JPH03185184A - Washability-improving agent for fiber product - Google Patents

Abstract

PURPOSE:To improve the subject agent preventing the generation, re-adhesion, etc., of scums produced in dying processes and having excellent metal ion chelate dispersibility by using a copolymer of a specific monomer with maleic acid, acrylic acid, etc., in a specified ratio, the copolymer having a specific mol.wt. CONSTITUTION:A washability-improving agent for fiber products comprises a copolymer of (A) a monomer of the formula (R1 is H or methyl; R2 is ethylene or propylene; R3 is H, methyl, etc.; l is 1-40) with (B) a monomer selected from maleic acid, (meth)acrylic acid and salts thereof in an A/B weight ratio of 0.06-1.0 (the weights of the structural monomers), the copolymer having an average mol.wt. of 1000-10000. When the agent is added in an amount of >=0.2g/l to a bath in dying and finishing processes, the agent forms a chelate with metal ions brought into the bath to prevent the re-adhesion of the metal ions to the web, prevent the produced scums and depress the re-adhesion. In an alkali weight-reducing process, the washing of oligomers, etc., is improved to provide a good touch for the web.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a detergency improver for textile products.

More specifically, the present invention applies to cellulose fibers such as cotton and hemp, synthetic fibers such as polyester, nylon, and acrylic, and mixed fibers thereof, including desizing, scouring, bleaching or soaping, mercerizing cotton, and mercerizing polyester. This invention relates to a detergency improver for textile products that can be used for alkali weight loss or cleaning dyeing cans, has good compatibility with nonionic surfactants and anionic surfactants, and has excellent alkali resistance.

[Conventional technology]

Cellulose fibers such as cotton and hemp contain large amounts of heavy metal ions such as iron, calcium, copper, manganese, and magnesium, and during the desizing, scouring, and bleaching processes, fibers become brittle, pinholes occur, roll stains, etc. is known to cause

In addition, during the scouring of synthetic fibers, especially polyester, water-insoluble salts are generated due to the reaction of acrylic glue and terephthalate with water and divalent or trivalent metal ions present in the fibers, and oligomers and matting agents in polyester are generated. It is known that scouring troubles due to the elution of the titanium oxide used and subsequent dyeing troubles occur.

In order to prevent the above-mentioned troubles with cellulose fibers, a stabilizer for hydrogen peroxide bleaching containing poly-α-hydroxyacrylate as a main component ( For example, it is known to use Neolate P1.C-7000 (manufactured by NICCA CHEMICAL). This prevents troubles caused by silicates conventionally used as stabilizers, and troubles such as the formation of pinholes due to the reaction between hydrogen peroxide, used as a bleaching agent, and the metal ions mentioned above.

Furthermore, in order to prevent troubles during polyester scouring, ethylenediaminetetraacetate acid (EDT) is used in the desizing, scouring, and bleaching processes of cellulose fibers.
A) A method is also used to increase cleaning efficiency by using a chelating agent such as diethylene triamine pentaacetic acid (DTPA) in combination with a polycarboxylic acid salt such as sodium polyacrylate, sodium polymethacrylate, or sodium polymaleate. (Special Publication No. 59-179681).

[Problem to be solved by the invention]

Polymerized phosphates used in conjunction with desizing, scouring, bleaching or soaping, mercerizing cotton, alkaline reduction of polyester, or cleaning of dyed can bodies, such as sodium tripolyphosphate, aminocarboxylate organic chelating agents,
For example, the solubility of EDTA and DTPA decreases in the high pHTiff range, resulting in a decrease in chelating ability.If the concentration of hardness components in water is higher than a certain level, the chelation efficiency decreases, and the hydration of polymerized phosphates decreases. There were problems such as scale formation due to decomposition, and it was not very effective.

It is also known that polycarboxylic acid salts such as polysodium acrylate, polysodium methacrylate, and polysodium maleate vary in their cleaning efficiency depending on the degree of polymerization, and that continuous processing causes variations in effectiveness due to selective adsorption. ing.

Furthermore, they have poor compatibility with nonionic and anionic surfactants, making it difficult to prepare concentrated stock solutions.

