JPH04142385A - Water-base thickening agent and warp sizing material - Google Patents

Abstract

PURPOSE:To obtain a water-base thickening agent which can maintain stable viscosity over a long period of time by using as effective component a high- molecular compound formed from a specified polyoxyalkylene compound, a dihydroxy carboxylic acid (salt), and an organic polyisocyanate. CONSTITUTION:A polyoxyalkylene compound (i) of the formula [wherein R is a residue of a 1-18C hydroxy compound R-(OH)n of a valence of n with the OH groups removed therefrom; A is 2-20C alkylene; m is 5 to 700; n is 1 to 8] is reacted with a dihydroxy carboxylic acid (salt) (ii) in an amount sufficient to provide a weight ratio of component (i) to component (ii) of 100:(0.01 to 50), and an organic polyisocyanate (iii) in an amount sufficient to provide an equivalent ratio of the total OH groups of components (i) and (ii) to the NCO groups of component (iii) of (2:1) to (1:2) at 30-150 deg.C for 1-30hr to give a water- soluble high-molecular compound having a molecular weight of 10,000 to 5,000,000. At least 10% of this compound is mixed, if necessary, with other water-soluble high-molecular compound to give a water-base thickening agent.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to an aqueous thickener and a warp sizing agent.

[Prior Art] Traditionally, water-based thickeners include starches, gums, cellulose derivatives, natural and semi-synthetic thickeners such as sodium alginate, or polyvinyl alcohol, polyacrylates, polyacrylamide, polyethylene oxide, etc. Synthetic thickeners are known.

1 Conventionally, natural and synthetic sizing agents such as starches, polyvinyl alcohol, and acrylic sizing agents have been known as warp sizing agents.

“Problems to be Solved by the Invention” However, with these conventional thickeners, the stability of the thickened aqueous solution is insufficient, and the viscosity changes over time, or the viscosity decreases due to mechanical tip stress. However, when thickeners are used together or when two or more types of thickeners are used together, there have been various problems such as insufficient compatibility and separation over time.

In addition, sizing using these conventional warp sizing agents cannot be said to have sufficient yarn binding properties, and polyvinyl alcohol, in particular, has a unique coating property that makes it suitable for various types of fibers, both hydrophilic and hydrophobic. Although it is widely used, it has had many problems such as thread breakage during weaving due to lack of smoothness and flexibility.

[Means for Solving the Problems] The present inventors have developed an aqueous thickener that maintains stable viscosity over a long period of time in an aqueous system and has excellent compatibility with other water-soluble thickeners, and a conjugating property. As a result of extensive research into a warp sizing agent with excellent properties, the present invention was developed.

That is, the present invention is based on the formula (1) [wherein R is a residue obtained by removing a hydroxyl group from an n-valent hydroxy compound R-(OH)n having 1 to 18 carbon atoms, and A is a carbon number 2 to 20 alkylene groups, m is a number of 5 to 700,
n represents a number from 1 to 8. Polyoxyalkylene compound (a) and diol carboxylic acid (salt) (b) shown in
) and a water-soluble polymer compound (1) with a molecular weight of 10.000 to 5.000,000 derived from an organic polyisocyanate (C); It is a warp sizing agent characterized by being an essential ingredient.

In the present invention, aliphatic alcohols (methanol,
(ethanol, octyl alcohol, dodecyl alcohol, tridecyl alcohol, stearyl alcohol, oleyl alcohol, etc.), -valent phenols (phenol, cresol, ethylphenol, isobutylphenol, octylphenol), polyhydric phenols (hydroquinone, catechol, etc.), bisphenol (such as bisphenol A), polyhydric alcohols (ethylene glycol, propylene glycol, hexylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, silosaccharide, etc.), and water. Among these, preferred are polyhydric phenols, polyhydric alcohols, and water, and particularly preferred are ethylene glycol, propylene glycol, and water.

The (OA)mOH part in general formula (1) has 2 carbon atoms.
Formed by addition of ~20 alkylene oxides. Specific examples of this alkylene oxide include ethylene oxide (EO), propylene oxide (PO), 1,2-butylene oxide (BO), tetrahydrofuran, α-olefin oxide (carbon number 5
-20), alkylene oxide substituted products (shrimp chlorohydrin, styrene oxide, etc.).

Among these, preferred are EO and a combination of EO and PO.

m is a number from 5 to 700, preferably from 25 to 500.

If m is less than 5, the obtained polymer compound will be insoluble in water, and if it exceeds 700, the reactivity with the organic polyisocyanate will be poor, making it difficult to obtain a polymer compound having the desired performance.

