JPH06346366A - Cellulosic fiber-containing fiber product and its production - Google Patents

Abstract

PURPOSE:To produce a cellulosic fiber-containing fiber structure sewing product improved in the balance between the W/W property (crease resistance) and the strength (tensile strength) and in the packering resistance. CONSTITUTION:The characteristics of this cellulosic fiber-containing fiber product and the production method thereof are to obtain a cellulosic fiber web in which fine pores contained in the fibers have preliminarily filled with (a) a monomer and/or its prepolymer having at least one double bond, (b) an aqueous polymeric compound, or (c) the mixture of the components (a) and (b), sew the web, and subsequently subject the sewed product to a gaseous formalin treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulosic fiber-containing fiber structure in which the strength of a product is suppressed to a minimum and the W / W property and puckering property are improved, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, when a cellulosic fiber-containing fiber structure, particularly a product of cellulosic fiber structure, is repeatedly washed, a puckering phenomenon (twitching phenomenon) caused by a difference in washing shrinkage ratio between a cloth and a sewing thread occurs. It was left unresolved. As a method for solving this problem, a method utilizing a gas phase reaction with formalin has recently been reviewed. According to this method, the puckering phenomenon can be certainly improved, but it is closed up as a new problem accompanied by a remarkable decrease in the strength of the cellulosic fibers, and it is desired to solve the problem.

[0003]

The present invention is excellent in puckering property and W / W property during repeated washing, and at the same time, the strength reduction due to the gas phase formalin (formaldehyde) treatment is suppressed as much as possible, that is, the processing balance is good. It is an object of the present invention to provide a cellulosic fiber-containing fiber structure and to provide a method excellent in industrial productivity.

[0004]

The present invention incorporates into the processing design the fine pores (pores) existing inside the single fiber, that is, the pores of the amorphous portion of the cellulose, which have not been sufficiently considered in the conventional resin processing. Thus, the present invention has been achieved. That is,
The polymer of fine particles inside the monofilament a) is a) a polymer of a monomer or / and a prepolymer having at least one polymerizable double bond, or b) an aqueous polymer compound, or c) a) and b) above. A cellulosic fiber-containing fiber product which is filled with a mixture and in which the cellulosic molecules of the cellulosic monofilament contain cellulosic fibers crosslinked by formaldehyde.

Further, a) a polymer of a monomer or / and a prepolymer having at least one polymerizable double bond in the micropores inside the cellulose single fiber, or b) a hydrogen polymer compound, or c) the a. ) And the above b) are pre-filled to obtain a fibrous structure containing cellulosic fibers, the structure is sewn, and the sewn product is then subjected to a vapor phase formalin treatment. Is the law.

In the present invention, when gelling the above-mentioned a), b) and c) filled in the pores of the cellulos according to need, it is preferable to utilize radiation, and further, electron beam irradiation Is preferably used.

Further, the above-mentioned a), b) and c) are applied to the cellulosic fiber-containing fiber structure, then irradiated with radiation after being wet or after drying, and if necessary, drying and heat treatment. You can also

The above-mentioned a), b) and c) in the present invention.
Cellulose fibers in which is filled in the pores inside the cellulose single fibers, and the cellulose fiber molecules are cross-linked with formaldehyde, the swelling by water is reduced as much as possible. That is, the degree of swelling of the cellulose monofilament with water (S
%) In terms of the cross-sectional area (Aw) after being immersed in water at room temperature for 2 hours and the cross-sectional area (Ad) after being dried at 105 ° C. for 2 hours.
= (Aw-Ad) / Ad * 100 is 1.0 or less.
Therefore, excellent puckering property is exhibited.

Further, the cross-linking distribution, cross-linking density, cross-linking length and the like of formaldehyde are controlled by the filling degree and filling state of the pores a), b) and c). Therefore, strength reduction due to formaldehyde crosslinking can be suppressed.

The technique of the present invention is directed to functional processing agents such as resins,
Monomer, surfactant, oil agent, antibacterial agent, hygroscopic agent, water repellent, antistatic agent, ultraviolet absorber, infrared absorber, optical brightener, swelling agent, dissolving agent, decomposing agent, embrittlement agent, foaming It is also possible to immobilize agents, metal particles, magnetic materials, flame retardants, dye-proofing agents, oxidizing agents, reducing agents, fragrances, antistatic agents, deodorants, bacteria, enzymes, coloring agents and the like.

