JPH10317278A - Fiber structure containing cellulosic fiber for form stabilizing processing and production of fiber structure containing form stabilizing cellulosic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber structure that contains cellulosic fiber for form stabilizing processing and is excellent in wrinkle resistance and wash and wear properties, by applying a compound bearing a plurality of active hydrogen atoms to be methylolated to a cellulosic fiber-containing fiber structure followed by treatment with gaseous formaldehyde. SOLUTION: Cotton woven fabric is treated with a compound bearing at least two active hydrogen atoms to be methylolated such as 4,5-dihydroxy-2- imidazolidinone together with 0.1-10 wt.%, preferably 0.5-5 wt.% of a latent acidic catalyst such as magnesium chloride. Then, the pH of the fabric is adjusted to >=7 with an alkali agent and the fabric is subjected to the treatment with gas phase formalin by using an aqueous formaldehyde solution thereby producing form-stabilized cotton woven fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cellulosic fibers suitable for clothing such as shirts, slacks and blouses, bedclothes such as blankets, sheets and pillowcases, and fiber miscellaneous goods such as hats, handkerchiefs and tablecloths. More specifically, the present invention relates to a cellulosic fiber-containing fiber structure which suppresses a decrease in the strength of a product and has improved shrinkage resistance, W & W (wash and wear) properties, pleating property and puckering property, and shape retention. The present invention relates to a fiber structure and a method for producing the same.

[0002]

2. Description of the Related Art Improvement of drawbacks such as easy wrinkling and shrinkage of cellulosic fibrous structures upon washing is a permanent problem. There is a strong demand for a puckering phenomenon (twitching phenomenon) caused by a difference in elasticity between the thread and the sewing thread or the fabric portion, and an improvement in the shape retention of the product shape. In an attempt to improve this problem, there is an attempt to utilize a gas phase reaction with formaldehyde in a product state. However, the problem of remarkable decrease in the strength of cellulose fibers has been highlighted, and a solution is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a good texture, is excellent in wrinkle resistance, and is excellent in puckering property after repeated washing, W & W property, shrinkproof property, shape retention property, and at the same time, has a strong strength reduction. In particular, it is an object of the present invention to provide a cellulosic fiber-containing fiber structure in which a reduction in abrasion strength is suppressed as much as possible, and a production method therefor excellent in industrial productivity.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, a compound having at least two or more active hydrogens capable of methylolation is added to the cellulosic fiber-containing fiber structure, and the fabric pH of the fiber structure is adjusted to an alkalinity of 7 or more. When performing a formaldehyde vapor processing on a cellulose fiber-containing fiber structure for morphological stability processing and a fiber structure containing cellulosic fibers, a compound having at least two or more active hydrogens capable of methylolation is added to the fiber structure, and A process for producing a morphologically stable cellulose fiber-containing fibrous structure, characterized in that the fabric pH of the fibrous structure is adjusted to an alkalinity of 7 or more and then gas phase processing is performed with formaldehyde.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The cellulose fiber-containing fiber structure referred to in the present invention includes natural cellulose fibers such as cotton, hemp, flax, pulp, and bacterial cellulose fibers, viscose rayon (including polynosic), and copper ammonia method. Regenerated cellulose fibers such as rayon and solvent spinning rayon, and cotton obtained by mixing these cellulosic fibers with synthetic fibers such as polyester, polyamide, acrylic, polyethylene, and polypropylene by blending, blending, weaving, and twisting. , Yarns, woven fabrics, knitted fabrics, non-woven fabrics and the like and fiber products made of them. When mixed with other fibers, the content of the cellulosic fibers is preferably 20% by weight or more, more preferably 30% by weight or more, and still more preferably 50% by weight or more, in order to sufficiently exhibit the effects of the present invention. is there.