The bonding order of the m alkylene oxides does not matter. Further, the bonding mode may be a single addition of these alkylene oxides, a random addition of two or more types, or a block addition. Among the oxyalkylene chains formed from these alkylene oxides, preferred are single addition chains of EO, or blocks or random addition chains of EO and PO. For block addition,
The terminal block of the oxyalkylene chain is preferably an EO-added chain from the viewpoint of reactivity with the organic polyisocyanate.

In the case of EO@PO adducts, the ratio of the sum of the molecular weights of the EO adducts and the sum of the molecular weights of the PO adducts is usually 100:O.
~100:80, preferably 100:O~100:
It is 50.

- Polyoxyalkylene compound represented by (1)
Among a), preferred examples include polyethylene glycol (average molecular weight 2,000.4.000.
G, 000120. (100, etc.): Polyoxyethylene nonylphenyl ether (number of moles of ethylene oxide added: 40 moles, 50 moles, 70 moles, etc.);
A copolymer in which ethylene oxide is block-added to a polyoxypropylene polymer (average molecular weight 6,000°9.
000. 12,000, etc.; ethylene oxide content 70%); Ethylene oxide adducts of polyhydric alcohols such as glycerin and trimethylolpropane (number of moles added: 50.100.200 mol, etc.); Polyhydric alcohols such as glycerin and trimethylolpropane Examples include compounds in which propylene oxide is added to , and then ethylene oxide is added to (total number of added moles, such as 50.1001200 moles; ethylene oxide content: 80%); and mixtures of two or more of these.

Examples of the diolcarboxylic acid (salt) (b) in the present invention include dimethylolacetic acid (salt), dimethylolpropionic acid (salt), dimethylolbutyric acid (salt), and mixtures of two or more thereof. Among these, preferred is dimethylolpropionic acid (salt). Examples of salts include alkali metal salts (L r, NaN
K, etc.), alkaline earth metal salts (Ca, Mg, etc.),
Examples include ammonium salts, alcamelamine salts (monoethanolamine, jetanolamine, triethanolamine, etc.), and mixtures of two or more of these. Among these, preferred are alkali metal salts and ammonium salts. Among the constituent components of (1), (a
) and (b) is usually a weight ratio of 100: O
,Of~100:50, preferably 100:0.1
~100:10. When (b) is less than 0.01, the effect of improving conjugation properties is small, and even when it exceeds 50, no good effect can be expected.

In the present invention, examples of the organic polyisocyanate (c) include ethylene diisocyanate, hexylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,
4'-Diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,41-dibenzyl diisocyanate, 1,3-
Phenylene diisocyanate, 1,4-phenylene diisocyanate, Tolylene diisocyanate (2,4
and isomers such as 2 and 6), diisocyanates such as isophorone diisocyanate and xylylene diisocyanate, reaction products of tolylene diisocyanate and trimethylolpropane, and polyamines obtained by reacting aniline with formaldehyde in the presence of hydrochloric acid. Examples include polyphenylmethane polyisocyanate obtained by phosgenation, crude incyanate obtained in the production process of these organic incyanates, and mixtures of two or more thereof. Among these, preferred are diisocyanates and crude diphenylmethane diisocyanate.

(1) constitutes (a) y (b) +
Of (c), the total OH equivalent of (a) and (b) and (c
) to the incyanate equivalent is usually 2/1 to 1/
It is 2.

Within the above range, the thickener of the present invention has good thickening properties, viscosity stability, and sizing agent binding properties.

To illustrate the method for producing water-soluble polymer compound (1), (a) and (
By reacting b) and (C), ■ is obtained.

The reaction temperature is usually 30-150°C, preferably 50-13°C.
It is 0°C. The reaction time is usually 1 to 30 hours, preferably 3 to 8 hours. This reaction may be carried out by adding a solvent, and examples of the solvent used include acetone, tetrahydrofuran, dimethylformamide dimethyl sulfoxide, toluene, and dioxane.

The molecular weight of the water-soluble polymer compound (1) obtained is usually 1
0.000~5,000. poo preferably 20,0
00~t, ooo, ooo.

The thickener of the present invention may be used in combination with other water-soluble polymers, if necessary. Examples of these water-soluble polymers include starch, starch derivatives (carboxymethyl starch, hydroxyethyl starch, cationized starch, etc.), cellulose derivatives (carboxymethyl cellulose,
Methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cationized cellulose (!'), gums (gum tragacanth, guar gum, gum arabic, etc.)
, polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, and mixtures of two or more thereof. In that case, the amount of the water-soluble polymer compound according to the present invention is usually 10% or more, preferably 50% or more in the thickener of the present invention.

The thickener of the present invention is not particularly limited depending on the application, but is usually used as an aqueous solution of 0.01% to 50%, preferably 0.1 to 30% by weight.

