JPH073629A - Production of low-shrinkable cellulosic fiber-containing fibrous structure - Google Patents

Abstract

PURPOSE:To obtain a cellulosic fiber-containing fibrous structure with hardly any deterioration in strength such as tensile strength and dimensional shrinkage factor in repetitive washing. CONSTITUTION:This method for producing a cellulosic fiber-containing fibrous structure is to expose pores present in the interior of cellulosic single fiber to radiation or fill and fix the pores with a gelatinized substance of (a) polymer of a monomer and/or a prepolymer having at least one polymerizable double bond by exposure to radiation, (b) a gelatinized substance of an aqueous polymeric compound or (c) the gelatinized substance of the components (a) and (b), reduce the pore volume and then subject the resultant fibrous structure to the relaxing 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 having a very small decrease in strength and a small shrinkage upon washing, and a method for producing the same. More specifically, the present invention relates to a method for producing a cellulose fiber-containing fiber structure which solves the problems of conventional resin processing methods such as the reduction of mechanical properties such as tensile strength, tear strength and abrasion strength, and has low shrinkage.

[0002]

2. Description of the Related Art Conventionally, when a cellulose fiber-containing fiber structure, particularly a product having a cellulose fiber structure, is repeatedly washed, it can be roughly classified into two types. That is, there are a type in which the shrinkability is satisfied but the mechanical properties such as tensile strength are significantly reduced, and a type in which the mechanical properties such as tensile strength are satisfied but the shrinkage is large. The former is a case where conventional resin processing is applied, and the latter is a case where resin processing is not performed.There is a case where a relaxation treatment typified by sanforize processing is applied to suppress initial shrinkage, but shrinkage during repeated washing Will not be resolved. In addition, the thread, woven structure, and processing design have been devised in consideration of deterioration of mechanical properties and reduction of shrinkage during resin processing, but it is still possible to realize one that satisfies both reduction of shrinkage and retention of strength. The current situation is not.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to provide a cellulose fiber-containing fibrous structure having a low shrinkage factor in repeated washing and a decrease in mechanical properties, and a method excellent in industrial productivity. The purpose is.

[0004]

The present invention has arrived at the present invention by incorporating into the processing design the pores of the amorphous portion of cellulose, which have not been sufficiently considered in conventional resin processing. That is, the cross-sectional area of the cellulose monofilament swells with water and shrinks when dried. Distortion occurs during this process. Removal of this strain results in contraction. Therefore, it is important to minimize the pore volume of the amorphous part, which is the main stage of water swelling. As a method for reducing the pore volume, the cellulose fiber is simply irradiated with radiation, or a polymer of a monomer or / and a prepolymer having at least one polymerizable double bond or a water-based polymer is used by applying the radiation force. It is effective to reduce the shrinkage by performing a step of filling and fixing the gelled product of the molecule, or the gelled product of the monomer or / and the prepolymer and the aqueous polymer into the pores and then relaxing the strain generated during the process. I found something.

That is, the present invention is a method for producing a low-shrinkage cellulose fiber-containing fiber structure, which comprises subjecting a cellulose fiber-containing fiber structure to radiation treatment and then performing a relaxation treatment.

By the irradiation of the present invention, the volume of pores existing inside the cellulose monofilament is reduced, or a monomer having at least one polymerizable double bond in the pore existing inside the cellulose monofilament in advance. Alternatively, the prepolymer, or the water-based polymer compound, or the monomer or / and the prepolymer and the water-based polymer compound may be filled before irradiation with radiation.

Further, after applying the above-mentioned monomer or / and prepolymer solution, or the monomer or / and prepolymer and the aqueous polymer solution to the cellulose fiber-containing fiber structure, if necessary, after wet or after drying. After irradiating with radiation, and if necessary drying and heat treatment, it can be subjected to relaxation treatment.

The pores referred to in the present invention are micropores existing inside the cellulose monofilament, and are described in JEStone et al. (Cellnlos
e Chem. Techmol., No.2, 343 ~ 358 (1968)) and Breder
It can be measured by the solute exclusion method described in ek et al. (Angew. Makromol. Chem., No. 95 13 (1981)).

When measured by this method, the pore volume in the cellulose monofilament in the present invention is reduced by irradiation with radiation. As solute sugar, particle size 1
The pore volume (Inaccessible Water) of cotton measured using 7 nm dextran 208000 is 0.31 ml / g for mercerized cotton, but the pore volume of the radiation-treated cotton of the present invention is 0.25 ml. / G or less,
It is preferably 0.23 ml / g or less in order to exert the effects of the present invention more.

The cellulose monofilament in the present invention is
Swelling due to water is suppressed by radiation treatment or the like. The degree of swelling with water S (%) is the cross-sectional area (Aw) after immersion in water at room temperature for 2 hours and the single area (Aw) after drying at 105 ° C. for 2 hours.
d) and S (%) = (Aw−Ad) / Ad × 1
00 is 1.0% or less. The low shrinkage of the fiber structure can be achieved by the presence of the cellulose fiber having the swelling degree S (%) of water of the cellulose fiber of 1.0% or less in the fiber structure.

The technique of the present invention relates to a functional processing agent such as resin,
Monomers, surfactants, oils, antibacterial agents, hygroscopic agents, water repellents, antistatic agents, ultraviolet absorbers, infrared absorbers, optical brighteners, swelling agents, dissolving agents, decomposing agents, embrittlement agents, foaming agents. It is also possible to immobilize metal particles, magnetic materials, flame retardants, anti-dye agents, oxidizing agents, reducing agents, fragrances, anti-static agents, deodorants, bacteria, enzymes, colorants and the like.