[Means to solve the problem]

In order to solve the above problems, the present invention is a copolymer of a monomer (A) represented by the following general formula and at least one monomer (B) selected from maleic acid, acrylic acid, methacrylic acid, and salts thereof. The present invention provides a detergency improver for textile products which is a combination of constituent monomers, has a weight ratio A/B of 0.05 to 1.0, and has an average molecular weight of too much to 10,000.

1 CH,=C(A) COO-←Rt O-+-R3 In the above formula, R1 represents hydrogen or methyl, R2 represents ethylene or propylene, R1 represents hydrogen, methyl or ethyl, l is 1 ~40 integer.

Examples of monomers (A) useful in the present invention include methoxypolyethylene glycol 1000 methacrylate, polyethylene glycol 400 methacrylate, and polypropylene glycol 600 methacrylate. It is also possible to use polypropylene glycol methacrylate and polyethylene glycol methacrylate together. be.

Monomer (B) is at least one monomer selected from maleic acid, acrylic acid, methacrylic acid, and salts thereof. Preferred salts are sodium, potassium,
Water-soluble salts such as ammonium, monoethanolamine, and jetanolamine salts.

The weight ratio A/B of the constituent monomers is 0.05 to 1. o, preferably 0.1 to 0.5. Moreover, the average molecular weight is suitably 1,000 to 10,000.

The polymerization to obtain the copolymer is carried out, for example, in a nitrogen stream in the presence of a radical initiator.

Useful initiators include persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, redox initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo initiators. can be mentioned. The amount of initiator is suitably 0.05 to 1.0 parts by weight per 100 parts by weight of monomer.

Suitable polymerization temperatures and times are 2-5 at 50-90"C.
It's time.

Monomer (A) and monomer (B) are used after being dissolved in water. When polypropylene glycol methacrylate or polypropylene glycol acrylate is used as monomer (B) or as part of monomer (B), it is preferred to add a water-miscible solvent such as isopropyl alcohol or butyl cellosolve.

For the purpose of controlling the degree of polymerization, it is also effective to use a chain transfer agent such as octyl thioglycolate.

The concentration of the detergency improver of the present invention is 0.05g #! when used as a product with a solid content of 30%. or more, preferably 0.2
It is preferable that gal1 or higher.

Examples of equipment in which the detergency improver of the present invention is used during desizing, scouring, bleaching, or soaping include Wince dyeing machines, jet dyeing machines, cheese dyeing machines, Zipper dyeing machines, batch-type machines such as washers, and J-boxes. There are continuous devices such as , shi-box, purple range, and open soaper.

When the detergency improver of the present invention is used for mercerizing cotton or linen, it can be used in the mercerizing bath and soaping bath of a yarn mercerizing machine and a mercerizing machine for knitting and textiles.

In alkaline weight loss processing of polyester, it can be used in Nt baths and soaping baths for hanging, pad steam and cold pad patches. In addition, as a dyeing can cleaning agent, it is used in jet dyeing machines, beam dyeing machines, cheese dyeing machines, Obermeyer dyeing machines, etc.

[Function] General polycarboxylic acids, i.e., homopolymers of maleic acid, acrylic acid, methacrylic acid, and their salts, have poor compatibility with nonionic surfactants and anionic surfactants, and can only be used in combination by dilution. It becomes possible. This is considered to be due to poor compatibility between the low molecular weight surfactant and the high molecular weight polycarboxylic acid due to the difference in molecular weight, and mismatch in the structural units of the two structures.

On the other hand, since the detergency improver of the present invention contains a polyethylene glycol or polypropylene glycol chain in the side chain, it has high compatibility with nonionic surfactants,
It is also highly compatible with anionic surfactants, especially sulfates and phosphate ester salts of alkyl allyl ether type nonionic compounds or alkyl ether type nonionic compounds.

High HLB can be achieved by changing the molecular weight of polyethylene glycol and polypropylene glycol or the composition ratio of polyethylene glycol and polypropylene glycol.
This makes it possible to mix at a high concentration with a low HLB nonionic surfactant or anionic surfactant.

