JP2623493B2 - pH buffering fiber structure and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fibrous structure having a pH buffering property and a method for producing the same.

[0002]

2. Description of the Related Art When a synthetic fiber or a natural fiber is treated with a strong acid or a strong base, the fiber is neutralized with a weak acid or a weak base after the treatment.
It cannot be buffered. In addition, commonly used antistatic processing, pH buffering in processing such as resin processing,
In particular, it is difficult to provide a wash-resistant pH buffer.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a method for treating fibers with pH.
By attaching a compound having buffering action, Western aggravated by the neutralizing capacity allowed imparting having washing durability against acid rain and the like which influence in Japan is concerned, the above acid rain
Structure and its manufacturing method that can solve the problems caused by
It is intended to provide.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a carboxyl group at least on the surface of a fiber and a neutralized salt form.
Polymer or copolymer containing carboxyl groups
Characterized in that it exhibits a pH of 5 to 7 when wet.
Carboxy for impact fiber structures and fiber structures
To a polymer or copolymer containing
Polymer or copolymer containing ruboxyl group, or base
Processing fluid with a pH value of 4 to 7
After the application, the heat treatment is followed by a heat treatment.
Achieved by a method for producing an impact fiber structure.
You. In particular, caps attached to the pH buffering fiber structure
Contains ruboxyl groups and carboxyl groups neutralized to salt form
The polymer or copolymer has a weight average molecular weight of 1,000 to
Preferably it is 1,000,000.

In the present invention, the fibrous structure is not particularly limited, and is a woven fabric, a knitted fabric or a non-woven fabric containing all natural fibers such as cotton, wool and silk, and synthetic fibers such as polyester, nylon, acrylic and acetate. Etc. are all included.

In the present invention, at least a carboxyl group and a carboxyl neutralized into a salt form are provided on at least the surface of the fiber.
It is necessary that a polymer or copolymer containing groups be attached.

The above carboxyl-containing polymer or copolymer
The union is a polymer or copolymer of an unsaturated carboxylic acid containing a hydrophobic monomer, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated monomer, or a mixture thereof. The degree of polymerization is controlled by changing the amount of a known chain transfer agent. The molecular weight of the above polymer and copolymer is 1,000 to 1,000.
0000, preferably 10,000 to 500,000
It is. For the molecular weight, a calibration curve was prepared by gel permeation chromatography using a water-soluble polymer of known molecular weight, pullulan as a standard substance, and the weight average molecular weight was determined using this. The copolymer of the unsaturated carboxylic acid and the ethylenically unsaturated monomer preferably contains 1 to 10 mol% of the ethylenically unsaturated monomer.

[0008] Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, oleic acid, cinnamic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and the like. Examples of the ethylenically unsaturated monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dihydroxy Ethyl methacrylamide and the like can be mentioned. Preferred polymers and
Examples thereof include a copolymer of acrylic acid and 2-hydroxyethyl acrylate, a copolymer of acrylic acid and N-methylolacrylamide, and a copolymer of acrylic acid, 2-hydroxyethyl methacrylate and acrylamide. The polymer sodium hydroxide, to generate a neutralized salt by base such as potassium hydroxide to a predetermined pH value.

The effect of the content of the ethylenically unsaturated monomer is pH
It is useful for improving the washing durability of cushioning. In order to further improve the washing durability of the pH buffer, it is preferable to add a water-soluble epoxy compound to the above-mentioned polymer and copolymer.