Examples of the monomer or prepolymer having a polymerizable double bond that can be used in the present invention include the following (meth) acrylates. Hereinafter, the term “(meth) acrylate” means both an acrylate and a metaacrylate.

Monomers include (meth) acrylic acid and its salts, and phenoxy polyethylene glycol (meth).
Acrylate, methoxy polyethylene glycol (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, mono (2
-(Meth) acroyloxyethyl) acid phosphate, N.I. Monofunctional (meth) acrylates represented by N-dimethylaminoethyl (meth) acrylate, (meth) acryloyloxyethylsuccinic acid and salts thereof, 2 (meth) acryloyloxyethylphthalic acid and salts thereof, and the like And polyfunctional (meth) acrylates represented by tris (2-hydroxyethyl) isocyanuric acid (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. And the like.

The prepolymer group includes ethylene glycol
3. Rudy (meth) acrylate, polyethylene glycol (meth) acrylate, ethylene oxide modified 4.
Polyethers such as 4-dihydroxydiphenyl sulfone di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene glycol diglycidyl di (meth) acrylate, polyethylene glycol Lugiglycidyl di (meth) acrylate
, Propylene glycol diglycidyl di (meth) acrylate, polypropylene glycol diglycidyl di (meth) acrylate, ethylene oxide modified bisphenol A diglycidyl di (meth) acrylate, propylene oxide modified bisphenol A Epoxy esters typified by diglycidyl di (meth) acrylate, phenylglycidyl ether (meth) acrylate hexamethylene diisocyanate, phenylglycidyl ether (meth) acrylate isophorone diisocyanate -To, phenylglycidyl ether (meth) acryl-
Totolylene diisocyanate, glycerin di (meth) acrylate hexamethylene diisocyanate, glycerin di (meth) acrylate isophorone diisocyanate
, Glycerin di (meth) acrylate tolylene diisocyanate, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate, pentaerythritol tri (meth) acrylate isophorone diisocyanate -, Pentaerythritol tri (meth) acrylate tolylene diisocyanate, polyethylene glycol di (meth) acrylate hexamethylene diisocyanate
Polyethylene glycol di (meth) acrylate isophorone diisocyanate, polyethylene glycol di (meth) acrylate tolylene diisocyanate, polypropylene glycol di (meth) acrylate hexamethylene diisocyanate -, Urethane (meth) acrylates represented by polypropylene glycol di (meth) acrylate isophorone diisocyanate, polypropylene glycol di (meth) acrylate tolylene diisocyanate, and the like. In addition, saturated polyester (meth) acrylates, unsaturated polyester (meth) acrylates, polyester / urethane (meth) acrylates, polyacetal (meth) acrylates,
Examples thereof include polybutadiene-based (meth) acrylates, (meth) acrylates of proteins such as collagen and keratin.

Further, the monomer or prepolymer having a polymerizable double bond is not limited to (meth) acrylate, but almost any one can be used as long as it is radically polymerized or ionically polymerized by irradiation with radiation.

The above-mentioned monomers and prepolymers use water as a main solvent. If necessary, a solvent selected from alcohols, cellosolves, ketones and amides, which are miscible with water, can be used. May be used together with.

The following are examples of the water-based polymer compound that can be used in the present invention. Starch such as citrus starch, potato starch, tapioca starch, wheat starch, cone starch, soluble starch, α-starch, fumes starch, mannans such as konjac, furi agar, seaweeds such as sodium alginate,
Plant mucilages such as Trolo mallow, tragacanth gum, gum arabic, locust bean gum, microbial mucilages such as dextran, levan and pullulan, natural polymers such as glue, gelatin, casein, collagen and other proteins Can be mentioned.

Cellulosic polymers such as viscose, methylcellulose, hydroxypropylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and the like. , Starch acetate, phosphate starch, hydroxyethyl starch, carboxymethyl starch, carboxyethyl starch, dialdehyde starch, cyanoethyl starch, and other starch-based polymers, polyvinyl alcohol, partial acetalization PVA, polyvinyl methyl ether, vinyl acetate / maleic acid copolymer, vinyl acetate / crotonic acid copolymer, styrene / maleic acid copolymer, styrene / crotonic acid copolymer, ethylene / acrylic acid Copolymers, vinyl polymers such as polyvinylpyrrolidone, poly Partially saponified acrylic acid ester, partially saponified polyacrylic acid ester copolymer, acrylic polymers such as polymethacrylate, polyacrylate, polyacrylamide, polyamines such as polyethyleneimine, and other water-dispersible polymers Examples thereof include polyester-based, polyurethane-based, epoxy-based and polyamide-based polymers.