[0006] The compound having two or more active hydrogens capable of being converted into methylol (hereinafter abbreviated as an active hydrogen compound) used in the present invention refers to a cellulose which is used to crosslink the inside of a cellulose fiber in a fiber structure with formaldehyde. This is for reducing the cross-linking strain generated in the microstructure, and this effect is exhibited by the so-called cross-linked chain length control effect in which the compound is cross-linked with cellulose after being methylolated. As a result, wrinkle resistance, puckering, and shape retention after washing of the product are improved, and at the same time, in addition to tearing strength and tensile strength, especially abrasion strength is significantly improved.

The following can be used as the active hydrogen compound usable in the present invention. Malonamide, organic carboxylic acid amide and organic oxycarboxylic acid amide compounds such as malic amide, acrylamide, polymers such as methacrylamide and copolymers thereof and other monomers,
Urea, ethylene urea, propylene urea, uron, tetrahydro-5- (2-hydroxyethyl) -1,3,5-
Urea-based and cyclic urea-based compounds such as triazin-2-one and 4,5-dihydroxy-2-imidazolidinone, and melamine-based compounds such as melamine, alone and in combination. Furthermore, these compounds are used alone or in a mixture of these compounds cross-linked with formaldehyde, glyoxal, or the like.
A mixture in which the H group is left or a crosslinked product of these with the above-mentioned urea-based compound or melamine-based compound can also be used.

[0008] The active hydrogen compound used in the present invention is (a) that it can be easily penetrated uniformly into cellulosic fibers. (B) The methylolation reaction with formaldehyde is easy. (C) Good compatibility with other chemicals (antistatic agent, optical brightener, bluing agent, latent acidic catalyst, formaldehyde scavenger, softener, etc.) Importantly, those that are water-soluble are desirable.

The amount of the active hydrogen compound applied to the fiber structure is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. If the amount is less than 0.1% by weight, the effect of the compound is insufficient, and if the amount is more than 10% by weight, not only the hand becomes coarse but also the shape retention is lowered.

Next, the dough pH, which is important in the present invention,
Is described. In the present invention, after the active hydrogen compound is applied to the fibrous structure, it is important to make the dough pH alkaline at 7 or more when performing the gas phase processing with formaldehyde.

The dough pH in the present invention is defined by JIS L
1096 6.40 (pH of the extract) refers to the pH of the extract obtained by extracting the test dough (fibrous structure) with 10 times the weight of distilled water.

The present inventors have studied in detail the reaction mechanism of the gas phase processing of cellulosic fibers with formaldehyde using an active hydrogen compound.
It has been found that the reaction mechanism is such that the H group or the like first reacts with formaldehyde to form a methylol group and then undergoes a cross-linking reaction with cellulose under an acidic catalyst. However, the methylolation reaction between active hydrogen groups such as -NH groups and formaldehyde is easily affected by the pH of the dough. In the acidic region where the pH of the dough is 7 or less, the methylolation does not proceed so much.
In the alkaline region having a pH of 7 or more, it was found that the dough pH was smaller when the dough pH was lower, and the present invention was also achieved.

As a method for adjusting the pH of the dough to an alkali of 7 or more, a method of simultaneously applying an aqueous solution of an active hydrogen compound and an alkali agent to the fiber structure, a method of applying an alkaline agent before or after applying the active hydrogen compound to the fiber structure, And a method of applying an active hydrogen compound to the fibrous structure, followed by treating the fibrous structure in a gaseous or vapor atmosphere of an alkali agent.

The alkaline agent that can be used in the present invention includes:
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Inorganic alkaline substances such as sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, and ammonia; monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine;
N, N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-
(2-aminoethyl) ethanolamine, N-methylethanolamine, 3-amino-1-propanol, ethylamine, propylamine, isopropylamine, diethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (methylamino ) Organic amine-based alkali substances such as propylamine, 3- (dimethylamino) propylamine, morpholine, N-methylmorpholine and N-ethylmorpholine can be used.

In order to sufficiently obtain the effects of the present invention, the dough pH is preferably alkalinity of 7 or more. However, the dough pH which is too high may be adjusted by using an acidic or latent acidic catalyst to obtain cellulose fibers and formaldehyde and It is not preferable because it hinders the crosslinking reaction with the methylolated active hydrogen compound. Preferred dough pH ranges include pH
It is 7-10, more preferably pH7-9.

