, the concentration of the aqueous solution must be increased in order to increase the amount of adhesive applied, and as a result, the viscosity increases sharply, so there is a problem in that the viscosity must be lowered by heating. Furthermore, if the amount of sizing is increased, a large amount of sizing residue is generated as the weaving speed increases, resulting in contamination of the fabric and a decrease in desizing performance, which increases the burden of post-processing.

Therefore, there is an urgent need for a sizing agent that has excellent binding power regardless of the amount of sizing applied, and the above-mentioned sizing agent exists.

[Means for Solving the Problem 1] However, the present inventors have long found that polyester resins with high molecular weight and high acid value have relatively excellent performance as fiber glue, and have conducted research on such polyester resins. However, as a result of further investigation, it was discovered that polyester resin obtained by a specific manufacturing method exhibits excellent physical properties, and the present invention was completed. That is, in the present invention, two or more polyester resins are used to obtain Otlag/g polyester resin, and then three or more polyester resins are obtained.
Number average molecular weight 5.000-50,000, acid 1i50-140K obtained by adding a polycarboxylic acid with a higher value
It is characterized by using a polyester resin of on g/g as a fiber sizing agent.

In the present invention, the initial effects can only be obtained by using a polyester resin obtained using such a manufacturing method, and the i! Even if the remaining resin is used as a sizing agent for fibers, it will not achieve the purpose of the present application, that is, a sizing agent with excellent binding power and desizing properties. Although the reason for this is not clear, it is thought to be due to differences in the molecular structures of the resins due to different manufacturing methods.

Hereinafter, the sizing agent for fibers of the present invention will be sequentially explained in relation to the production of polyester resin.

First, as the polyester 171 resin used in the reaction with the epoxy compound, any general-purpose polyester 171 resin can be used, but it is preferable that the number average molecular weight is about 700 to 4.500 and the acid value is about 2.
5 to 140 KOHmg/g of polyester resin is preferred. Further, the resin is preferably linear rather than branched. For this purpose, a dicarboxylic acid is mainly used as the acid component, and a dihydric alcohol is mainly used as the polyhydric alcohol. Dicarboxylic acids include terephthalic acid, isophthalic acid, malonic acid, dimethylmalonic acid, succinic acid, geltaric acid, 7
Nopic acid, trimenoic acid, itafonic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, l,3-cyclopentanedicarboxylic acid, 1,4-
Cyclohexanedicarboxylic acid, 2゜5-flupornannocarboxylic acid, 1.4-naphthalic acid, nofenic acid, 4
, 4'-oxybenzoic acid, nobricolic acid, thionopropion, and 2,5-naphthalene dicarboxylic acid.

These may be acid anhydrides, esters, Chlorai V, etc., such as dimethyl 1,4-cyclohexanenocarboxylate, dimethyl 2,6-7taledicarboxylate, dimethyl isophthalate, dimethyl terephthalate, and dimethyl terephthalate. and nophenyl terephthalate.

Examples of dihydric alcohols include ethylene glyfur, diethylene glycol, propylene gelicol, 1,3-propantool, 2,4-dimethyl-2-ethylhexane-1°3-nool, 2,2-dimethyl-1, 3-7'
Ropanol (neopentyl glycol), 2-ethyl-2-buf-1,3-propantool, 2-ethyl-2-isobutyfurane 1,3-propanedio-J,
1.3-butanol, 1,4-l, 1,2-cyclohexanenomethanol, 1.3-cyclohexanenomethanol, 1.4-cyclohexanenomethanol, 2,
2,4,4-tetramethyl-1,3-cyclobutanol, 4,4'-thionophenol, 4,4'-methylenezphenol, 4,4'-(2-norbornylidene)
nophenol, 4,4'-dihydroxybiphenol,
0-m- and p-nohydroxybenzene, 4.4'-isopropylidenephenol, 4,4'-isopropylidene bis(2,6-cyclophenol/di), 2.5
-S7tale diol and p-xylene diol.

