JPH0621418B2 - Method for refining cellulosic fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for scouring cellulosic fibers. More specifically, it relates to a method for improving the scouring property by using a specific water-soluble copolymer when scouring cellulosic fibers such as cotton and hemp.

(Prior art) Cellulosic fiber refining removes primary impurities such as pectin, wax and fat contained in the fiber and secondary impurities such as oil agents, sizing agents and machine oils added during processing. It imparts wettability and water absorbency to the fiber, and makes the penetration of the chemicals even in the bleaching, dyeing, and finishing processes that follow the scouring process evenly,
This is done as a preparatory step to enhance the value of the product while facilitating its operation. Conventionally, it is common to use an alkali agent, a surfactant or a solvent for this scouring, and among them, a method of using a surfactant in combination with an alkali agent such as sodium hydroxide or sodium silicate is widely used. .

However, in this method, the fat or oil component in the cellulose fibers contained as the primary impurities is hydrolyzed by the alkaline agent to be produced, or the silicic acid when a silicic acid-based agent such as sodium silicate is used as the alkaline agent. And polysilicic acid are combined with various polyvalent metal ions such as calcium ion, magnesium ion, iron ion, aluminum ion generated from hardness components in water used during scouring and inorganic substances contained in fibers. So-called insoluble salts (scales) are formed and deposited on the fibers and equipment during the refining process. This insoluble salt (scale)
Since it is difficult to emulsify and disperse the usual surfactants used in the refining step, they remain on the fiber and the device after the refining step. When it remains on the fiber, the water repellent property is developed in the fiber, impairing the required wettability and water absorption of the fiber, causing poor penetration of chemicals in the bleaching, dyeing and finishing processes following the scouring process. Becomes

In addition, if the deposit is continued on the scouring device for a long time, it causes a serious accident called scale trouble.

In order to overcome these problems, in the refining process, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxylethylenediaminetriacetic acid, aminocarboxylic acid such as nitrilotriacetic acid, or condensed phosphoric acid-based refining such as tripolyphosphoric acid, hexametaphosphoric acid, pyrophosphoric acid A sex improver is used. However, the aminocarboxylic acid type agents require a large amount of addition because their emulsifying and dispersing powers against these insoluble salts (scales) are weak. Further, the condensed phosphoric acid-based agent is hydrolyzed into phosphoric acid under high temperature and high alkaline conditions in the refining step, and the effect is reduced, and phosphoric acid produced by hydrolysis is combined with the various polyvalent metal ions. It became a causative substance that promotes insoluble salt (scale).

In order to eliminate the drawbacks of such aminocarboxylic acid-based and condensed phosphoric acid-based refining property improvers, JP-A-59-1
87669, JP-A-59-192770, JP-A-6
No. 1-266665 proposes the use of a (co) polymer using one or more unsaturated carboxylic acid type monomers such as (meth) acrylic acid and maleic acid. However, these (co) polymers are apt to generate insoluble salts (scales) with the polyvalent metal ions themselves, and the present situation is that these (co) polymers have not been radically solved.

Also, JP-A-60-146074 and JP-A-61-224
It has been proposed to use a copolymer of an unsaturated carboxylic acid type monomer and a polyoxyalkylene monoallyl ether type monomer in Japanese Patent No. 5366, JP-A No. 61-275466 and the like. However, these copolymers are relatively effective in preventing the deposition of insoluble salts (scales) due to fatty acids, but have a low ability to prevent the deposition of insoluble salts (scales) due to silicic acid or polymerized silicic acid. It was still a problem.
In addition, since polyoxyalkylene monoallyl ether-based monomers have poor copolymerizability with unsaturated carboxylic acid-based monomers, a relatively large amount of unreacted monomer remains, resulting in a product with high purity. There was also a drawback that it was difficult to obtain.

Further, JP-A-62-15379 proposes the use of a copolymer of an unsaturated monocarboxylic acid type monomer and a sulfoalkyl (meth) acrylate type monomer. Although these copolymers have been relatively well evaluated, the ester bond in such copolymers is easily hydrolyzed under high temperature and high alkaline conditions in the refining process, resulting in the unsaturated monocarboxylic acid type. Similar to the (co) polymer, polyvalent metal ions and an insoluble salt (scale) are produced, and the scouring property and the prevention of insoluble salt deposition on the scouring device become insufficient.

(Problems to be Solved by the Invention) The present invention has a conventional refining property improving agent when refining cellulosic fibers with an alkali agent such as sodium hydroxide or sodium silicate or a surfactant. The above problems are solved.

Therefore, an object of the present invention is to produce any insoluble salt (scale) due to (polymerized) silicic acid from a fatty acid or an alkaline agent generated by hydrolysis of an oil and fat component with an alkaline agent when scouring a cellulosic fiber. Suppress
It is an object of the present invention to provide a method of improving scouring property and preventing accidents due to deposition of insoluble salt (scale) on a device.