The pH-buffering fiber structure of the present invention is different from the fiber structure in a polymer containing a carboxyl group.
Alternatively, the copolymer contains a salt-neutralized carboxyl group.
Add a polymer or copolymer, or a basic substance
After applying a working fluid having a pH value of 4 to 7,
And a heat treatment method. In the production method of the present invention , neutralization to a carboxyl group and a salt form
The polymer or copolymer containing a carboxyl group is as described above. Basic substances are substances that generate hydroxide ions in an aqueous solution or have hydroxide ions when reacted with an acid, such as ammonia, sodium, potassium,
Metal hydroxides such as calcium, barium, and magnesium. A polymer containing the carboxyl group or
The copolymer containing a carboxyl group neutralized into a salt form
The pH value of the working fluid to which the coalesced or copolymerized material or the basic substance is added is weakly acidic (4 to 7). This predetermined pH value is determined by the polymer containing carboxyl groups or the copolymer.
Contains neutralized carboxyl groups in the salt form to be added to the polymer
It can be controlled by the amount of the added polymer or copolymer or basic substance.

The processing method of the present invention is not particularly limited, and may be a method capable of forming a thin film on at least the surface of the fiber of the fiber structure, such as a coating method, a patto dry method, a put steam method, a spray method, and an immersion method. I just need. For example, the resin of the present invention is impregnated with a predetermined amount in a pate-drying method, which is generally used as a resin processing method, then squeezed, dried at 100 to 130 ° C., and heat-treated at 150 to 180 ° C., so that excellent adhesion can be obtained. It is.

In the above-mentioned processing method, a coating method is particularly preferable, and examples of the coating resin used in the present invention include an acrylic resin, a urethane resin, and a silicone resin. The pH buffering property has a large effect in a porous resin, and examples thereof include a urethane-based porous resin. In addition, the pH buffering effect can be increased by kneading porous particles of silicon dioxide, titanium dioxide, alumina, zirconia, magnesia, titanium nitride, zirconium carbide, zirconium oxide, etc. into the resin. The coating method of the resin liquid may be either dry coating or wet coating, and a coating method such as a floating knife coater, a knife over roll coater, a reverse roll coater, a roll doctor coater, a gravure roll coater, a kiss roll coater or the like can be used. . Further, the coating film may be made porous by a known method. In the present invention, it goes without saying that various treatments such as water repellency and flexibility may be performed in addition to the coating process. However, the water-repellent processing can be performed before or after the coating processing. However, when the water-repelling processing is performed before the coating processing, it is necessary to pay sufficient attention to the adhesive strength.

In the application of the present invention, the control of the amount of the compound adhering to the fiber can be controlled by the concentration of the compound in the aqueous solution. The amount of the compound attached on the fiber is preferably 0.05 to 5% by weight in terms of solid content. 0.0
If the content is less than 5% by weight, the desired pH buffering effect cannot be easily obtained, which is not preferable. On the other hand, if it exceeds 5% by weight, depending on the form of the treated cloth, not only the feel becomes rough and hard, but also it tends to hinder other processing.

[0014]

The present invention will be described in more detail with reference to the following examples. The pH measurement method and the washing test of the processed fabric in the examples are as follows. (1) The pH value of the solution was measured by Horiba Seisakusho's F-12 pH
Measure with meter

(2) The pH value measuring method A for evaluating the pH buffering property of the cloth was measured by bringing the cloth moistened with a fixed amount of liquid into contact with the electrode part of a TwinB-112 pH meter manufactured by Horiba, Ltd. The weight of the fabric is 0.02 g, and 0.1 ml
And subjected to pH measurement. A solution prepared with distilled water and an acid or alkali was used as a liquid for wetting the cloth. It is determined that the closer the value measured when the fabric is wetted with a liquid having a pH of 3, for example, to the value measured when the fabric is wetted with distilled water, the higher the pH buffering property is.

(3) A pH value measuring method B for evaluating the pH buffering property of the cloth is as follows. 2 g of the cloth is placed on a Nutsche funnel having a diameter of about 9 cm, and 50 ml of a solution prepared with distilled water and acid or alkali is placed on the cloth. The pH value of the filtrate obtained by pouring and filtering the cloth was measured. As the pH value of the filtrate is, for example, a value measured when a solution having a pH of 4 is poured is closer to the value obtained when the distilled water is poured, it is determined that there is a pH buffering property.