In the present invention, an acidic or latent acidic catalyst can be used to cause a cross-linking reaction between cellulose fibers and formaldehyde and a methylolated active hydrogen compound.

The acidic catalysts usable in the present invention include gases such as hydrogen chloride gas and SO ₂ gas, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, glycolic acid, maleic acid, lactic acid, citric acid, tartaric acid and oxalic acid. And other organic acids can be used.

The latent acidic catalysts usable in the present invention include AlCl ₃ , Al ₂ (SO ₄ ) ₃ , MgCl ₂ , Mg
(H ₂ PO ₄ ) ₂ , Zn (BF ₄ ) ₂ , Zn (NO ₃ )
₂ , ZnCl ₂ , Mg (BF ₄ ) ₂ , Mg (ClO ₄ )
₂ , various metal salts (including those containing water of crystallization) such as Al ₂ (OH) ₄ Cl ₂ , acid salts of various alkanolamines such as hydrochloride of 2-amino-2-methyl-1-propanol, nitric acid, hydrochloric acid And ammonium salts of strong acids such as sulfuric acid and phosphoric acid, and mixtures thereof.

As a method for applying these acidic or latent acidic catalysts to the fibrous structure, a gaseous one is brought into direct contact with the fibrous structure in the gas phase, or is brought into direct contact with the fibrous structure together with steam. Methods are available. For the liquid or solid, a method of applying a solution such as an aqueous solution to the fiber structure by immersion treatment, a method of spraying the solution onto the fiber structure by a spray method or the like can be used.

The formaldehyde used in the present invention includes:
Paraformaldehyde, an aqueous formaldehyde solution, an ester compound of dihydroxymethylene and formic acid and the like can be used as the generating agent.

As a method for producing the cellulose fiber-containing fiber structure in the present invention, for example, the following method can be used depending on the catalyst and the alkali agent used.

When an acidic gas catalyst and a gas alkali such as ammonia are used, an active hydrogen compound, a humectant,
A fibrous structure provided with a softening agent or the like is charged into a reaction vessel, and ammonia and steam are injected as necessary to adjust the dough pH of the fibrous structure to 7 or more. Then, the ammonia is removed to formaldehyde aqueous solution. With steam. After injecting formaldehyde and leaving it for a while, a methylolation reaction between the active hydrogen compound and formaldehyde takes place, and then a method of injecting an acidic gas catalyst and then raising the temperature to effect a crosslinking reaction can be used.

When using an acidic gas catalyst and an alkaline agent in the form of an aqueous solution, an aqueous solution comprising an alkaline agent, an active hydrogen compound, a humectant, a softener and the like is applied in advance and dried, and the pH of the dough is adjusted.
After the fibrous structure adjusted to 7 or more was charged into the reaction vessel, an aqueous formaldehyde solution was injected with steam, and the mixture was allowed to stand for a while to cause a methylolation reaction between the active hydrogen compound and formaldehyde. A method of raising the temperature and causing a crosslinking reaction can be used.

When using a latent acidic catalyst and an alkaline agent in an aqueous solution, a latent acidic catalyst, an alkaline agent,
An aqueous solution comprising an active hydrogen compound, a humectant, a softener, etc. is applied and dried, and a fibrous structure having a dough pH adjusted to 7 or more is charged into a reaction vessel. Then, an aqueous formaldehyde solution is injected together with steam, and the active hydrogen is left for a while. After the methylolation reaction between the compound and formaldehyde occurs, a method of raising the temperature and causing a cross-linking reaction can be used.

In addition to these, a suitable production method can be selected and used according to the catalyst, alkali agent and formaldehyde generating agent used.

The humectant that can be used in the present invention is not particularly limited as long as it can absorb and hold water.
Polyols, squalane and the like can be used.

The polyols usable in the present invention include ethylene glycol-based and propylene glycol-based compounds, copolymers of ethylene oxide and propylene oxide, glycerin, neopentyl glycol, trimethylolpropane, erythritol, pentaerythritol, sorbitol, and the like. Adducts of these ethylene oxides and / or propylene oxides can be used.