The method of use can be the same as for conventional water-soluble thickeners, and it can be dissolved by gradually adding it to cold water while stirring, or it can be easily made into a highly viscous aqueous solution by heating if necessary. can be obtained.

The warp sizing agent of the present invention contains the water-soluble polymer compound (1) obtained by the method exemplified above as an essential component. Since the sizing agent of the invention has excellent water solubility, it can be used alone or in combination with various oils in the form of an aqueous solution, and it can be used alone or as a melt size with wax as a solvent when heated above the melting point. You can. Furthermore, a smoothing agent (mineral oil, animal and vegetable oil, wax, higher alcohol, higher fatty acid and other oil derivatives, low-molecular polyolefin and other hydrophobic organic compounds; preferably those with poor compatibility with the sizing agent) and, if necessary, an emulsifier. (Various anionic and nonionic surfactants) may be dispersed in water and/or organic solvents (lower alcohols, acetone, etc.) (sizing oil), or organic solvents (lower alcohols, etc.) It can also be used as a dry size.

The sizing agent of the present invention can be used with other sizing agents (natural sizing agents such as starch, funori, sodium alginate, rubbers, glue, linseed oil, etc.)
Semi-synthetic thickeners such as carboxymethylcellulose, methylcellulose, carboxymethyl starch, hydroxyethyl starch, cyanoethyl starch, etc., and polyvinyl alcohol-based, polyvinyl acetate-based, polyvinyl ether-based, polyacrylic-based, maleic acid copolymer, crotonic acid copolymer It may also be used in combination with synthetic adhesives (such as synthetic adhesives).

The ratio of the sizing agent of the present invention to other sizing agents is not particularly limited, but is usually 1 to 100:99 to 0, preferably 20 to 100:80 to 0, by weight.

In addition, various surfactants 1, colorants (dyes, etc.), antistatic agents (surfactant-based, polymer-based, oxidized low-molecular-weight polyolefins, etc.), auxiliary lubricants, softeners, conditioning agents, etc. are added as necessary. Can be added.

The amount of these additives to be added is preferably 20% by weight or less based on the sizing agent, and if a large amount is added, the conjugation property will decrease.

When sizing fibers using the sizing agent of the present invention, the amount of sizing agent used in the sizing composition is determined by the usage form (
Although it varies depending on the type of fiber (aqueous solution, melt size, oil agent, dry size) and applied fiber, it is generally 70 to 70% of the total weight.
99.5% by weight, preferably 85-98% by weight.

The fibers to which the sizing agent of the present invention is applied are not particularly limited, and include synthetic fibers such as polyamide, polyester, acrylic, and polyolefin, regenerated cellulose fibers such as viscose rayon and acetate fiber, braided wire, wool, hemp, etc. It can also be applied to natural fibers.

Furthermore, the form of the fibers is not particularly limited, and both filament yarns and spun yarns are applicable.

The sizing agent of the present invention may be applied to fibers by any conventional method, such as roller sizing, pot sizing, skein sizing, cheese sizing, or slasher sizing. The gluing temperature, gluing speed, drying method, etc. may be the same as the usual method. The gluing temperature is usually 10 to 100°C, preferably 1
5-70°C.

When applying the sizing agent of the present invention to fibers, the amount of sizing to the fibers is not particularly limited depending on the type of fibers and the intended use, and is usually 0.5 to 15% by weight, preferably 1 to 10% by weight.

[Example] The present invention will be further explained with reference to Examples below, but the present invention is not limited thereto.

The polyoxyalkylene compound, diolcarboxylic acid, and polyiso/anate used in the thickener and sizing agent of the present invention are as follows.

(Polyoxyalkylene compound) Polyoxyalkylene compound 1 = polyethylene glycol (average molecular weight [1200]) Polyoxyalkylene compound 2 = polyethylene glycol (average molecular weight 20000) Polyoxyalkylene compound 3 = polypropylene glycol (average molecular weight 3300) ethylene oxide 80 weight % adduct polyoxyalkylene compound 4 = polypropylene glycol (average molecular weight 1700) ethylene oxide 80% by weight adduct (diol carboxylic acid) dimethylolpropionic acid (hereinafter abbreviated as DMPA) (organic polyisocyanate) organic polyisocyanate 1 = 4. 4--Diphenylmethane diisonanate Organic polyisocyanate 2 = 2.4-Tolylene diisocyanate Examples 1 to 4, Comparative Examples 1 to 4 (Used as thickener and sizing agent) Above polyoxyalkylene compound, diol carbon The thickener and sizing agent of the present invention were obtained by reacting the combinations shown in Table 1 at a reaction temperature of 80°C for 12 hours using an acid and an organic polyisocyanate. used.

In addition, as a comparative example, a system not using DMPA, polyvinyl alcohol, and polyethylene oxide shown in Table 1 were used.

