JPS6367581B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agent for improving scouring properties of cellulose fibers. Scouring of cellulose fibers removes primary impurities such as pectin, wax, and fat contained in the fibers, as well as secondary impurities such as oils, glues, and machine oil added during processing, and improves the wettability of the fibers. It is used as a preparatory process to provide water absorption and improve the uniform penetration of chemicals in processes such as bleaching, dyeing, and finishing that follow the scouring process, making the process easier and at the same time increasing the value of the product. . Conventionally, it has been common to use a surfactant or a solvent as an alkaline agent for this scouring, and among these methods, a method of using a combination of an alkaline agent and a surfactant is widely practiced. However, in this method, the oil and fat components in the cellulose fibers contained as primary impurities are hydrolyzed by an alkaline agent, and the fatty acids produced at this time are contained in the hardness components in the water used during scouring and in the fibers. It combines with various metal ions such as calcium ions generated from inorganic substances to form so-called metal soaps, which are deposited on the fibers during the scouring process. Since this metal soap cannot be easily emulsified or dispersed with the usual surfactants used in the scouring process, it remains on the fibers even after the scouring process. This causes the fibers to develop water repellency, impairing the required wettability and water absorption of the fibers, and causing poor penetration of chemicals in processes such as bleaching, dyeing, and finishing that follow the scouring process, which poses a problem.
In order to overcome this problem, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxylethylenediaminetriacetic acid, nitrilotriacetic acid, sodium tripolyphosphate, etc. are sometimes used in combination as scouring improvers, but the results are not always satisfactory and cannot be completely eliminated. The current situation is that no solution has been reached. The present inventors have arrived at the present invention as a result of intensive research aimed at solving the problem of poor scouring caused by the formation and deposition of metal soap in the conventional scouring process of cellulose fibers as described above. Therefore, an object of the present invention is to impart superior wettability and water absorption to cellulose fibers after the scouring process compared to conventional scouring methods, and to improve the scouring process. The scouring properties of cellulose fibers have excellent performance, which allows for uniform penetration of chemicals in subsequent processes such as bleaching, dyeing, and finishing, making operations easier in each process, and increasing the value of textile products. The purpose of the present invention is to provide an improving agent. That is, the present invention is based on the general formula (However, in the formula, R ₁ represents hydrogen or a methyl group,
a and b are each 0 or a positive integer, and a+b=1 to 100, -(C ₂ H ₄ O-) unit and -(
C ₃ H ₆ O−) units may be bonded in any order. ) Repeating structural unit (A) shown by and general formula (However, in the formula, X is −(C ₂ H ₄ O−) _n −(C ₃ H ₆ O−) _o R ₄ (R ₄
represents hydrogen or an alkyl group having 1 to 20 carbon atoms, m and n are each 0 or a positive integer, and m+n=0 to 100, and -(C ₂ H ₄ O-) unit and -( C ₃ H ₆ O−) units may be bonded in any order. ), represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group, and Y represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) as a main component, and the total amount of (A) and the total amount of (B) are in a molar ratio of (A)/(B)=
The present invention relates to a scouring property improver for cellulose fibers comprising a copolymer having a ratio of 40/60 to 60/40. The above-mentioned copolymer used as a scouring property improver for cellulose fibers in the present invention has the general formula (However, in the formula, R ₁ represents hydrogen or a methyl group,
a and b are each 0 or a positive integer, and a+b=1 to 100, -(C ₂ H ₄ O-) unit and -(
The OC ₃ H ₆ −) units may be bonded in any order. ) Mono(meth)allyl ether monomer () and general formula (However, in the formula, X is −(C ₂ H ₄ O−) _n −(C ₃ H ₆ O−) _o R ₄ (R ₄