The above-mentioned water-based polymer compound uses water as a main solvent. If necessary, a solvent selected from alcohols, cellosolves, ketones and amides, which are miscible with water, is used as water. You may use it together.

Radiation irradiation used in the present invention includes γ-ray irradiation and electron beam irradiation, but electron beam irradiation is excellent in terms of safety, operability and economy.

Further, the water-based polymer compound, the monomer having a polymerizable double bond and the prepolymer in the processing liquid preferably have a molecular size smaller than the pore size of the cellulose, and the methacrylic acid is more preferable in view of the polymerization rate upon irradiation with radiation. In general, an acrylate compound has a higher curing rate than a compound and is preferable.

The amount of the water-based polymer compound, the monomer having a polymerizable double bond, and the prepolymer added to the cellulose fiber-containing fiber structure is 0.1 to 20% by weight, respectively.
It is preferably 0.1 to 5% by weight, more preferably 0.1 to 2.0% by weight.

Water-based polymer compounds, monomers having a polymerizable double bond, prepolymers, etc. are generally used as an aqueous solution, but if necessary, alcohols miscible with water,
A solvent selected from cellosolves, ketones, and amides is used in combination with water, and a processing solution is prepared in a mixed solution and further in the form of an emulsion using a surfactant, and then applied to the cellulose fiber-containing fiber structure. After being wet or after drying,
Any method of irradiating with an electron beam and drying and heat treatment may be used, and the order of these steps is not limited in the present invention.

Irradiation is carried out in an amount of 0.5 to 10 M in consideration of the decrease in strength of the cellulose fiber-containing structure, gelation and decomposition of the water-based polymer, and the polymerizability of the polymerizable monomer and prepolymer.
rad, but preferably 0.5-5 Mra
d, and more preferably 0.5 to 3 Mrad.

The fiber structure which can be used in the present invention includes natural cellulosic fibers such as cotton, hemp, flax and pulp, viscose rayon (including polynosic rayon), copper ammonia ray. Solvent spinning method Recycled cellulose fiber such as rayon and 100% cellulose fiber product such as bacterial cellulose fiber and their mixed products, or mixture with synthetic fiber such as polyester, acrylic, polyamide, polyethylene and polypropylene Goods are listed. Especially for cotton, it can be used regardless of whether it has been scoured, mercerized or liquid. Examples of the form of the structure include a sliver, a thread, a woven fabric, a knitted fabric, a non-woven fabric, a paper, and the like. A sewn product of the structure is a fiber product according to the present invention. Done.

[0025]

A polymerizable monomer or / and a prepolymer or a polymer thereof or an aqueous polymer compound or a gelled product thereof or the monomer or / and the prepolymer is provided in at least the inside of the pores of the cellulose single fiber according to the present invention. By filling with the aqueous polymer compound or a gelled product thereof,
Since the distribution and density of crosslinks during the formalin crosslinking reaction can be controlled, the strength reduction that was not possible with conventional gas-phase formalin processing was suppressed, and the swelling of cellulose monofilaments with water was reduced as much as possible. Ringability, W /
It can be provided as a cellulosic fiber-containing fiber structure having excellent W property.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Prior to the examples, the evaluation methods used in the examples will be shown.

Wrinkle resistance: The wrinkle recovery angle (indicated by DCR and WCR, respectively) in dry and in wet according to JIS L-1059 B method (Monsanto method) was evaluated.

Tensile strength: It was evaluated by JIS L-1094 grab method (horizontal direction). Retention rate: The ratio of the tensile strength after processing to the tensile strength before processing was shown in percentage.

Puckering property: JIS L-0217
The sewn product was evaluated by the four-stage method by visual inspection after the washing was performed 5 times by the 103 method. ◎ Very good ○ Good △ Normal × Poor