The softener which can be used in the present invention is used for improving the texture of the fibrous structure or for improving the tear strength when the fibrous structure is a woven fabric. Silicone softeners such as epoxy-modified silicone, amino-modified silicone, water-soluble silicone, wax-based softener, polyethylene-based softener, fatty acid amide-based softener, polyurethane-based softener, polyester-based softener, acrylic ester-based softener, Nonionic, anionic, cationic, amphoteric surfactants and the like can be used.

Further, in the present invention, functional processing agents such as a water repellent, an antibacterial agent, a deodorant and an antistatic agent can be used simultaneously.

In the present invention, the degree of the cross-linking reaction can be represented by the total amount of formaldehyde that has been directly cross-linked to the cellulosic fiber and formaldehyde that has been methylolated to an active hydrogen compound and then cross-linked to the cellulosic fiber. The amount of bound formaldehyde in the cellulose fiber required to achieve the object of the present invention is 0.2% by weight or more, preferably 0.5% by weight.
That is all. When the amount of bound formaldehyde is less than 0.2% by weight, a sufficient modifying effect cannot be obtained. That is, the puckering property, the W & W property, the shape retention property, and the pleating property are insufficient.

The cellulosic fiber-containing fibrous structure of the present invention may be an ordinary mercerized or liquid ammonia treated with sodium hydroxide, or a mercury-treated liquid ammonia or a dyed product such as first dyeing, dip dyeing or printing. it can. When mixed with a synthetic fiber represented by polyester, if necessary, heat setting may be performed.

Vapor-phase processing with formaldehyde can be performed in any of cotton, thread, fabric and sewn products. However, it is more economical to process the sewn products and then process the sewn products. This is a preferred embodiment, since puckering and shape retention are markedly improved.

By the above-mentioned vapor phase processing with formaldehyde, it is excellent in wrinkle resistance, puckling property after repeated washing, W & W property, shrinkproof property, shape retention property, and at the same time, has high wear resistance in addition to tensile strength and tear strength by processing. It becomes possible to produce a morphologically stable cellulosic fiber-containing fibrous structure in which the decrease in strength is suppressed as much as possible.

[0034]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation method used in the examples is shown below. Fabric pH; JIS L 1096 6.40 Tear strength; JIS L 1096 6.15.5 D method (horizontal direction) Tensile strength: JIS L 1096 6.12.1 A method (5 cm width horizontal direction) Flexural wear; JIS L 1096 6.17.1 A-
Method 2 (Horizontal direction) W & W property: After repeating washing by JIS L 0217 103 method 5 times, JIS L 1042 6.9.
2 Perform tumble drying by the I-2 method.
After leaving overnight in a room at 0 ° C. and 65% RH, AATCC
Judgment was made based on the 124-1984 5-step replica method. 5th grade (good)-1st grade (bad)

Puckling property: JIS L 0217
After repeating washing by the 103 method five times, JIS L
1042 6.9.2 Perform tumble drying by the I-2 method, leave the sample in a room at 20 ° C. and 65% RH overnight, and then stitch 5 of the AATCC 88-B-1984 method.
Evaluated by step replica. 5th grade (good)-1st grade (bad)

Retainability: After repeating washing according to JIS L 0217 103 method 5 times, JIS L 1042
6.9.2 Tumble drying was performed according to the I-2 method, and the sample was left overnight in a room at 20 ° C. and 65% RH. 5 (grade): very good 4 〃: good 3 〃: normal 2 ：: slightly bad 1 〃: very bad

Amount of bound formaldehyde: Approximately 2 g of a work cloth is treated in boiling water for 15 minutes, washed with water, absolutely dried and weighed, and then decomposed in 20% sulfuric acid by a steam distillation method to recover formaldehyde formed in an aqueous sodium hydrogen sulfite solution. After the excess sodium bisulfite is oxidized by iodometric titration, the adduct is decomposed with an alkali to determine the amount of formaldehyde and the added sodium bisulfite. Indicated by