represents hydrogen or an alkyl group having 1 to 20 carbon atoms, m and n are each 0 or a positive integer, and m+n=0 to 100, and -(C ₂ H ₄ O-) unit and -( C ₃ H ₆ O−) units may be bonded in any order. ), represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group, and Y represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) as a main component, and if necessary co-contained with monomer () and monomer () to the extent that the performance as a scouring improver for cellulose fibers is not impaired. It can be obtained by copolymerizing a monomer mixture containing a polymerizable monomer () using a polymerization initiator and, if necessary, further neutralizing with an alkaline substance. The mono(meth)allyl ether monomer () is represented by the general formula above, and it directly adds alkylene oxide to (meth)allylic alcohol using an alkaline substance such as an alkali metal hydroxide as a catalyst. It can be easily synthesized by a known method. The number of moles a+b of alkylene oxide added in the mono(meth)allyl ether monomer () is 1 to 100. When a+b is 0, that is, (meth)allylic alcohol, the resulting copolymer does not have a sufficiently satisfactory effect as a scouring property improver. Conversely, when a+b exceeds 100, the copolymerization reactivity of such polyalkylene glycol mono(meth)allyl ether is low, and a copolymer effective as a scouring property improver for cellulose fibers of the present invention cannot be obtained. do not have. The maleic acid monomer () is represented by the above general formula, and specifically includes maleic acid, fumaric acid, monovalent metal salts, divalent metal salts, ammonium salts, and organic Amine salts and these acids and HO−(C ₂ H ₄ O−) _n −(C ₃ H ₆ O−) _o R ₄ (However, R ₄
represents hydrogen or an alkyl group having 1 to 20 carbon atoms, m and n are each 0 or a positive integer, and m+n=0 to 100, and -(C ₂ H ₄ O-) unit and -( C ₃ H ₆ O−) units may be bonded in any order. ) alcohol (hereinafter referred to as
It is called alcohol(d). ), and one or more of these can be used. In addition, a scouring property improver for cellulose fibers of a copolymer that can obtain a monomer () copolymerizable with the mono(meth)allyl ether monomer () and maleic acid monomer () described above They can be used together as long as their performance is not impaired. Monomers () include, for example, diesters obtained from maleic acid, fumaric acid, citraconic acid or mesaconic acid and alcohol (d); acrylic acid, methacrylic acid, crotonic acid, itaconic acid and monovalent metals of these acids. Salts, divalent metal salts, ammonium salts, organic amine salts and their acids and alcohols (d)
and various sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-sulfoethyl (meth)acrylate, and their monohydric acids. Metal salts, ammonium salts and organic amine salts; 2
- Various (meth)acrylic acid esters such as hydroxyethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; various types such as (meth)acrylamide, N-methylol (meth)acrylamide, etc. (meth)acrylamide; styrene, p
- Aromatic vinyl compounds such as methylstyrene; examples include vinyl acetate, propenyl acetate, vinyl chloride, etc., and one or more of these can be used. The monomer () constitutes the repeating structural unit (C) in the copolymer obtained by copolymerizing with the mono(meth)allyl ether monomer () and the maleic acid monomer (). It is. In the copolymer used as the scouring property improver for cellulose fibers of the present invention, the total amount of repeating structural units (A) and the total amount of repeating structural units (B) are in a molar ratio.
It is necessary that (A)/(B)=40/60 to 60/40. Therefore, when producing a copolymer, mono(meth)allyl ether monomer ()
And the charging ratio of maleic acid monomer () is:
The total amount of repeating structural units (A) and the total amount of repeating structural units (B) in the resulting copolymer must fall within the above ratio range. In addition, the amount of the copolymerizable monomer () used as the third component is 50 mol based on the total of the mono(meth)allyl ether monomer () and the maleic acid monomer (). % or less, preferably 25 mol%
It is necessary to do the following. If the ratio is outside of these ranges, the scouring property improving agent for cellulose fibers will not have excellent performance. Mono(meth)allyl ether monomer (),
In order to produce a copolymer used as a scouring property improver for cellulose fibers of the present invention using a maleic acid monomer () and, if necessary, a monomer copolymerizable with the same (), polymerization is necessary. Copolymerization may be carried out using an initiator. Copolymerization can be carried out by various methods such as polymerization in a solvent or bulk polymerization, but polymerization in a solvent is preferred from the viewpoint of ease of controlling the reaction. Polymerization in a solvent can be carried out either batchwise or continuously. At that time, the solvent used is
Examples include water, lower alcohols, mixed solvents of water and lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ketone compounds, and ethyl acetate. When polymerization is carried out in an aqueous medium, a water-soluble polymerization initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used as the polymerization initiator. At this time, sodium hydrogen sulfite, L-
Accelerators such as ascorbic acid can also be used in combination. In addition, when lower alcohols or other solvents are used, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; and aliphatic azo compounds such as azobisisobutyronitrile are polymerized. Used as an initiator. At this time, a promoter such as an amine compound can also be used in combination. Furthermore,
When using a water-lower alcohol mixed solvent,