By using the detergency improver of the present invention in combination, the scouring and soaping effects of the nonionic surfactant or anionic surfactant are synergistically improved.

Furthermore, the action of the copolymerized polycarboxylic acid prevents the generation and re-deposition of various types of scum from metal ions such as iron, copper, and calcium and glues, oils, unfixed dyes, etc., and improves dispersibility. improved results in subsequent dyeing and finishing.

When used for mercerizing cotton and linen, the detergency improver of the present invention has good alkali resistance, so it does not decompose or separate itself, prevents scale adhesion to rolls, etc., and improves bath dispersion. It has the effect of improving sex.

When the detergency improver of the present invention is used to reduce the amount of polyester with alkali, the detergency of polyester oligomers, terephthalates, titanium oxide, etc. is improved, a good texture is obtained, and it is evened out in the next dyeing process. dyeing is obtained. In addition, when used in conjunction with cleaning the dyeing can body, it has the effect of improving the dispersibility of polyester oligomers, dye complexes, various scums, etc.

〔Example〕

Next, the present invention will be further explained based on examples. However, the present invention is not limited only to these examples.

Place 140 g of water in a 500 d four-eye flask and heat to 75°C under a stream of nitrogen. Next, in water, 76.5 g of sodium acrylate (in terms of solid content), 11,400 methoxypolyethylene glycol, and 13.5 g of methacrylate were added.
5 g, 150 g of monomer solution containing 0.1 g of octyl thioglycolate and 0.12 g of potassium persulfate.
An initiator solution prepared by dissolving 10g of
Approximately 300 g of brown transparent liquid was obtained (referred to as Invention Product 1).
.

110 g of water and 30 g of butyl cellosolve are added to a 500 d four-eye flask and heated to 75°C under a nitrogen stream. Then add 76% sodium acrylate in water.
5g (solid content equivalent), polyethylene glycol"10
150 g of monomer solution in which 9.0 g of 00 methacrylate, 4.5 g of polypropylene glycol 400 methacrylate, and 0.1 g of octyl thioglycolate were dissolved.
An initiator solution prepared by dissolving 0.09 g of ammonium persulfate and 10 g of water was added dropwise over 1 hour, polymerized at 80-85°C for 2 hours, and then cooled to form a brown transparent liquid with a viscosity of 60 cp.
00g was obtained (referred to as product 2 of the present invention).

1515 parts of nonylphenol added with 10 moles of ethylene oxide were added to 85 parts (parts by weight, same hereinafter) of Inventive Product 1 based on gold to make a total amount of 100 parts, to obtain a yellow transparent liquid with a viscosity of 110 cp (referred to as Inventive Product 3). .

Add 70 parts of the product of the present invention to the phosphoric acid ester sodium salt of a 9 mol ethylene oxide adduct of nonylphenol (50 parts
% product) Add 30 parts to make the total amount 100 parts, and make the viscosity 100 parts.
A yellow transparent liquid of cp was obtained (referred to as product 4 of the present invention).

30g of sodium polyacrylate (converted to solid content, molecular weight approximately 5
000) with water to make a total amount of 100g, the viscosity is 250
A yellow transparent liquid of cp was obtained (referred to as comparative product 1).

Stop Comparison 2 Ethylenetetraacetic acid 4Na salt (EDTA-4Na
) was made up to 100 g with water to obtain a pale yellow transparent liquid with a viscosity of 8 cp (referred to as Comparative Product 2).

Compatibility with nonionic surfactants and anionic surfactants The sample and surfactant were mixed at room temperature in the proportions shown below, and allowed to stand at room temperature and 45°C for 7 days. Stability is determined by the presence or absence of precipitates and surface separation.

Unlike aqueous solutions of polycarboxylic acids and their salts, the products of the present invention have good compatibility with nonionic and anionic surfactants in a wide range of blending ratios, so they can be used as scouring agents while maintaining the dispersion effect of polycarboxylic acids. and double the performance of soaping agents.

-2 Alkaline Blank A bath having the following composition is allowed to stand at room temperature for 24 hours, and the stability and alkali resistance are determined by the presence or absence of precipitates and surface separation.