(4) A pH value measuring method C for evaluating the pH buffering property of a cloth is as follows: 1 g of a cloth is immersed in a liquid prepared with 50 times the volume of distilled water and an acid or alkali for 10 minutes, and then the pH value of the immersion liquid is measured. Was measured. It is determined that the closer the value of the pH value of the immersion liquid to a solution having a pH of 4, for example, to the value of the distilled water, the higher the pH buffering property.

(5) Washing test JIS L-0217
103 method

(6) Amount of adhesion

(Equation 1)

In the examples, "parts" means "parts by weight", and the moisture permeability and the water resistance are based on JIS-L-1099 and JIS-L-
It was measured by 1092 (Method A).

Example 1 A polyester having a weight-average molecular weight of 85,000 neutralized to a sodium salt with a composition of acrylic acid (90 mol%), butadiene (10 mol%) and a chain transfer agent was added to a polyester fabric. A polymer having a composition of acid (95 mol%), 2-hydroxyethyl methacrylate (5 mol%) and a chain transfer agent and having a weight average molecular weight of 160,000 was mixed at a ratio of 6: 2, and 1.2 wt% (based on Fiber). The application method was such that the woven fabric was immersed in a processing solution prepared from an aqueous solution of the polymer, squeezed with a mangle, and then dried and heat-treated with a pin tenter type hot air dryer. As Comparative Example 1, a polyester fabric was manufactured using PMX-56 (antistatic agent) manufactured by Yoshimura Oil Chemical Co., Ltd.
Using a 5% aqueous solution as a processing liquid, processing was performed in the same manner as in the application method of Example 1. Table 1 shows the measurement results of the pH value of the work cloth.

[0022]

[Table 1]

From the results shown in Table 1, the processed fabric of the present invention has a pH of 3
Has a buffering effect on the liquid. On the other hand, the work cloth of Comparative Example 1 does not show a buffering action. This indicates that the magnitude of the buffering action, that is, the buffer capacity of the work cloth of the present invention is large.

Example 2 A polymer having a weight-average molecular weight of 85,000 neutralized to a sodium salt with a composition of acrylic acid (95 mol%), butadiene (10 mol%) and a chain transfer agent was added to a polyester fabric. A polymer having a weight-average molecular weight of 100,000 and a composition of acid (95 mol%), 2-hydroxyethyl methacrylate (2.5 mol%), N-methylolacrylamide (2.5 mol%) and a chain transfer agent was prepared as follows: 3 to give 1.5% by weight (based on fiber). The application method was the same as in Example 1. As Comparative Example 2, ELETAT AK-10 manufactured by YAS Co., Ltd. was applied to a polyester fabric.
Using a 2% aqueous solution of (antistatic agent) as a processing liquid, processing was performed in the same manner as in the application method of Example 1. Table 2 shows the measurement results of the pH value of the work cloth.

[0025]

[Table 2]

From the results in Table 2, the work cloth of Comparative Example 2 has a pH value of
No buffer action was exhibited for the solution of No. 3. The processed fabric of the present invention has a buffering effect on a liquid having a pH of 3.

Example 3 A polyester fabric was mixed with acrylic acid (80 mol%), maleic acid (10 mol%), isoamylene (10 mol%) and a chain transfer agent, and was neutralized to a potassium salt with a weight average molecular weight of 50, 000 polymer and 6% by weight of acrylic acid (95%
Mol%) and 2-hydroxyethyl methacrylate (5
Mol%) and the weight average molecular weight of 35 in the composition of the chain transfer agent.
An aqueous solution of a mixture of 000 polymer 2% by weight and ethylene glycol diglycidyl ether 3% by weight was applied in the same manner as in Example 1 as a working fluid. After the application, the substrate was further washed with hot water at 50 ° C. for 10 minutes. As Comparative Example 3, 0.3% by weight of Beckamine APM manufactured by Dainippon Ink and 0.3% by weight of Catalyst 376 were applied to a polyester fabric as a working liquid in the same manner as in Example 1. Table 3 shows the measurement results of the pH value of the work cloth.