The polymerization initiator or a combination of a polymerization initiator and an accelerator can be appropriately selected and used from the above-mentioned various polymerization initiators or combinations of a polymerization initiator and an accelerator. The polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but is usually within the range of 0 to 120°C. When producing a copolymer in this way,
Charge ratio of mono(meth)allyl ether monomer (), maleic acid monomer () and monomer copolymerizable with them (), amount of polymerization initiator used, polymerization temperature, in solvent In the case of polymerization, the molecular weight of the resulting copolymer can be adjusted as appropriate by adjusting the type and amount of the solvent, the amount of the chain transfer agent, etc. The copolymer used as the scouring property improver for cellulose fibers of the present invention is effective over a wide range of molecular weights, but those with molecular weights in the range of 400 to 50,000 are particularly effective. The copolymer thus obtained can be used as it is as a scouring property improver for cellulose fibers of the present invention, but if necessary, it may be further neutralized with an alkaline substance. Preferred examples of such alkaline substances include monovalent metal hydroxides, ammonia, and organic amines. The thus obtained cellulose fiber scouring improver of the present invention can be used in combination with the conventional scouring process using an alkaline agent and a surfactant to greatly enhance the scouring effect of the conventional method and improve the scouring property. It exhibits excellent performance by ensuring uniform penetration of chemicals in subsequent processes such as bleaching, dyeing, and finishing, making operations easier, and increasing the value of the final product. Although its mechanism of action is not necessarily clear, it is thought to be based on the extremely excellent metal ion trapping ability and separation performance of the copolymer used as the scouring property improver for cellulose fibers of the present invention. In addition, the scouring property improver for cellulose fibers of the present invention can be applied to cellulose fibers such as cellulose natural fibers such as cotton and hemp, and cellulose regenerated fibers such as rayon and Kyupora, as well as nylon, polyester, acrylic fibers, etc. It can be applied to mixed fibers with synthetic fibers, and even mixed fibers with semi-synthetic fibers such as acetate.
The form during scouring may be any form such as fiber, thread, skein, cheese, woven fabric, knitted fabric, non-woven fabric, or final fiber products such as clothing and bedding products. As the scouring method, ordinary methods can be used, and pad steam method, pressure boiling method, boiling barrier method, immersion method, or other methods can be selected as appropriate. Furthermore, the scouring property improver of the present invention can be used not only for the scouring mentioned above, but also for other processes such as desizing/scouring, scouring/bleaching, desizing/scouring/bleaching, etc. in one bath. It can also be applied to the scouring process. The present invention will be described below with reference to Reference Examples and Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified in the examples,
All parts are parts by weight, and all percentages are percentages by weight. All viscosities in the reference examples were measured using a Bismethron viscometer manufactured by Seiki Kogyo Research Institute at 25°C and 60 rpm. Moreover, the unreacted rate of each monomer was determined using gel permeation chromatography (manufactured by Waters, Model 242) and gas chromatography. Reference Example 1 Polyalkylene glycol monoallyl ether (on average 5 ethylene oxides per molecule) as a monomer () was placed in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, gas inlet tube, and reflux condenser. 334 parts (containing units) and 100 parts of water were charged, the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95°C in a nitrogen atmosphere. Thereafter, an aqueous solution in which 117.7 parts of maleic anhydride and 14.2 parts of ammonium persulfate as monomers (2) were dissolved in 246.6 parts of water was added over 120 minutes. After the addition was completed, 14.2 parts of a 20% ammonium persulfate aqueous solution was further added over 20 minutes. After the addition was completed, the temperature inside the reaction vessel was maintained at 95° C. for 100 minutes to complete the polymerization reaction, and an aqueous copolymer solution was obtained. Next, neutralize by adding 40% caustic soda aqueous solution,
An aqueous solution of copolymer (1) was obtained. The molar ratio of repeating structural units determined from the pH, viscosity, and monomer reaction rate of the aqueous solution of copolymer (1) was as shown in Table 1. Reference Example 3 Into the same reaction vessel as in Reference Example 1, 349 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) as a monomer () and 64.7 parts of water were charged and reacted with stirring. The inside of the container was replaced with nitrogen and heated to 65℃ in a nitrogen atmosphere.
heated to. Then, 116 parts of maleic acid and 24.5 parts of ammonium persulfate were added to 174 parts of water as a monomer ().