NaOH (flake) x g/1 sample
2 g/1 Keiguo Stable Δ Inventive products 1 and 2, which show some separation, show good alkali resistance similar to general polycarboxylate salts, and surfactant-containing inventive products 3 and 4. It also provides good alkali resistance due to the effect of polyalkylene glycol methacrylate copolymerization.

3. Clearing of ions The following test solution is prepared, and the chelate dispersion ability is evaluated based on the state of the bath after heating at 90 to 95°C for 30 minutes and the presence or absence of filtration residue from the filtration method.

Metal ions x ppm NaOH (flake) 2gN1 Sample 1g/I! .

臇 Fruit ○ Stable Δ Slightly stable Unstable × The product of the present invention has excellent metal ion chelate dispersion ability, which is the inherent performance of polycarboxylate.

4 Upper dye scum (disperse dye/cationic dye complex)
In order to compare the dispersibility of polyester fiber oligomer scum and polyester fiber oligomer scum, a mini color manufactured by Chixam Giken was used which was treated at 130°C for 45 minutes according to the following recipe, and then 90°C.
Filter at °C and evaluate for the presence of residue.

Scum 0.1g/l High Fo Sodium Sulfide 2
g/12NaOH (flake)
2g/l sample 2g#! Sunmol DMC1gel (can body cleaning agent manufactured by NICCA Chemical Co., Ltd.) In addition, when products 3 and 4 of the present invention were used, Sunmol DMC was not used.

Results ○ No scum Δ Some scum × Scum The products of the present invention have the effect of improving scum dispersion, and in particular, products 3 and 4 of the present invention provide good cleaning effects without the need for a new can cleaning agent.

i 5 f Spot 2 drops of commercially available knitting oil (Bexilar A manufactured by Showa Shell Sekiyu) on scouring and bleached cotton knitting, drying at 120°C for 5 minutes, and then applying 90°C according to the following scouring recipe.
Scour for 5 minutes at °C.

Next, a direct dye, Kayarus 5upra Blu
e BWL 143 (Nippon Kayaku) 0.1g #! The sample was placed in a dyeing bath with a concentration of , heated to 60° C. for 5 minutes, and the scouring property (uneven dyeing and wrinkles) was examined after dyeing.

Sample 1 g/I NazCO: + 1 g/ 12 Sunmol BH-20, 5 gel (scouring agent manufactured by Nicca Chemical Co., Ltd.) Note that when using products 3 and 4 of the present invention, Sunmol B) I-2 was used. There wasn't.

Supervision ○ Good Δ Average × Poor The products of the present invention have the effect of improving scouring properties, and in particular, products 3 and 4 of the present invention provide good scouring effects without the need for a new scouring agent.

〔Effect of the invention〕

By using the detergency improver of the present invention, it is possible to chelate the metal components brought in from the used water and fibers, and also to prevent the insolubilization of pastes, oils, and decomposition product salts of esters due to heavy metal ions.

This prevents re-adhesion to the scouring and soaping fabrics and prevents troubles in the next dyeing and finishing steps.

Furthermore, since the product of the present invention has good compatibility with nonionic surfactants and anionic surfactants, it has the advantage of doubling the performance of the surfactant when used in combination with these surfactants.

In addition, since the product of the present invention has a structure similar to that of a surfactant,
It can be mixed with a surfactant at a high concentration, and a high concentration mixture of the polycarboxylic acid or salt of the present invention and a low-molecular-weight surfactant can be obtained, and workability on site can also be improved.

Claims (1)

[Claims] 1. A copolymer of a monomer (A) represented by the following general formula and at least one monomer (B) selected from maleic acid, acrylic acid, methacrylic acid and salts thereof. The weight ratio A/B of the constituent monomers is 0.05 to 1.0.
A detergency improver for textile products having an average molecular weight of 1,000 to 10,000. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) In the above formula, R_1 represents hydrogen or methyl, R_2 represents ethylene or propylene, R_3 represents hydrogen, methyl or ethyl, and l is an integer from 1 to 40. It is.