JPH054465B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a sizing agent for hydrophobic fibers, which has improved binding power and desizing properties, and which exhibits sufficient performance with a smaller amount of sizing than conventional ones, and whose main ingredient is a polyester resin. [Prior art and its problems] Recently, waterjet weaving machines, which manufacture textiles by flying warp threads with a jet of water instead of the shuttle in conventional weaving machines, 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 weaving machine 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 desizing properties, and a sizing agent for water jet rooms must be able to fully satisfy the contradictory properties of water resistance and desizing properties. The most typical type of sizing agent is an acrylic ester-acrylic acid copolymer sizing agent, but its binding power to polyester fibers is unsatisfactory and efficient sizing is not possible. This is the reality. In addition, polyester-based adhesives have been disclosed in Japanese Patent Publication No. 47-40873, Japanese Patent Publication No. 55-51071, Japanese Patent Application Laid-Open No. 150176-1980, etc., but these adhesives have not been able to meet recent performance requirements. is no longer able to respond adequately. That is, in the weaving industry, there is a trend to further increase the operating speed of water jet looms in order to further improve weaving efficiency, but weaving machines that have sufficient binding power to withstand such speed increases I still can't find the glue.
For this reason, the method of increasing the binding force by increasing the amount of glue applied to the fibers is exclusively adopted, but of course the amount of glue used increases, which not only results in a large economic loss, but also There is a problem in that the concentration of the aqueous solution must be increased in order to increase the amount of pasting, and as a result, the viscosity increases sharply, so the viscosity must be lowered by heating. Furthermore, when the amount of glue is increased, a large amount of starch is generated due to the faster weaving, which may contaminate the woven fabric.
It has the disadvantage that the post-processing burden increases, such as a decrease in desizing properties. Therefore, there is an urgent need for a sizing agent that has excellent binding power regardless of the amount of glue applied, but as mentioned earlier, binding power and desizing performance are contradictory to each other. However, there were various problems such as a decrease in desizing properties when the conjugation strength was improved. [Means for Solving the Problems] 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, polyester resin is chain-extended with an epoxy compound having two or more glycidyl groups to obtain a polyester resin with a number average molecular weight of 4000 to 50000 and a hydroxyl value.
Obtain a polyester resin with a content of 25 to 100 KOHmg/g and further add a trivalent or higher polycarboxylic acid to the resulting polyester resin with a number average molecular weight of 5000 to 50000 and an acid value of 50 to 50.
It is characterized by using a polyester resin containing 140 KOHmg/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 production method, and polyester resins obtained by other than such methods, such as acid components, glycol components, and Even if a resin produced by adding trivalent or higher polycarboxylic acid components at once and making the final composition ratio equal to that of the present application is used as a sizing agent for fibers, it will not meet the objectives of the present application, that is, it has excellent binding power and is This does not result in a sizing agent with excellent removability.
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 fiber sizing agent of the present invention will be explained in the order of production of polyester resin. First, as the polyester resin used for the reaction with the polyester compound, any general-purpose polyester resin can be used, but preferably a polyester resin having a number average molecular weight of about 700 to 4,500 and an acid value of 25 to 140 KOHmg/g. 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, 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, 2,5-norbornanedicarboxylic acid, 1,4-naphthalic acid, diphenic acid, 4,
Examples include 4'-oxybenzoic acid, diglycolic acid, thiodipropion, and 2,5-naphthalene dicarboxylic acid. These may be acid anhydrides, esters, chlorides, etc., such as dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl isophthalate, dimethyl terephthalate, dimethyl terephthalate, and diphenyl terephthalate. Including etc. Further, dihydric alcohols include ethylene glycol, diethylene glycol, propylene 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-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,
2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, 4,
4'-methylene diphenol, 4,4'-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidene diphenol, 4 ,4'-isopropylidene bis(2,6
-dichlorophenol), 2,5-naphthalene 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 polyhydric alcohol 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 perform dehydration condensation. Catalysts used in this case include zinc acetate, zinc chloride,
Stannous lauryl, dibutyltin oxide, etc. are used, and these usually have a concentration of 0.05 to
Contains 0.15 parts by weight. A solvent is not particularly required, but if necessary, an inert solvent such as methyl acetate, benzene, acetone, xylene, toluene, etc. may be used. Chain extension is performed by reacting such a polyester resin with an epoxy compound having two or more glycidyl groups. Such epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 6-hexanediol diglycidyl ether, bisphenol A type diglycidyl ether, bisphenol A
type ethylene oxide adduct diglycidyl ether, bisphenol type A propylene oxide adduct diglycidyl ether, hydrogenated bisphenol type A diglycidyl ether, hydrogenated bisphenol type A ethylene oxide adduct diglycidyl ether, hydrogenated bisphenol type A propylene oxide Adduct diglycidyl ether, diglycidyl oxalate, diglycidyl malonate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, diglycidyl sebacate, diglycidyl phthalate. Glycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, o, m, p-hydroxybenzoic acid diglycidyl ester ether, 1,3-diglycidyl-
In addition to 5,5 dimethylhydantoin, alicyclic epoxy compounds such as cyclohexanediol diglycidyl ether and cyclohexanedicarboxylic acid diglycidyl ester, and at least two of the hydroxyl groups of polyhydric alcohols such as glycerin, pentaerythritol, and trimethylolpropane. It is possible to optionally use glycidyl ether groups in which at least two of the carboxyl groups of polybasic acids such as trimellitic acid and pyromellitic acid are glycidyl ether groups. When reacting the epoxy compound with the polyester resin to extend the chain, the epoxy compound is present in a ratio of (n-2) moles to n moles of carboxyl groups of the polyester resin,
It is preferably carried out under a nitrogen atmosphere, under normal pressure or, if necessary, under increased pressure at a temperature of 60 to 180°C for about 5 to 24 hours. In this way, one glycidyl group in the epoxy compound and the carboxyl group in the polyester resin bond through an ester reaction, leading to chain extension, that is, polymerization, and hydroxyl groups equivalent to the number of glycidyl groups involved in the reaction are generated in the polyester resin. However, in the present invention, the number average molecular weight and hydroxyl value of the polyester resin obtained by such a reaction are each 4000 to 50000, more preferably 6000 to 50000.