(Means and Actions for Solving the Problems) The present invention provides a general formula for scouring a cellulosic fiber with an alkali agent and a surfactant. (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ² and A ¹ and A ² do not become simultaneously —COOX ^2, and A ³ represents a hydrogen, a methyl group or Represents —CH ₂ COOX ³ and A ³ represents —CH ₂
In the case of COOX ³ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹ , X ² and X ³ each independently or together represent hydrogen,
It represents a monovalent metal, a divalent metal, an ammonium group or an organic amine group. ) Unsaturated carboxylic acid monomer (I) 40-9
9.5 mol% and general formula (In the formula, R ¹ represents hydrogen or a methyl group, and a,
b, d and f each independently represent O or a positive integer, and a + b + d + f = 0 to 100, May be bonded in any order, and when d + f is 0, Z is a hydroxyl group, a sulfonic acid group or its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt or (sub) phosphorus. Acid group or its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, and d +
When f is a positive integer of 1 to 100, Z represents a hydroxyl group. ) An unsaturated (meth) allyl ether-based monomer (I
I) Scouring of a cellulosic fiber characterized by using a water-soluble copolymer (A) having an average molecular weight of 1,000 to 100,000 derived from a monomer component consisting of 0.5 to 60 mol% It is about the method.

It is not clear why the water-soluble copolymer (A) shows excellent refining properties and the reason why insoluble salt (scale) deposits on refining equipment, etc. are eliminated, but it is presumed as follows. There is.

That is, when the polyvalent metal ion is in a relatively small amount, due to the high chelating ability of the water-soluble copolymer (A), the polyvalent metal ion is combined with a fatty acid or silicic acid to form an insoluble salt. As a result of binding to the water-soluble copolymer (A), it is presumed that these polyvalent metal ions do not form an insoluble salt or become extremely difficult to form, and will not be deposited on the fiber or the scouring device.

Further, when the amount of polyvalent metal ion is large, an insoluble salt is formed, but since the insoluble salt exists in an extremely fine particle state by the action of the water-soluble copolymer (A), the water-soluble copolymer is also present.
It is speculated that the insoluble salt does not deposit on the fiber or the scouring device due to the emulsifying / dispersing action of (A).

Examples of the unsaturated carboxylic acid type monomer (I) represented by the above general formula used in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or the like. Acid monovalent metal,
Partially neutralized products or completely neutralized products with divalent metals, ammonia and organic amines can be mentioned. Examples of the monovalent metal include sodium and potassium, and examples of the divalent metal include calcium, magnesium and zinc. Also,
As the organic amine, alkylamines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine and triethylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and dimethylethanolamine; pyridine and the like. I can give you.

Examples of the unsaturated (meth) allyl ether-based monomer (II) represented by the above general formula include glycerol mono (meth) allyl ether and 3- (meth) allyloxy-2.
-Hydroxypropane sulfonic acid (salt), 3- (meth)
Examples thereof include compounds in which 1 to 100 mol of ethylene oxide and / or propylene oxide is added to 1 mol of allyloxy-2-hydroxypropanephosphoric acid (salt) and the (meth) allyl ether-based monomer. The number of kinds of ethylene oxide and propylene oxide may be one or two, and in the case of adding many kinds, there is no limitation on the bonding order. The added mole number of alkylene oxide is 0 to 100 moles, preferably 0 to 50 moles. The number of added moles of alkylene oxide is 100.
If it exceeds the molar amount, a large amount of addition is required, which is not preferable.

The water-soluble copolymer (A) used in the present invention is an unsaturated carboxylic acid-based monomer (I) 40-9 represented by the above general formula.
The average molecular weight derived by polymerizing a monomer component consisting of 9.5 mol% and 0.5 to 60 mol% of an unsaturated (meth) allyl ether monomer (II) is 1,000 to 1.
Copolymers of 0,000, and those outside of any of these ranges have poor scouring properties, and insoluble salt deposition on the scouring device cannot be prevented.

To obtain the water-soluble copolymer (A) used in the present invention, a monomer comprising these unsaturated carboxylic acid type monomer (I) and unsaturated (meth) allyl ether type monomer (II) The components may be polymerized by known techniques. For example, in the case of water-soluble polymerization, persulfates such as sodium persulfate and potassium persulfate;
Hydrogen peroxide; a water-soluble azo compound such as 2,2'-azobis (2-amidinopropane) hydrochloride or 4,4'-azobis-4-cyanovaleric acid can be used as a polymerization catalyst to be produced by a conventional method. Further, alcohols such as methanol and isopropyl alcohol, ethers such as tetrahydrofuran and dioxane, benzene, xylene,
In the case of polymerization in an organic solvent such as an aromatic type such as toluene or a ketone type such as methyl ethyl ketone or methyl isobutyl ketone, benzoyl peroxide lauroyl peroxide, organic peroxide such as peracetic acid; azobisisobutyronitrile,
An oil-soluble azo compound such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) or the like can be produced by a conventional method as a polymerization catalyst.

