JPH054466B2 - - Google Patents

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a fiber glue based on a polyester resin that has improved binding power and desizing properties, and exhibits sufficient performance with a smaller amount of glue than before. Regarding drugs. [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. Recently, various polyester-based glues have been reported as water-soluble resins by introducing sulfonic acid groups because they have superior binding power than such acrylic fiber glues.
(For example, Japanese Patent Publication No. 47-40873, Publication No. 53-18638
However, although glues using these polyester resins have excellent binding power, they are unsatisfactory in terms of desizing properties. There are many. Particularly in the weaving industry, there is a tendency to increase the operating speed of weaving machines in order to improve weaving efficiency, and the current situation is that conventionally known sizing agents are no longer able to adequately cope with this problem. [Means for Solving the Problems] As a result of intensive research to solve these problems, the present inventors have developed a polyethylene glycol alkylamine monomer represented by the following general formula (wherein R is , hydrogen or an alkyl group or an aryl group,
x, y are integers greater than or equal to 1) The present inventors have discovered that the above object can be achieved when a water-soluble polyester resin containing a sulfonic acid group as a condensation component and a sulfonic acid group in the resin is used as a fiber sizing agent, and has completed the present invention. The greatest feature of the present invention is that it uses a water-soluble polyester containing a polyethylene glycol alkylamine monomer as a condensation component, which was completely unknown until now, as a polyester fiber glue, and the polyester resin thus obtained has a conjugation strength. Of course,
This results in a sizing agent that also has excellent desizing properties. The polyester resin will be explained below. First, in the polyethylene glycol alkylamine monomer represented by the above general formula, R is usually hydrogen or an alkyl group, more preferably having 2 to 2 carbon atoms.
It is about 20 lower alkyl groups or aryl groups.
The aryl group may be a lower alkyl-substituted aryl group. Further, x and y may be equal or different, and each is an integer of 1 or more, preferably the sum of x and y is 3 or more, particularly preferably each is an integer of 2 to 20. Further, although the molecular weight of the monomer is not particularly limited, good results can usually be expected when it is in the range of 200 to 2000. The content of the monomer in the polyester resin is usually 0.1 to 20 mol%, preferably 1 to 10 mol%, based on the glycol component, which is a condensation component described below, from the viewpoint of the balance between desizing properties and binding strength. is within the range of It is essential that the polyester resin of the present invention containing the above monomer as an essential condensation component further contains a sulfonic acid group in the resin. Each group can be incorporated by conventionally known methods, and the following methods are commonly used. (1) A method in which a polyhydric carboxylic acid having a sulfonic acid group is used as a condensation component. (2) A method in which a polyhydric alcohol having a sulfonic acid group is used as a condensation component. (3) A method in which an acidic acid is added to the unsaturated bonds of an unsaturated polyester resin. Method for reacting sulfites, etc. In the above, the polyhydric carboxylic acids having a sulfonic acid group include 5-sodiosulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 2-sodiosulfoterephthalic acid, and 2-potassium sulfoterephthalic acid. etc., and as the polyhydric alcohol having a sulfonic acid group, a product obtained by reacting an unsaturated polyhydric alcohol with an acidic sulfite is usually used, and such an unsaturated polyhydric alcohol includes 3-butene-
1,2-diol, 2-butene-1,4-diol, 2,5-dimethyl-3-hexene-2,5-
In addition to olefin glycols such as diols, 1,
Diolefin glycols such as 5-hexadiene-3,4-diol can also be used. Therefore, the content of the sulfonic acid group in the resin is 2.5 to 10 mol%, particularly preferably 4 to 8 mol%, based on the total amount of the acid component and glycol component, which will be described later, from the viewpoint of the physical properties of the sizing agent. At 2.5 mol% or less, the desizing property decreases, and at 10 mol%, the binding power decreases. In the present invention, if a sulfonic acid group is present, it can exhibit excellent conjugation power and desizing properties due to the synergistic effect with the polyethylene glycol alkylamine monomer. The use of carboxylic acids or polyhydric alcohols is most preferably used in the preparation. As condensation components other than those mentioned above in the polyester resin containing a sulfonic acid group of the present invention, ordinary acid components and glycol components can be arbitrarily used. Such acid components 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, 4,4'-oxybenzoic acid, diglycolic acid, thiodipropion, and 2,5-