30000, 25~140KOHmg/g, more preferably 35~
A range of 90 KOHmg/g is desirable from the standpoint of ultimately producing the resin of the present invention. If the number average molecular weight is larger than this or the hydroxyl value is smaller than this, even if a trivalent or higher polycarboxylic acid is added by the means described below, the desizing property as a sizing agent will decrease, and conversely, the molecular weight will decrease. If the hydroxyl value is small or the hydroxyl value is large, the conjugation power tends to decrease, making it impossible to achieve the object of the present invention. A trifunctional or more functional polycarboxylic acid is added to the polyester resin obtained as described above to obtain the resin targeted by the present invention. Examples of trivalent or higher polyhydric carboxylic acids include trimellitic acid, trimetic anhydride, pyromellitic acid, pyromellitic anhydride, and 4-methylcyclohexene.
Examples include 1,2,3-tricarboxylic anhydride and trimesic acid. These may be used alone or in combination of two or more. Since this reaction is usually carried out continuously following the above chain extension, no particular solvent replacement is required. The amount to be charged is preferably such that the polyhydric carboxylic acid is equivalent to the equivalent mole of carboxyl groups to the hydroxyl groups in the polyester resin. When preparing polyhydric carboxylic acid,
Esterification 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. In this case, the polyhydric carboxylic acid is
The method may be arbitrary, whether it is charged all at once or continuously. At the same time, additional catalyst may be added. The polyester resin thus obtained has a number average molecular weight of 5,000 to 50,000, more preferably 8,000 to 50,000.
30000, acid value 50-140KOHmg/g, more preferably
Must be in the range 60-140 KOHmg/g.
If it is less than 5000 or higher than 140KOHmg/g, the conjugation power will decrease, and if it is greater than 50000 or 50KOH
If it is less than mg/g, desizing properties will be reduced. In the present invention, when preparing a sizing agent using the above-mentioned polyester resin, it is usually necessary to dissolve it in alkaline water such as aqueous ammonia. The solid content concentration of the size liquid is 5 to 20% by weight considering workability.
degree, and its viscosity is 5 to 5 at a concentration of 10% by weight.
It is appropriate to keep it within a range of about 20 cps (measured at 20°C). The liquid contains any fiber processing agent,
Softeners, plasticizers, textile auxiliaries, etc. may be used in combination. In addition, an acrylic resin paste, a polyvinyl alcohol resin paste, a starch paste, a conventionally known polyester resin paste, etc. may be used together with the above polyester resin within a range that does not impair the effects of the present invention. The sizing agent of the present invention is widely used in weaving using a waterjet type weaving machine, 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 sizing agent for weaving. Of course, any method other than this method can also be used for gluing. [Effects] As mentioned repeatedly, the fiber sizing agent of the present invention has much better binding power than conventionally known polyester fiber sizing agents, and of course also has very good desizing properties. [Example] Next, the present invention will be explained in more detail by giving examples. In addition, "parts" and "%" in the examples are based on weight unless otherwise specified. Further, the abbreviations in the examples have the following meanings, and the units of acid value and hydroxyl value are both KOH mg/g. TPA: Terephthalic acid, IPA: Isophthalic acid,
EG: ethylene glycol, DEG: diethylene glycol, TEG: triethylene glycol,
BisA-DGE: bisphenol A diglycidyl ether, TMAn: trimellitic anhydride, AA:
Acrylic acid, MA: methyl acrylate, EA: ethyl acrylate, BA: butyl acrylate,
MMA: methyl methacrylate AV: acid value, OHV: hydroxyl value, Mn: number average molecular weight In the example, the acid value, hydroxyl value, and number average molecular weight were calculated from the following formula. ●Acid value (AV) AV (KOHmg/g) = (a-b) x 5.611 x f/W a (mg): Titration amount of sample (resin) b (mg): Titration amount of blank W (g): Weight of sample f: Potency of 0.1N KOH titration power used ● Hydroxyl value (OHV) OHV (KOHmg/g) = 5.611 x (ba-a) x f/W + AV a, b, f, W are as above. Same number average molecular weight (Mn) Mn=56.11×1000/OHV×m m: total number of carboxyl groups and hydroxyl groups in one molecular weight of resin Production example of polyester as a raw material Stirrer, rectification column, nitrogen introduction tube, vacuum device Add 1.1 mol of TPA, 1.1 mol of IPA to a 1-volume reaction vessel with
2.3 moles of EG, 1.1 moles of TEG, 0.1 part of dibutyltin oxide, and 0.1 part of antimony trioxide are charged, and after esterification at 170 to 260°C, 0.1 to 1.0 mm
Polycondensation was performed under Hg vacuum to obtain polyesters of AV1 and An20000. Furthermore, 0.6 mol of IPA was added to the system and depolymerized at 180 to 220°C for 2 hours.