No special operation is required to produce a polyester resin by condensing the acid component mainly consisting of dicarboxylic acid and dihydric alcohol, and the polyhydric alcohol component, and any conventionally known method may be used. For example, a polyvalent furfur component in an amount of 1.1 to 1.7 times the mole of the acid component is charged into a reactor together with a catalyst, and the temperature is raised to 140 to 230°C to carry out dehydration condensation. As catalysts used in this case, zinc acetate, zinc chloride, stannous lauryl, butyltin oxide, etc. are used, and these are usually 0.0% of the dicarboxylic acid.
5 to 0.15 parts by weight of the polyester resin is reacted with an epoxy compound having two or more glycidyl groups to effect chain extension. Such epoxy compounds include ethylene glycol noglycinole ether, noethylene glycol noglycinole ether, triethylene glycol noglycinole ether, polyethylene glycol diglycidyl ether, propylene glycol noglycidyl ether, polypropylene glycol diglycidyl ether,
Neopentyl glycol diglycinol ether, 1.6
-Hexanesiol diglycidyl ether, bisphenol A type noglycidyl ether, bisphenol A type ethylene oxide adduct noglycidyl ether, bisphenol A type propylene oxide 7 duct noglycidyl ether, hydrogenated bisphenol A type noglycidyl ether, water temperature bisphenol A type ethylene oxide Adduct diglycinole ether, hydrogenated bisphenol A type propylene oxide 7 duct no glycidyl ether,
Noglycinol 7 dipic acid diglycinol ester, diglycidyl pimelic acid diglycinol ester, diglycidyl isophthalate ester, noglycidyl terephthalate, 01
cycloaliphatic epoxy compounds such as al+ll-hydroxybenzoic acid diglycidyl ester ether, 1,3-diglycidyl-5.5-methylhydantoin, cyclohexanenool noglycidyl ether, cyclohexanenocarboxylic acid noglycidyl ester, etc. glycerin,
+ such as pentaerythritol, trimethylolpropane, etc.
(1i furfur in which at least two of the hydroxyl groups are glycidyl ether groups, or polybasic acids such as trimellitic acid and pyromellitic acid in which at least two of the carboxyl groups are glycidyl esters can be used as desired.

In order to extend the chain by reacting the epoxy compound with the polyester resin, (n-2) of the epoxy compound is added to n moles of carboxyl groups of the polyester resin.
Do it to a certain extent.

In this way, one glycidyl group in the epoxy compound and the carboxyl group in the polyester resin are bonded by an ester reaction, resulting in chain extension, that is, crystallization, and hydroxyl groups corresponding to the number of glycidyl groups involved in the reaction are generated in the polyester resin. However, in the present invention, such 6
, 000~30, 000, 25~140 KOl1
mg/g, more preferably 35-90 KOHmg/g
It is desirable for the resin of the present invention to be within this range. If the number average molecular weight is larger than this,
Alternatively, if the hydroxyl value is smaller than this, even if a trivalent or higher polyvalent carboxylic acid is added by the means described below, the desizing property as a sizing agent will be reduced, and conversely, if the molecular weight is small5), if the hydroxyl value is large, Since the conjugation strength tends to decrease, the object of the present invention cannot be achieved.

Polyester method obtained as above (3% for fat)
Acids that are used for the purpose of the present invention include 4-methylcyclohexene-1.2.3-tricarboxylic anhydride, trimesic acid, etc., which are added with polyvalent carboxylic acids having a higher functional level. These may be used alone or in combination of two or more.

This reaction is usually carried out continuously following the above chain extension, so no particular solvent replacement is required.6 The amount charged is polyester +
The ratio of the polyhydric carboxylic acid to the hydroxyl group in one fat is preferably equivalent to the equivalent mole in terms of carboxyl group. When a polyhydric carboxylic acid is charged, it is carried out at a temperature of 150 to 200° C. under normal pressure or, if necessary, under increased pressure, and the reaction is allowed to proceed for 1 to 10 hours to advance esterification. When darning, the polyhydric carboxylic acid may be added all at once or continuously, but the method is very sensitive. At the same time, additional catalyst may be added.

The polyester resin thus obtained has a number average molecular weight of 5.
,000~so,ooo, more preferably 5,000~
30,000, acid value 50-140 KOH bias g/g, preferably in the range of f3G-140 to QhiI/g. Less than 5,000 or 140 KOs
tlB In the present invention, when preparing a sizing agent using the above-mentioned polyester type 1 (fat), it is usually necessary to dissolve it in alkaline water such as ammonia water.The solid content concentration of the sizing agent is determined in consideration of workability. It is appropriate that the viscosity is in the range of about 5 to 20 cps (measured at 20°C) at a concentration of 10% by weight.For vaginal fluid, any textile processing agent, Softeners, plasticizers, fiber auxiliaries, etc. may be used in combination with the polyester resin, as long as the effects of the present invention are not impaired, and acrylic resin pastes, polyvinyl alcohol resin pastes, starch pastes, and conventionally known pastes may be used. A polyester resin glue or the like may be used in combination.

The sizing agent of the present invention is widely used in weaving using an automatic jet-armed textile machine, regardless of the type of sizing yarn, for example, hydrophobicity, strength or weakness, synthetic fiber, natural fiber, filament yarn, or spun yarn. It is suitable as a sizing agent for fiber manufacturing. Of course, any method other than this method can also be used for gluing.

[Effect 1 It is much better, and of course the desizing properties are also very good.

(Implementation example 1 Next, the present invention will be explained in more detail by giving examples.

In the examples, "parts" and "1%" are based on weight unless otherwise specified.

Further, the abbreviations in the examples have the following meanings, and the 3'l' position of the acid value and hydroxyl value is 011 mg; g.