Example 1 Cotton fabric (50/1 × 50/1/144 × 81: fabric pH
6.5) was immersed in a working fluid (A) having the following composition, dried, immersed in a working fluid (B), squeezed so as to have a squeezing ratio of 70%, dried at 120 ° C. for 1 minute, and then subjected to sanforizing processing. . The cloth pH of the obtained cotton fabric was 8.2. Using this cotton fabric, a shirt was sewn by an ordinary method. This shirt was placed in a closed container and subjected to a conventional gas phase processing using formaldehyde using a 37% aqueous formaldehyde solution to obtain a shirt of Example 1 of the present invention. Table 1 shows the evaluation results of the obtained shirts. Working fluid (A): 0.05 parts by weight of sodium carbonate 99.95 parts by weight of water Processing solution (B): 3 parts by weight of 4,5-dihydroxy-2-imidazolidinone 4 parts by weight of magnesium chloride (43% aqueous solution) Polyethylene Glycol (average molecular weight 200) 6 parts by weight Parasilicone AYR20 (manufactured by Ohara Palladium Co., Ltd., silicone softener) 4 parts by weight PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener) 3 parts by weight Water 80 parts by weight

Example 2 A processing liquid (C) having the following composition was prepared by using the cotton fabric used in Example 1
, Squeezed to a squeezing ratio of 70%, dried at 120 ° C. for 1 minute, and then subjected to sunphorization. The cloth pH of the obtained cotton fabric was 7.8. Using this cotton fabric, a shirt was sewn by an ordinary method. This shirt was subjected to the same gas phase processing using formaldehyde as in Example 1 to obtain a shirt of Example 2 of the present invention. Table 1 shows the evaluation results of the obtained shirts. Working fluid (C): 4,5-dihydroxy-2-imidazolidinone 3 parts by weight Magnesium chloride (43% aqueous solution) 4 parts by weight Polyethylene glycol (average molecular weight 200) 6 parts by weight Parasilicon AYR20 (manufactured by Ohara Palladium, silicon 4 parts by weight PEN (manufactured by Dainippon Ink and Chemicals, Inc., polyethylene softener 3 parts by weight triethanolamine 0.2 parts by weight water 79.8 parts by weight

Comparative Example 1 The cotton fabric used in Example 1 was immersed in the working fluid (B) used in Example 1, and squeezed so that the squeezing ratio became 70%.
It was dried at 20 ° C. for 1 minute, and then subjected to sunphorization. The cloth pH of the obtained cotton fabric was 6.3. Using this cotton fabric, a shirt was sewn by an ordinary method. This shirt was subjected to the same gas phase processing using formaldehyde as in Example 1 to obtain a shirt of Comparative Example 1. Table 1 shows the evaluation results of the obtained shirts.

COMPARATIVE EXAMPLE 2 The cotton fabric used in Example 1 was processed with the following composition (D)
, Squeezed to a squeezing ratio of 70%, dried at 120 ° C. for 1 minute, and then subjected to sunphorization. The cloth pH of the obtained cotton fabric was 6.5. Using this cotton fabric, a shirt was sewn by an ordinary method. This shirt was subjected to the same gas phase processing with formaldehyde as in Example 1 to obtain a shirt of Example 2. Table 1 shows the evaluation results of the obtained shirts. Working fluid (D): Magnesium chloride (43% aqueous solution) 4 parts by weight Polyethylene glycol (average molecular weight 200) 6 parts by weight Parasilicon AYR20 (manufactured by Ohara Palladium Co., Ltd., silicon softener) 4 parts by weight PEN (Dainippon Ink & Chemicals, Inc.) Made of polyethylene softener) 3 parts by weight Water 83 parts by weight

Comparative Example 3 The cotton fabric used in Example 1 was treated with the working fluid (A) of Example 1.
After being immersed and dried, it was immersed in the working fluid (D) of Comparative Example 2, squeezed so as to have a squeezing ratio of 70%, dried at 120 ° C. for 1 minute, and then subjected to sanforizing. The cloth pH of the obtained cotton fabric was 8.1. Using this cotton fabric, a shirt was sewn by an ordinary method. This shirt was subjected to the same gas phase processing as in Example 1 using formaldehyde,
The shirt of Comparative Example 3 was obtained. Table 1 shows the evaluation results of the obtained shirts.