Example 1 Cotton fabric mercerized (50 × 50/144 × 81,
110 g / m ² ) was dipped in the processing agent shown in Table 1, squeezed to a 70% pickup, irradiated with an electron beam of 3 Mrad, and then dried in a pin tenter at 120 ° C. for 2.5 minutes. Carried out. Using the cotton fabric that has been subjected to this pretreatment process, it was sewn by a conventional method to obtain a shirt product. 25kg of this sewn product is set in the gas phase reaction treatment tank and
% Formalin aqueous solution (2 lkg) was uniformly injected in a mist state together with steam, and then 400 g of SO ₂ gas was added to the gate at a pressure of 1 kg.
It was injected at a pressure of / cm ² . Furthermore, low pressure steaming treatment was carried out for 10 seconds. Then, the temperature of the gas phase reaction treatment tank was raised to 126 ° C., and the treatment was carried out at the same temperature for 25 minutes, then a high-pressure steam of 3.5 kg / cm ² was blown for 6 minutes, and then a small amount of ammonia water was added. It was injected with steam, and low-pressure steaming treatment was further carried out for 4 minutes for deammonification and deformalization. The puckering property, wrinkle resistance, and tensile strength of the sewn product thus treated were measured. The results are shown in Table 2. The sewn product of the present invention has an improved balance of anti-wrinkle property, puckering property and tensile strength. Especially, the puckering property was remarkably improved.

Comparative Example 1 Cotton mercerized ascent (50 × 50/144 × 81, 11
0 g / m ² ) is shown in Table 1. Immerse in the solution of the processing agent bath composition,
Pick it up to 70% and use a pin tenter to dry at 120 ° C for 2.5 minutes and then 155 ° C for 3 minutes.
It was cured for a minute. This cotton fabric was sewn by a conventional method using a cotton thread to obtain a shirt product. Table 2 shows the evaluation results of the finished sewn product. The wrinkle resistance and tensile strength were in a good balance, but the puckering property was not good.

Comparative Example 2 All were carried out in the same manner as in Example 1 except that the pretreatment in Example 1 was not carried out. The results are shown in Table 2. The packerability was remarkably improved, but the WCR was slightly low and the tensile strength retention was low.

Examples 2 to 4 Pretreatment was performed in the same manner as in Example 1 using the same dough as in Example 1 using the processing agent composition shown in Table 1. Further, gas phase formalin treatment was carried out in the same manner as in Example 1. Table 2 shows the results of the evaluation of the sewn shirt product using the finished fabric.
In all cases, the puckering property was remarkably improved, and the balance between wrinkle resistance and tensile strength retention was also improved.

Example 5.6 Cotton mercerized ascent (50 × 50/144 × 81, 11
0 g / m ² ) is immersed in the processing agent bath shown in Table 1, squeezed so that the pickup becomes 70%, and 1 using a pin tenter.
It was dried at 20 ° C. for 2.5 minutes. The pre-treated woven fabric thus treated was sewn by a conventional method using a cotton thread to obtain a shirt product. After that, the same formalin vapor phase treatment as in Example 1 was performed. The evaluation results are shown in Table 2. Packing showed a marked improvement. The balance between wrinkle resistance and tensile strength was also improved.

Comparative Examples 3 to 4 Cotton mercerized ascent (50 × 50/144 × 81, 11
0 g / m ² ) is shown in Table 1. It was immersed in a processing agent bath, squeezed so that the pickup was 70%, and dried using a pin tenter at 120 ° C. for 2.5 minutes. The pre-treated woven fabric thus treated was sewn by a conventional method using a cotton thread to obtain a shirt product. After that, the same formalin vapor phase treatment as in Example 1 was performed. The evaluation results are shown in Table 2. The packer was remarkably improved, but the balance between wrinkle resistance and tensile strength was not improved.

A sewn product made of a structure containing cellulose fibers processed by the method of the present invention has wrinkle resistance and tensile strength well balanced, and puckering after repeated washing, as is apparent from the examples. It is recognized that it is particularly excellent in sex.

[0037]

[Table 1]

[0038]

[Table 2]

Claims (2)

[Claims] 1. A polymer of a monomer or / and a prepolymer in which micropores inside the cellulose single fiber have at least one polymerizable double bond, or b) an aqueous polymer compound, or c) the above. filled with a mixture of a) and b) above,
A cellulose fiber-containing fiber product containing cellulose fibers obtained by crosslinking the cellulose molecules of the cellulose single fiber with formaldehyde. 2. In the micropores inside the cellulose monofilament, a)
A monomer having at least one polymerizable double bond or /
And a polymer of a prepolymer, or b) an aqueous polymer compound, or c) a fibrous structure containing cellulosic fibers pre-filled with a mixture of a) and b) is obtained, the structure is sewn, and then A process for producing a cellulose-containing fiber product, which comprises subjecting the sewn product to gas-phase formalin treatment.