Aqueous solution, sodium bisulfite dissolved in 11.2 parts
An aqueous solution in which 1 part was dissolved in 44.8 parts of water and 25.8 parts of vinyl acetate as a monomer (2) were each added over 120 minutes. After the addition was completed, the temperature in the reaction vessel was maintained at 65°C for 120 minutes to complete the polymerization reaction, and then for 40 minutes.
% caustic soda aqueous solution was added to perform neutralization, and an aqueous solution of copolymer (3) was obtained. An aqueous solution of this copolymer (3)
The molar ratio of the repeating structural units determined from the pH, viscosity, and monomer reaction rate was as shown in Table 1. Reference Example 2 In the same reaction vessel as Reference Example 1, 220.6 parts of polyalkylene glycol monoallyl ether (containing on average 3 ethylene oxide units and 2 propylene oxide units per molecule) and 3 moles of maleic acid mono-secondary alcohol. Ethoxylate (“SOFTANOL-30”, manufactured by Nippon Shokubai Chemical Co., Ltd.)
344.3 parts of ester, 8.3 parts of styrene, 241.4 parts of isopropyl alcohol, and benzoyl peroxide
Prepare 246.5 parts of the mixed solution consisting of 16.9 parts,
The inside of the reaction vessel was purged with nitrogen while stirring, and heated to the boiling point of the mixed solution in a nitrogen atmosphere. Thereafter, the remaining 585 parts of the mixed solution was added over 120 minutes. After addition,
The polymerization reaction was continued by maintaining the temperature in the reaction vessel at the boiling point for 120 minutes. Thereafter, the temperature inside the reaction vessel was returned to room temperature, 16.9 parts of benzoyl peroxide was added and heated again, and the isopropyl alcohol was distilled off to obtain a copolymer. Next, a 40% aqueous solution of caustic soda and deionized water were added to neutralize the mixture to obtain an aqueous solution of copolymer (2). An aqueous solution of this copolymer (2)
The molar ratio of the repeating structural units determined from the pH, viscosity, and monomer reaction rate was as shown in Table 1.

[Table] Examples 1 to 2 Desized cotton gear bagine was subjected to scouring treatment under the scouring conditions shown below, and its scouring properties were examined. <Scouring conditions> Hardness of water used: 20゜DH Bath ratio: 1:30 Temperature: 95-100℃ Time: 60 minutes Chemicals used: Alkaline agent: Sodium hydroxide 10g/Surfactant (product name: Score Roll M-360, Kao Soap Copolymers (1) to (4) shown in Table 2
2g/ The evaluation of the scouring property is based on the width of the fabric after the scouring process.
A sample of 20 mm in length and 300 mm in length was hung over a vat filled with dye water obtained by dissolving the dye so that one end of the sample was immersed in the dye water, and the height at which the dye water was sucked up for 30 seconds was measured. (mm) was measured and used as a measure of scouring property. The results are shown in Table 2. For comparison, Table 2 also shows the results when no scouring improver was used and when ethylenediaminetetraacetic acid or sodium tripolyphosphate was used as the scouring improver. As is clear from the results in Table 2, when the scouring property improver of the present invention was not used, the wettability was poor, indicating that scouring was insufficient. Further, even when ethylenediaminetetraacetic acid and sodium tripolyphosphate were used together with an alkali agent and a surfactant as a scouring property improver, no significant improvement in scouring property was observed. On the other hand, when the scouring property improver of the present invention was used in combination, the water absorption height was high and the wettability was excellent, and a significant improvement in the scouring property was observed.

【table】

Claims (1)

[Claims] 1. General formula (However, in the formula, R ₁ represents hydrogen or a methyl group,
a and b are each 0 or a positive integer, and a+b=1 to 100, -(C ₂ H ₄ O-) unit and -(
C ₃ H ₆ O−) units may be bonded in any order. ) Repeating structural unit (A) shown by and general formula (However, in the formula, X is −(C ₂ H ₄ O−) _n −(C ₃ H ₆ O−) _o R ₄ (R ₄
represents hydrogen or an alkyl group having 1 to 20 carbon atoms, m and n are each 0 or a positive integer, and m+n=0 to 100, and -(C ₂ H ₄ O-) unit and -( C ₃ H ₆ O−) units may be bonded in any order. ), represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group, and Y represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) as a main component, and the total amount of (A) and the total amount of (B) are in a molar ratio of (A)/(B)=
A scouring property improver for cellulose fibers comprising a copolymer having a ratio of 40/60 to 60/40.