Further, when the water-soluble copolymer (A) is obtained, the unsaturated carboxylic acid-based monomer (I) is used within a range that does not impair the effects of the present invention.
It is of course possible to copolymerize the other monomer which is copolymerizable with the unsaturated (meth) allyl ether monomer (II). Other copolymerizable monomers include, for example, amide-based monomers such as (meth) acrylamide and t-butyl (meth) acrylamide; (meth) acrylic acid ester, styrene, 2-methylstyrene, vinyl acetate, etc. Hydrophobic monomer of vinyl sulfonic acid, allyl sulfonic acid,
Methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxysulfopropyl (meth) acrylate, sulfoethyl maleimide or one of them.
Unsaturated sulfonic acid type monomers such as partially neutralized products and completely neutralized products of valent metals, divalent metals, ammonia, organic amines;
2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, allyl alcohol, polyethylene glycol monoallyl ether,
Polypropylene glycol monoallyl ether, 3-methyl-3-buten-1-ol (isoprenol), polyethylene glycol monoisoprenol ether, polypropylene glycol monoisoprenol ether,
3-methyl-2-buten-1-ol (prenol),
Polyethylene glycol monoprenol ether, polypropylene glycol monoprenol ether, 2-methyl-3-buten-2-ol (isoprene alcohol), polyethylene glycol monoisoprene alcohol ether, polypropylene glycol monoisoprene alcohol ether, α-hydroxyacrylic acid, N-
Hydroxyl group-containing unsaturated monomers such as methylol (meth) acrylamide, glycerol mono (meth) acrylate and vinyl alcohol; cationic monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide; ) Nitrile monomers such as acrylonitrile; (meth) acrylamidomethanephosphonic acid, (meth) acrylamidomethanephosphonic acid methyl ester, 2- (meth) acrylamide-2
-Phosphorus-containing monomers such as methylpropanephosphonic acid; ethylene, propylene, 1-butene, isobutylene, α-amylene, 2-methyl-1-butene, 3-methyl-1-butene (α-isoamylene), 1- Examples include α-olefin monomers such as hexene and 1-heptene.

In the present invention, as the cellulosic fibers that can be preferably refined using the water-soluble copolymer (A), for example, cellulosic natural fibers such as cotton and hemp, rayon, and other cellulosic regenerated fibers such as cupola. , Nylon, polyester, mixed fibers with synthetic fibers such as acrylic, further mixed fibers with semi-synthetic fibers such as acetate, the form at the time of refining fiber, yarn, cheese, woven, knit, It does not matter whether it is in the form of a non-woven fabric or a final fiber product such as clothes and bedding products.

As a scouring method, a usual method can be applied, and a pad / steam method, a pressure boiling method, a boiling method, a dipping method or other methods can be appropriately selected. Furthermore, the water-soluble copolymer (A)
Can be applied not only to the scouring described so far, but also to scouring performed in one bath at the same time as other processes such as desizing / scouring, scouring / bleaching, and descaling / scouring / bleaching. .

(Effects of the Invention) According to the method for scouring a cellulosic fiber of the present invention, the scouring effect is significantly enhanced as compared with the conventional method using a scouring agent, and in the steps such as bleaching, dyeing and finishing following the scouring step. It is possible to uniformly improve the penetration of the drug, facilitate its operation, and enhance the value of the final product.

In addition, insoluble salts (scale) such as metallic soap and polyvalent metal salts of silicic acid are rarely produced during the scouring process, and even if they are produced, they are deposited on the fibers and the scouring device, which reduces the scouring property. And no scale problems will occur.

(Examples) Hereinafter, the present invention will be described with reference to Reference Examples and Examples, but the present invention is not limited to these Examples.
Unless otherwise specified, all parts are parts by weight and%
All represent% by weight.

Examples 1-13 2 g of the salt of the copolymer shown in Table 1 was used as a scouring agent.
/ Used and desized, cotton gabardine was scoured under the following conditions.

<Scouring conditions> Hardness of water used 25 ° DH bath ratio 1 to 25 temperature 95 to 100 ° C. time 60 minutes Chemicals used Alkaline agent Sodium hydroxide 10 g / Surfactant (trade name, Score Roll M-360, Kao ( Manufactured by K.K.) 2g / Scouring property is 20 mm wide from the cloth after the scouring treatment.
A sample with a length of 300 mm was sampled and suspended so that one end of the sample was immersed in dye water on a vat filled with dye water obtained by dissolving dye, and the suction height of the dye water for 30 seconds (mm ) Was measured and it was performed as a measure of refinement.
The results are shown in Table 1.