[0028]

[Table 3]

From the results shown in Table 3, the buffering effect was not obtained in Comparative Example 3, but the buffering effect was obtained in Example 3. In Example 3, the washing durability was further improved by the addition of the water-soluble epoxy compound.

Example 4 A plain weave made of warp and weft # 40 cotton yarn was processed in the same manner as in Example 1 using the working fluid shown in Example 1. As Comparative Example 4, 3 wt% of Superflex E2000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was applied to the above-mentioned cotton fabric in the same manner as in Example 1 as a working fluid. Table 4 shows the results of measuring the pH value of the processed fabric.

[0031]

[Table 4] From the results in Table 4, the present invention can impart pH buffering properties to cotton fabrics.

Example 5 A polyester fabric was provided with 1.2% by weight (based on fiber) of a pH buffer substance having a pH in the range of 5 to 7. The application method is pH
The fabric was immersed in an aqueous solution of a buffer substance as a processing liquid, squeezed with a mangle, and then dried and heat-treated with a pin tenter-type hot-air dryer. The processed fabric was measured for its wet pH value by pH value measurement method A in order to evaluate the pH buffering property.
Table 5 shows the results.

[0033]

[Table 5]

From the results shown in Table 5, by selecting and applying a pH buffer substance, pH 5 to 7 is obtained when wet with distilled water, and the pH value when wet with the pH 3 solution also shows a value having a buffering effect. Thus, a work cloth having a pH buffering property is obtained. However, washing durability was not obtained.

Example 6 The processed cloths obtained in Example 1 and Comparative Example 1 were evaluated by the pH value measuring method B. Table 6 shows the results.

[Table 6] From the results in Table 6, p of the filtrate obtained by filtering the processed cloth according to the present invention was obtained.
From the H value, the pH buffering property of the processed fabric of the present invention is recognized.

Example 7 The processed cloths obtained in Example 3 and Comparative Example 3 were subjected to a pH value measuring method A.
Was measured by Table 7 shows the results. PH 8 in Table 7
And pH 10 was prepared with sodium carbonate.

[Table 7] As a result of Table 7, the product of the present invention has a wash-resistant pH buffering property against alkali.

Example 8 Plain woven fabric using a 60d / 48f polyester filament yarn (coarse density: 98 / inch, weft density: 94 / in)
ch) was subjected to dyeing and water-repellent treatment with a fluorine-based water-repellent to obtain a fabric. Then, an acrylic resin (Teisan Resin SG-51 (17% solid content) manufactured by Teikoku Chemical Co., Ltd.) 100
A polymer having a weight average molecular weight of 85,000 neutralized to a sodium salt with a composition of acrylic acid (90 mol%), butadiene (10 mol%) and a chain transfer agent (solid content: 30%)
12 parts by weight of a polymer having a weight average molecular weight of 160,000 (solid content: 30%) composed of acrylic acid (95 mol%), 2-hydroxyethyl methacrylate (5 mol%) and a chain transfer agent.
%), And 6.4 g / m ^{2 was} applied using a floating knife coater. Immediately, drying was performed at a temperature of 120 ° C., and heat treatment (170 ° C.) was performed. In addition, as Comparative Example 8, only an acrylic resin was applied to a polyester fabric using a floating knife coater in the same manner as in Example 8. Table 8 shows the physical property results of the processed fabric. Here, W = 5 indicates the result of washing five times.

[0038]

[Table 8] From the results in Table 8, p of the filtrate obtained by filtering the processed fabric of the present invention was obtained.
From the H value, the pH buffering property of the processed fabric of the present invention is recognized.