A polyester resin with AV112 and Mn1000 was obtained. This resin is designated as raw material polyester (number 1). Two types of raw polyesters having different compositions were separately produced in the same manner. These are numbered 2 and 3, respectively. Each resin composition AV and Mn are shown below. ●Resin No. 2 Composition TPA/IPA/EG/DEG=1.1/1.4/
2.3/1.1 (mol) *However, 0.3 mol out of 1.4 mol of IPA is used for depolymerization reaction AV56, Mn2000 ●Resin number 3 Composition TPA/IPA/EG/TEG=1.1/1.3/
2.1/1.3 (mol) *However, 0.2 mol out of 1.3 mol of IPA is used for depolymerization reaction AV45, Mn2500 Example of manufacturing polyester resin by chain extension Raw material polyester (number 1) 500g, and Bisa
141 g of -DGE was charged at once and the reaction was carried out at a temperature of 170 to 180° C. for 5 hours under a nitrogen atmosphere. The obtained polyester resin had OHV79 and Mn12800.
Chain-extended polyester resins (denoted as prepolymers in Table 1) were obtained in the same manner as for the raw material polyester resins No. 2 and below. The results are shown in Table 1. Example of production of polyester resin by addition reaction: Using 500 g of the chain-extended polyester resin shown in Table 2, it was charged with 0.92 mole of TMAn and subjected to an addition reaction at a temperature of 160 to 170°C for 2 hours.
A polyester resin of AV124 and Mn16300 was obtained.
This polyester resin is designated as No. 1. in the same way
Nos. 2 to 6 were manufactured. The results are also shown in Table 1. The manufacturing method is the same as No. 1 polyester resin, but BisA-DEG used for chain extension and addition reaction.
For comparison, the raw material polyester was AV220, Mn500 and
Using two types of resins, AV22 and Mn5000, chain extension and addition reactions were carried out in the same manner as in No. 1, and finally AV180 and Mn18500 resins, AV21,
A resin with Mn10700 was produced. These are each No. 7,
8. Example 100 g of resins No. 1 to 6 obtained above were dissolved in 895 g of water containing ammonia water (concentration 28%) in an amount equal to the carboxyl group equivalent in the polyester resin to create a 10% aqueous solution. was prepared. This was used as a glue for water jet rooms and its performance was evaluated. The results are shown in Table 2. Comparative Example Nos. 7 and 8 and two types of commercially available acrylic water jet room glues (hereinafter referred to as Nos. 9 and 10) were used as glues in accordance with the Examples. The results are also shown in Table 2. However, performance evaluation was performed as follows. Raw yarn; polyester yarn (50d/24 filament) Sizing conditions: ○Isizer Warping slatshear ○B Sizing temperature 20℃ ○C Sizing speed 100m/min ○D Drying speed Chamber 120℃ Cylinder adhesion rate Sizing yarn 2 to 3 g was placed in 100 times the amount of 0.5% sodium carbonate aqueous solution, and desizing was carried out three times at 90°C. After washing and drying, the weight was measured, and the weight was calculated from the difference in weight between the sized yarn and the sized yarn. Squeezing rate: Divide the adhesion amount (%) by the gluing temperature (%),
I calculated it by multiplying it by 100. Conjugation force test Using Matsui Seiki's TM type conjugation force tester,
The average number of frictions until yarn breakage was measured at 100g and at an angle of 145° (10mm). Desizing rate: Put 2 to 3 g of sizing thread in 100 times the amount of water, 80 to 85
Desizing was performed at ℃ for 5 minutes, washed with water, and after drying, the weight was measured, and the amount of desizing was calculated from the difference in weight between the sizing thread and the desizing thread.
The ratio to the amount of adhesion is shown.

【table】

【table】

Claims (1)

[Claims] 1 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 to 50,000 and a hydroxyl value of 25 to 100 KOHmg/
For hydrophobic fibers whose main ingredient is a polyester resin with a number average molecular weight of 5,000 to 50,000 and an acid value of 50 to 140 KOHmg/g obtained by obtaining a polyester resin of Gluing agent.