TPA: tele-7-talic acid, IP^: iso-7-talic acid, EG:
Ethylene glycol, DEC:noethylene glycol, TE(::)lyethylene glycol, Bis^-DG
E: Bisphenol A type diglycinol ether, TH8: trimellitic anhydride, ^^ nialic acid, H methyl acrylate, ε^ ethyl niarylate, 13A bunal niacrylate, MM methyl methacrylate ^V: acid value ,
0IIV: hydroxyl value, Mn average molecular weight, acid value,
The hydroxyl value and number average molecular weight were calculated using the following formula.

- Acid fIIIi (AV) aiog): Sample ((J (fat) titration b (mg) Ni blank titration.

W (g): Weight of sample ": Titer and hydroxyl value (OHV") of the used 0, IN KOH titrant solution 1 a, b, f, l!l are the same as above ・Number average molecular weight (Ha) m: Total number of carboxyl groups and hydroxyl groups in one molecular weight of resin Production of polyester as raw material (1) 1.1 mol of TPA and IP^1. 1 mol, EC
2.3 mol, TE (: 1.1 mol, and 0.1 part of dibutyltin oxide, 0.ill! 7thimony dioxide!
After charging and esterifying at 170-260°C, 0.
Perform polycondensation under vacuum with 1 to 1.0 mm 1 g, ^v 1,
A polyester resin with Mn 1,000 was obtained. Using this resin as a raw material polyester (No. 1), two types of raw material polyesters having different compositions were separately produced in the same manner. These are each numbered 2.3. Each U (fat composition ^V, Mn is shown below.

・Resin composition of number 2 TP^/IPA/EC/[1EG= 1.1/1
．． 4/2.1/1.1 (mol) x However, IP^ is 1.・1
Of the moles, 0.3 moles were subjected to depolymerization reaction l.
3/2.1/1.3 (mol) x However, for IP^, 0.2 mol out of 1.3 mol is used for depolymerization reaction AV 45, Hn 2,500 Manufacturing side of polyester resin by chain extension Raw material polyester (Number 1) 500. and Bis^-D(:E 14
Pour 1g at once and heat to 170-18% under nitrogen atmosphere.
The reaction was carried out at 0'C for 5 hours. The resulting polyester resin was OHV 79.1 (denoted as prepolymer in the table). The results are shown in Table 1.

Production of polyester resin by f1 addition reaction Temperature 500g of the above chain-extended polyester resin as shown in Table 2
AV 124
, a polyester resin having an Mn of 16,300 was obtained. This polyester resin is designated as N001. Similarly, N00
2 to 6 were manufactured. The results are also shown in Table 1.

The manufacturing method is the same as that for polyester resin N091, but Bis^-DEG and T used for chain extension and addition reaction.
For comparison, the raw material polyester was ^V220, Mn 500, and AV 22, M by changing the amount of MAo charged.
These are NO6 using two types of resins of n5.000.
Chain extension and addition reaction are carried out according to case 1, and finally ^
v180, Mn 18.500 resin, AV 21, M
A resin of n10.700 was produced. Each of these is NO,
7, 8.

EXAMPLE A Bolier aqueous solution was prepared from 100 g of the resins N001 to 6 obtained in the above manner. This was used as a glue for an over-the-counter room, and its performance was evaluated.

The results are shown in Table 2.

Comparative Examples No. 7, 8 and two types of commercially available acrylic Water Noette room glues (these will be referred to as No. 9, 10)
was used as a sizing agent according to the example.

The results are also shown in Table 2.

However, performance evaluation was performed as follows.

Raw yarn: Polyester yarn (50d/24 filament) Sizing conditions: ■Sizer Warping Slanosha @ Sizing temperature 20°C θ Sizing speed 100 m/win: @Drying speed Chamber 120°C Cylinder 90°C Input 90°C Desizing was carried out three times, and the weight was measured after washing with water and drying, and the weight was calculated from the difference in weight between the sized yarn and the sized yarn.

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

Conjugation force test Using Matsui Seiki TM type conjugation force test rock, a load of 100g,
The average number of frictions until yarn breakage was measured at an angle of 145° (10 mm).

Desizing rate Sized thread 2-3. Add 100 g to 100 times the amount of water and add 80 to 85 g.
Desizing was performed at ℃ for 5 minutes, washed with water, and after drying, the weight was measured, and the amount of desizing was determined from the difference in weight between the sizing yarn and the desizing yarn, and the ratio to the adhesion amount was shown.

(Margin below) Table 2

Claims (1)

[Claims] Polyester resin is chain-extended with an epoxy compound having two or more glycidyl groups to obtain a number average molecular weight of 4,000.
0-50,000, hydroxyl value 25-100KOHmg/
A number average molecular weight of 5,000 obtained by obtaining a polyester resin of g and further adding a trivalent or higher polyvalent carboxylic acid to this.
50,000 and an acid value of 50 to 140 KOHmg/g. A sizing agent for hydrophobic fibers whose main ingredient is a polyester resin.