Example 9 Acrylic acid (90 mol%), butadiene (10 mol%) and chain transfer were added to 100 parts of a porous urethane resin (Heimlen X-3040 (solid content: 30%) manufactured by Dainichi Seika Kogyo Co., Ltd.). 12 parts of a polymer having a weight average molecular weight of 85,000 (solid content: 30%) neutralized to a sodium salt by the composition of the agent, acrylic acid (95 mol%), 2-hydroxyethyl methacrylate (5 mol%) and chain transfer A mixture of 4 parts of a polymer having a weight average molecular weight of 160,000 (solid content: 30%) in a solvent composition of 34 parts of water and 5 parts of methyl ethyl ketone was gradually dropped to prepare a mixture. Then, 11.7 g / m _{2 was} applied to the dough used in Example 8 using a knife over roll coater, immediately dried at a temperature of 80 ° C., and subjected to a heat treatment (170 ° C.). In addition, as Comparative Example 9, only a urethane-based resin was processed on a polyester fabric using a knife over roll coater in the same manner as in Example 9. Table 9 shows the physical property results of the processed fabric.

[0040]

[Table 9] From the results shown in Table 9, p of the filtrate obtained by filtering the processed cloth of the present invention was obtained.
From the H value, the pH buffering property of the processed fabric of the present invention is recognized.

Example 10 An acrylic resin (Teisan Resin SG-51 (17% solid content), Teikoku Chemical Co., Ltd.) was used as the fabric used in Example 8.
In 0 parts, silicon dioxide porous particles (average particle diameter 2.7
μ) 40 parts and isopropyl alcohol 60 parts are mixed,
13 parts of the prepared porous silica solution was added, and acrylic acid (90 mol%), butadiene (10 mol%)
And a polymer having a weight average molecular weight of 85,000 (solid content 30%) neutralized to a sodium salt with a composition of a chain transfer agent 12
Part and a polymer having a weight average molecular weight of 160,000 (solid content: 30 mol%) comprising acrylic acid (95 mol%), 2-hydroxyethyl methacrylate (5 mol%) and a chain transfer agent.
%), And 8.0 g / m ^{2 was} applied using a floating knife coater, immediately dried at a temperature of 120 ° C., and subjected to a heat treatment (170 ° C.). As Comparative Example 10, only a polyester fabric prepared by adjusting an acrylic resin and a porous silica liquid was processed by a floating knife coater in the same manner as in Example 10.
Table 10 shows the physical property results of the processed fabric.

[0042]

[Table 10] From the results shown in Table 10, the pH value of the filtrate obtained by filtering the processed cloth of the present invention indicates the pH buffering property of the processed cloth of the present invention.

Example 11 A nylon knitted fabric was composed of acrylic acid (90 mol%), butadiene (8 mol%), 2-hydroxyethyl methacrylate (2 mol%) and a chain transfer agent, and had a weight average molecular weight of 85,000. An aqueous solution of potassium hydroxide was added to 3 parts of the above polymer to give a processing liquid having a pH value of 5 when the total amount was adjusted to 100 parts, to give 1.5% by weight (based on fiber). The application method was as follows. The knitted fabric was immersed in a working fluid prepared by preparing an aqueous solution of the polymer, squeezed with a mangle, and then dried and heat-treated with a pin tenter type hot air dryer. As Comparative Example 11, a nylon knit was processed in the same manner as in Example 11 using a 1% aqueous solution of Derektor GX (antistatic agent) manufactured by Meisei Chemical Co., Ltd. as a processing liquid.

Example 12 Polyester thin fabric was mixed with acrylic acid (90 mol%),
The composition of butadiene (5 mol%), 2-hydroxyethyl methacrylate (2.5 mol%), N-methylolacrylamide (2.5 mol%) and a chain transfer agent was added to 5 parts of a polymer having a weight average molecular weight of 75,000. An aqueous sodium hydroxide solution was added to adjust the pH value to 6 when the total amount was 100 parts.
1.2 wt% (based on fiber) was applied.
The application method was as follows. The woven fabric was immersed in a processing solution prepared from an aqueous solution of the polymer, squeezed with a mangle, and then dried and heat-treated with a pin tenter type hot air dryer. As Comparative Example 12, Eletat AK-10 manufactured by YAS Co., Ltd.
Example 12 Using a 2% aqueous solution of (antistatic agent) as a working fluid
Was processed in the same manner as the method of applying.