Comparative Example 4 The cotton fabric used in Example 1 was immersed in a working liquid (E) containing only a softener having the following composition, squeezed to a squeezing ratio of 70%, dried at 120 ° C. for 1 minute, and then dried. Sanforized. The cloth pH of the obtained cotton fabric was 7.5. Using this cotton fabric, a shirt was sewn by an ordinary method. This shirt was evaluated as an unprocessed shirt of Comparative Example 4 for comparison without performing vapor phase processing with formaldehyde, and the evaluation results are shown in Table 1. Processing fluid (E): Parasilicon AYR20 (manufactured by Ohara Palladium Co., Ltd., silicone softener) 4 parts by weight PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener) 3 parts by weight Water 93 parts by weight

[0044]

[Table 1]

As is clear from the results in Table 1, Examples 1 and 2 and Comparative Example 1 gave the same active hydrogen compound to the dough,
Although the shirts were processed almost the same except that the fabric pH was different, the shirts of the present invention of Examples 1 and 2 had W & W properties,
The shape retention and puckling properties are superior to Comparative Example 1, and the tensile strength,
Strength such as tearing strength and bending wear is high.
It is considered that the reason for this is that the methylolation rate of the active hydrogen compound, which is the object of the present invention, was improved, and formaldehyde that had undergone methylolation into the active hydrogen compound and then crosslinked with cotton increased. However, when no active hydrogen compound was used, the results of Comparative Examples 2 and 3 showed that
When H is increased to an alkalinity of 7 or more, only a decrease in reforming is observed, in which the W & W property is reduced and the strength is increased with a decrease in the amount of bound formaldehyde. Although the effect of improving the reforming balance of the active hydrogen compound in the vapor phase processing of formaldehyde is apparent from the results of Comparative Examples 1 and 2, the reforming balance can be further improved in Examples 1 and 2 of the present invention. As described above, the effect of improving the reforming balance in the vapor phase processing of formaldehyde using the active hydrogen compound according to the present invention is apparent.

[0046]

EFFECTS OF THE INVENTION A compound having at least two methylolable active hydrogens is added to a fibrous structure containing cellulosic fibers, and the dough pH of the fibrous structure is adjusted to an alkalinity of 7 or more. The fiber structure obtained by performing the gas-phase processing by the method described above has a good texture, a small decrease in the strength of cellulosic fiber, such as tensile strength, tear strength, and bending wear strength, excellent W & W properties even after repeated washing, and packing. It shows ring properties, shrink-proof properties, and shape retention properties, and is excellent in shape retention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaya Shinjo 50 Inukai, Daimon-cho, Imizu-gun, Toyama Prefecture Toyobo Co., Ltd.

Claims (3)

[Claims] The present invention is characterized in that a cellulosic fiber-containing fiber structure is provided with a compound having at least two or more active hydrogens capable of being converted into methylol, and that the dough pH of the fiber structure is adjusted to an alkalinity of 7 or more. A cellulosic fiber-containing fiber structure for form stable processing. 2. The cellulosic fiber-containing fiber structure for morphologically stable processing according to claim 1, wherein the cellulosic fiber-containing fiber structure is provided with a compound having two or more active hydrogens that can be converted into methylol and a latent acidic catalyst. . 3. A process for producing a fibrous structure containing cellulosic fibers by formaldehyde vapor-phase processing, wherein a compound having two or more active hydrogens capable of methylolation is added to the fibrous structure, and the dough pH of the fibrous structure is adjusted. A process for producing a morphologically stable cellulose fiber-containing fiber structure, which comprises adjusting the pH of the mixture to 7 or more and then performing a gas phase processing with formaldehyde.