Examples include 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. Further, as trivalent or higher polyhydric carboxylic acids, trimellitic acid, trimellitic anhydride, pyromellitic acid, 4-methylcyclohexene-1,2,3 tricarboxylic acid anhydride, trimesic acid, etc. can also be used in small amounts. In addition, glycol components 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. In addition to the above, trivalent or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, etc. can also be used in small amounts. be. No special means are required to produce the resin targeted by the present invention, and it may be carried out in accordance with conventionally known methods. Typically, the polyethylene glycol alkylamine monomer, a polyhydric carboxylic acid having a sulfonic acid group or a polyhydric alcohol having the group, an acid component, and a glycol component are charged into a reactor together with a catalyst, and the temperature is heated at 140 to 230°C. Dehydration condensation is carried out by raising the temperature to . The catalyst used in this case is zinc acetate,
Zinc chloride, stannous lauryl, dibutyltin oxide, etc. are used, and these are usually effective against acid components.
0.05-0.15 parts by weight is added. A solvent is not particularly required, but if necessary, an inert solvent such as methyl acetate, benzene, acetone, xylene, toluene, etc. may be used. The polyester resin thus obtained has a number average molecular weight of 10,000 to 25,000, more preferably 15,000 to 25,000.
25000, acid value 5KOHmg/g or less, more preferably
Although it is desirable that the content be 3KOHmg/g or less, it is not necessarily limited to this. If the molecular weight is too low, the binding strength tends to decrease, while if the molecular weight is too high, the desizing properties tend to decrease. When preparing a sizing agent using the polyester resin, the solid concentration of the sizing solution should be approximately 5 to 20% by weight in consideration of workability, and the viscosity should be approximately 5 to 20 cps (at 20°C) at a concentration of 10% by weight. It is appropriate to set the value within the range of (measurement). Any fiber processing agent, softener, plasticizer, fiber auxiliary agent, etc. may be used in combination with the liquid. Further, an acrylic resin paste, a polyvinyl alcohol resin paste, a starch paste, a conventionally known polyester resin paste, etc. may be used in combination 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] Thus, as stated repeatedly, the fiber size agent of the present invention has much better desizing properties than conventionally known polyester fiber size agents, and of course also has very good binding power. [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 KOHmg/g. TPA: Terephthalic acid, IPA: Isophthalic acid,
AdA: adipic acid, SIPM: 5-sodiosulfoisophthalic acid, EG: ethylene glycol, TEG:
Triethylene glycol, SBD: 3-sodiosulfo-1,2-butanediol, PEGA: polyethylene glycol alkylamine monomer AV: acid value, OHV: hydroxyl value, Mn: number average molecular weight, AV, OHV measurement method example The middle, oxidation, hydroxyl value, and number average molecular weight were calculated using the following formulas.・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: Titer and hydroxyl value (OHV) of the 0.1N KOHmg/g titrant used OHV (KOHmg/g) = 5.611 x (b-a) x f/W a, b, f, and W are as above Same as ・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 Resin production example Equipped with a stirrer, rectification column, nitrogen introduction tube, and vacuum device 0.45 mol of TPA, 0.45 mol of IPA,
SIPM0.10mol, EG1.40mol, TEG0.35mol,
As PEGA, 0.05 mol of N,N-di-tetraoxyethylene-propylamine, 0.1 part of butyltin tin oxide, and 0.1 part of antimony trioxide were prepared, and after esterification at 170 to 260°C, 0.1 to 1.0
Perform polycondensation under vacuum of mmHg, AV1, Mn20000
A polyester resin was obtained. This resin is designated as No. 1 resin. Four types of polyester resins having different compositions were separately produced in a similar manner. These are designated as Nos. 2 to 5, respectively. However, PEGA No. 2 uses N,N-di-tetraoxyethylene-propylamine, and No. 2 uses N,N-di-tetraoxyethylene-propylamine.
In No. 3 and No. 4, N,N-di-pentadecaoxyethylene-stearylamine was used, and in No. 5, N,N-di-ethanolamine was used. The resin compositions, AV, and Mn of Nos. 1 to 5 are summarized in the table. For comparison, polyester resins as shown in the table (referred to as Nos. 6 and 7) were produced in the same manner as No. 1 resin. Evaluation of performance as glue The resins Nos. 1 to 8 obtained above were adjusted to 10% aqueous solutions, used as glue for water jet rooms, and evaluated for their performance. 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 90℃ Adhesion rate Glue 2 to 3 g of the attached yarn was placed in 100 times the amount of 0.5% sodium carbonate aqueous solution, and the size was removed 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】

Claims (1)

[Scope of Claims] 1 A polyethylene glycol alkylamine monomer represented by the following general formula (wherein R is hydrogen, an alkyl group, or an aryl group, and x and y are integers of 1 or more) as a condensation component, A warp sizing agent for fibers, the main ingredient of which is a water-soluble polyester resin containing a sulfonic acid group in the resin.