Example 13 Composition of acrylic acid (75 mol%), maleic acid (10 mol%), isoamylene (10 mol%), 2-hydroxyethyl methacrylate (5 mol%), and chain transfer agent on cotton broad An aqueous sodium hydroxide solution was added to 5 parts of a polymer having a weight average molecular weight of 150,000 with
The working fluid adjusted to have a pH value of 5 was 1.3% by weight (relative to the fiber). The application method is to immerse cotton broad in a processing solution prepared from an aqueous solution of the polymer and squeeze it with a mangle,
Then, drying and heat treatment were performed with a pin tenter type hot air dryer. As Comparative Example 13, cotton broad was processed in the same manner as in Example 13 by using 3% by weight of Superflex E2000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a processing liquid.

Example 14 In 93 parts of the working fluid of Example 11, 5 parts of a water / oil repellent (Asahigard AG923 manufactured by Asahi Glass Co., Ltd.), 0.4 parts of an aminoplast resin (Becamine APM manufactured by Dainippon Ink and Chemicals), and a catalyst ( Dainippon Ink Co., Ltd. Catalyst 376) 0.3
0.8 parts by weight of a working fluid containing 0.3 parts of dimethylpolysiloxane (Dick Nippon Ink Co., Ltd. Dick Silicon Softener 500) and 1 part of antistatic agent (Meisei Chemical Co., Ltd. Derektor GX). Granted. The application method was as follows. A polyester feather double woven fabric was immersed in a processing solution prepared from an aqueous solution of a polymer, squeezed with a mangle, and then dried and heat-treated with a pin tenter type hot air dryer. As Comparative Example 14, a processing liquid obtained by adding the agent of Example 14 to 93 parts of water instead of the processing liquid of Example 11 was processed into a polyester feather double woven fabric by the same method as that of Example 11. Examples 11 to
Table 11 shows the measurement results of the pH values of the work cloths obtained in No. 14 and Comparative Examples 11 to 14.

[0047]

[Table 11]

[0048]

According to the present invention, it has a pH buffering action.
Carboxyl groups and carboxyl groups neutralized to salt form
By adhering the polymer or copolymer containing the fibers to the fibers, the acid rain and the like attached to the fibers are neutralized, and the pH value of the acid rain and the like that has passed through the fiber structure and contacted the skin is averaged on the skin surface. Yes it is closer to pH5~7 which are said to pH value
Can solve problems caused by acid rain, etc.
And its neutralizing ability is resistant to washing against alkali.
It has the effect of having longevity.

 ──────────────────────────────────────────────────続 き Continuation of the front page Examiner Masato Matsunawa (56) Reference JP-A-53-126394 (JP, A) JP-A-4-214467 (JP, A)

Claims (3)

(57) [Claims] Claims: 1. A carboxyl on at least the surface of a fiber.
Containing carboxyl groups neutralized in the form of
Is a pH buffering fibrous structure to which a copolymer is attached and which exhibits a pH of 5 to 7 when wet. 2. A neutralized carboxyl group and a salt form.
The pH buffering fiber structure according to claim 1, wherein the polymer or copolymer containing a ruboxyl group has a weight average molecular weight of 1,000 to 1,000,000. 3. A carboxyl group is added to a fiber structure.
Carboxyl neutralized to a salt form in the polymer or copolymer containing
A pH buffering fibrous structure comprising a polymer or copolymer containing a sil group, or a basic substance added thereto, and a heat treatment after applying a working fluid having a pH value of 4 to 7 and then applying a heat treatment. Manufacturing method.