Comparative Examples 1 to 15 Scouring was carried out in exactly the same manner as in Examples 1 to 13 except that the polymer salts shown in Table 2 were used as the scouring improver. The results obtained are shown in Table 2.

Comparative Example 16 Scouring was carried out in the same manner as in Examples 1 to 13 except that sodium ethylenediaminetetraacetate was used as the scouring property improver. The results obtained are shown in Table 2.

Comparative Example 17 Scouring was carried out in the same manner as in Examples 1 to 13 except that sodium tripolyphosphate was used as the scouring property improver. The results obtained are shown in Table 2.

The meanings of the monomer abbreviations in Tables 1, 2, 3, and 4 are as follows.

MA: maleic acid FA: fumaric acid IA: itaconic acid AA: acrylic acid MAA: methacrylic acid CA: crotonic acid SEM: Sulfoethyl methacrylate VS: Vinyl sulfonic acid Examples 14-26 The following tests were conducted to evaluate the extent of silicate scale deposition on fibers or scouring equipment.

Magnesium sulfate 140 mg / (CaCO ₃ conversion amount), silica 175 mg / (SiO ₂ conversion amount), M alkalinity 3 by adding magnesium sulfate, sodium metasilicate, sodium hydrogen carbonate and sodium hydroxide to distilled water.
After adjusting the pH to 00 mg / (CaCO ₃ equivalent) and pH to 9.0, test water containing 200 mg / salt of the copolymer shown in Table 3 as a refiner is added to a 225 ml glass mayonnaise bottle and sealed. After that, put in a constant temperature bath at 70 ° C for 10
Let stand for hours.

Then, test water was passed through a 0.1 μ filter, and the amount of silicic acid in the solution was measured by the method described in JIS K 0101.

The silicate scale inhibition rate (%) was calculated by the following formula, and the results are shown in Table 3.

However, A: SiO ₂ concentration before the test (= 175 ppm) B: SiO ₂ concentration in the liquid after the test without addition of the scouring agent (ppm) C: SiO ₂ concentration in the liquid after the scouring agent addition test ( ppm) Comparative Examples 18 to 32 The scale inhibition rate was calculated in exactly the same manner as in Examples 14 to 26 except that the salt of the copolymer shown in Table 4 was used as the scouring agent. The results are shown in Table 4.

Comparative Example 33 The scale inhibition rate was calculated in exactly the same manner as in Examples 14 to 26 except that sodium ethylenediaminetetraacetate was used as the refiner. The results are shown in Table 4.

Comparative Example 34 The scale inhibition rate was calculated in exactly the same manner as in Examples 14 to 26 except that sodium tripolyphosphate was used as the refiner. The results are shown in Table 4.

Claims (5)

[Claims] 1. When scouring a cellulosic fiber with an alkali agent and a surfactant, a general formula (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ² and A ¹ and A ² do not become simultaneously —COOX ² ; A ³ represents a hydrogen, a methyl group or ^{a 1} and a when -CH ₂ COOX ³ a represents and ^{a 3} is _-CH 2 COOX ^3
2 each independently represents hydrogen or a methyl group, X ¹ , X ² and X ³ are each independently or together hydrogen;
It represents a monovalent metal, a divalent metal, an ammonium group or an organic amine group. ) Unsaturated carboxylic acid monomer (I) 40-9
9.5 mol% and general formula (In the formula, R ¹ represents hydrogen or a methyl group, and a,
b, d and f each independently represent O or a positive integer, and a + b + d + f = 0 to 100, When May be bonded in any order, and when d + f is 0, Z is a hydroxyl group, a sulfonic acid group or its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt or (sub) phosphorus. Acid group or its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, and d +
When f is a positive integer of 1 to 100, Z represents a hydroxyl group. ) An unsaturated (meth) allyl ether-based monomer (I
I) Scouring of a cellulosic fiber characterized by using a water-soluble copolymer (A) having an average molecular weight of 1,000 to 100,000 derived from a monomer component consisting of 0.5 to 60 mol% Method. 2. The scouring method according to claim 1, wherein a water-soluble copolymer (A) in which a + b + d + f is 0 and Z is a hydroxyl group is used. 3. The scouring method according to claim 1, wherein a water-soluble copolymer (A) in which a + b + d + f is 0 and Z is a sulfonic acid (salt) group is used. 4. The scouring method according to claim 1, wherein the water-soluble copolymer (A) in which b + f is 0 and a + d is a positive integer of 1 to 50 is used. 5. The scouring method according to claim 1, wherein the water-soluble copolymer (A) having an average molecular weight of 2,000 to 70,000 is used.