Table 1 Note 1) a = polyoxyalkylene compound b diolcarboxylic acid C = organic polyisocyanate.

2) In Examples 1 to 4, the total OH equivalent of aNb and the NCO equivalent of C were reacted in an amount such that 1=1. Also, DMP
A is 1.0% by weight based on the polyoxyalkylene compound
used.

3) In Comparative Example 1, the OH equivalent of a and the NGO equivalent of C are 1=
The reaction was carried out in an amount of 1.

(Stability test as a thickener) 10% aqueous solutions of the thickeners of the present invention (Examples 1 to 4) and the compounds of Comparative Examples 1 to 3 were prepared, and heated at 5°C and 130°C for 1 day and 5 days. Viscosity change over time after being left unused and ultrasonic shear stability tester (output 150w, frequency 10kc)
) was used to measure the change in viscosity after irradiation with ultrasonic waves for 60 minutes at 20"CX. In the oral stability test, the viscosity immediately after dissolution was set as 100, and the change in viscosity after 11 and 15 days was expressed as an index, and the shear stability is expressed as the ratio of (viscosity after ultrasonic irradiation/viscosity before ultrasonic irradiation).The results are shown in Table 2. Table 2 (Compatibility test as thickener) Thickeners of Examples 1 to 4 , 5% each of the compound of Comparative Example 2.3
Aqueous solution and starch (Matsunorin M22, Matsutani Chemical) 5
% aqueous solution was prepared and the state of separation was visually observed. The results are shown in Table-3.

Table 3 (Note) 0: Completely compatible △: Separation tendency ×: Complete separation (performance test as a glue) Table -
Using the DMPA-free system described in 1 (Comparative Example 1) and polyvinyl alcohol (Comparative Example 2), cotton thread (30 count) was glued with cheese oil according to the following conditions, and tested using a TM conjugation tester. A conjugation test was conducted on the sized thread.

Gluing conditions Glue concentration 2 8% aqueous solution Gluing temperature: 50℃ Gluing speed: E35m/min Drying temperature: 130℃ The results are shown in Table 4.

Table 4 Slasher-sizing machine to polyester cotton blended yarn (65% polyester, 35% cotton) using Rivinyl alcohol and Brimar P-E3N (Nippon Acrylic Co., Ltd., acrylic type) 80:20 mixture (Comparative Example 4) The sizing was carried out using a TM-type conjugation tester, and the conjugation property test of the sized yarn was conducted using a TM conjugation property tester.

Gluing conditions Glue concentration: 5% aqueous solution Gluing temperature: 50℃ Gluing speed: 65m/min Drying temperature = 130″C The results are shown in Table-5.

Table 5 [Effects of the Invention] The thickener of the present invention has superior stability of thickened aqueous solutions compared to conventional thickeners, and is particularly superior in oral stability and mechanical shearing stability. Because of these characteristics, it is sometimes possible to prepare a large amount of aqueous solution, and it is possible to provide an aqueous solution of stable quality over a long period of time.

In addition, since it has excellent compatibility with other water-based thickeners such as starch, it is suitable as a mixed water-based thickener with excellent economic efficiency and workability.

The thickening agent of the present invention has an excellent thickening effect even in a small amount, and the viscosity of the aqueous solution does not change due to external conditions. Inorganic organic binder Can be used in fields such as emulsification/dispersion stabilizers, water-based lubricating oil bases, cosmetics, and water-based paints.

Furthermore, the sizing agent of the present invention is superior to conventional sizing agents in its ability to bind sized yarns, and greatly improves weavability. In addition, because it is soluble in cold water, there is no need to cook the size, and it is easy to remove the size, and the size solution has excellent oral stability and mechanical shearing stability. By using this method, it is possible to provide paste liquid of stable quality over a long period of time. In addition, starch, polyvinyl alcohol, etc.
It has various advantages as a warp sizing agent, such as excellent compatibility with other sizing agents.

Claims (1)

[Claims] 1. General formula R[(OA)_mOH]_n (1) [In the formula, R is an n-valent hydroxy compound R-(OH)_n having 1 to 18 carbon atoms with the hydroxyl group removed. residue, A
represents an alkylene group having 2 to 20 carbon atoms, m represents a number from 5 to 700, and n represents a number from 1 to 8. ] Polyoxyalkylene compound (a) and diol carboxylic acid (salt) (
b) and a water-soluble polymer compound (1) with a molecular weight of 10,000 to 5,000,000 derived from organic polyisocyanate (c). 2. The aqueous thickener according to claim 1, wherein the ratio of (a) and (b) among the constituent components (1) is 100:0.01 to 100:50 by weight. 3. A warp sizing agent comprising the water-soluble polymer compound (1) according to any one of claims 1 to 2 as an essential component.