The following (meth) acrylates can be mentioned as the monomer or prepolymer having a polymerizable double bond that can be used in the present invention as required. Hereinafter, the term “(meth) acrylate” means both acrylate and methacrylate.

Monomer groups 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, 2 (meth) acryloyloxyethyl succinic acid and salts thereof, 2 (meth) acryloyloxyethyl phthalic acid and salts thereof, and tris ( Examples thereof include polyfunctional (meth) acrylates represented by 2-hydroxyethyl) isocyanuric acid (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.

As the prepolymer group, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylates, ethylene oxide modified 4.
4-dihydroxydiphenylsulfone di (meth) acrylate, polyethers such as ethylene oxide modified bisphenol A di (meth) acrylate, ethylene glycol diglycidyl di (meth) acrylate, polyethylene glycol diglycidyl di (meth) acrylate, propylene glycol di Epoxy esters represented by glycidyl di (meth) acrylate, polypropylene glycol diglycidyl di (meth) acrylate, ethylene oxide modified bisphenol A diglycidyl di (meth) acrylate, propylene oxide modified bisphenol A diglycidyl di (meth) acrylate, phenylglycidyl ether (Meth) acrylate hexamethylene diisocyanate, phenylglycidyl ether (meth) acry Isophorone diisocyanate, phenylglycidyl ether (meth) acrylate tolylene 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 Urethane (meth) acrylate represented by rudi (meth) acrylate tolylene diisocyanate, polypropylene glycol di (meth) acrylate hexamethylene diisocyanate, polypropylene glycol di (meth) acrylate isophorone diisocyanate, polypropylene glycol di (meth) acrylate tolylene diisocyanate, etc. In addition to these, saturated polyester (meth) acrylates, unsaturated polyester (meth) acrylates, polyester / urethane (meth) acrylates, polyacetal (meth) acrylates,
Examples thereof include poly (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 are used with water as a main solvent, but if necessary, a solvent selected from alcohols, cellosolves, ketones and amides which is miscible with water is used in combination with water. It doesn't matter.

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

Further, cellulosic polymers such as viscose, methyl cellulose, hydroxypropyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, starch acetate, starch phosphate, hydroxyethyl starch, carboxymethyl starch, carboxyethyl. Starch, starch-based polymers such as dialdehyde starch, cyanoethyl starch, polyvinyl alcohol, partially acetalized PVA, polyvinyl methyl ether, vinyl acetate / maleic acid copolymer, vinyl acetate / crotonic acid copolymer, styrene / maleic acid Copolymers, styrene / crotonic acid copolymers, 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, water-soluble collagen, water-soluble Keratin, water-soluble proteins such as water-soluble silk fibroin, polyester-based, polyurethane-based as other water-dispersible polymers,
Examples thereof include epoxy type and polyamide type 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 in combination with water. It doesn't matter.

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, 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 cellulose. Further, from the polymerization rate at the time of irradiation with radiation, the acrylate compound is more preferable than the methacrylate compound. In general, the curing rate is high and it is preferable.

Although no processing agent is required, if a processing agent is used, the water-based polymer, the monomer having a polymerizable double bond, and the prepolymer may be added to the cellulose fiber-containing fiber structure in an amount of 0 if necessary. 0.1 to 20% by weight is preferably 0.1 to 5% by weight, more preferably 0.1 to 2.0% by weight.

The water-based polymer, the monomer having a polymerizable double bond, the prepolymer and the like are generally used as an aqueous solution, but if necessary, they are selected from water-miscible alcohols, cellosolves, ketones and amides. The solvent is used together with water to prepare a mixed solution, and further a processing agent is prepared in an emulsion state using a surfactant, and is applied to the cellulose fiber-containing fiber structure and then irradiated with an electron beam after being wet or dried. If necessary, any method of drying and heat treatment may be used, and the order of these steps is not limited in the present invention.

Radiation irradiation is 0.5 to 10 M in consideration of the decrease in strength of the cellulose fiber-containing structure, gelation and decomposition of the aqueous 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.

Examples of the relaxing method for removing the strain generated during the working process which can be used in the present invention include steam treatment, a method of overfeeding in the vertical direction while mechanically rubbing, and a combination method thereof. Preferred is sanforizing. The overfeed in this case is 0
It is -6%, preferably 1-4%.

The fibrous structure usable in the present invention includes natural cellulose fibers such as cotton, hemp, flax and pulp, regenerated cellulose fibers such as viscose rayon (including polynosic rayon), copper ammonia ray and solvent spinning rayon. And 100% cellulose fiber products such as bacterial cellulose fibers and mixed products thereof, or mixed products with synthetic fibers such as polyester, acrylic, polyamide, polyethylene and polypropylene. Further, for the cellulose fiber, a usual mercerization treatment, liquid ammonia treatment or a combination treatment product thereof is also mentioned as a preferable example. Examples of the form of the structure include sliver, yarn, woven fabric, knitted fabric, non-woven fabric, paper and the like.

[0027]

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. Shrinkage: Washing shrinkage was evaluated by the following method. 20c
A sample cloth measuring mx 15 cm, with warp, weft, each 10.00
Marked at cm intervals, washed and dried under the following conditions. Detergent: Phosphorus-free synthetic detergent 1 g / l Washing machine: Household 2-tank washing machine Bath ratio: 1:30 (supplement of sample weight was compensated with dummy cloth) Temperature: Washing: 40 ° C, Rinse: Room temperature Process: Washing 5 minutes → dehydration 1 minute → rinse (overflow) 2 minutes → dehydration 1 minute → rinse (overflow) 2 minutes →
Dehydration 1 minute → drying (pantex) 180 ° C. × 20 seconds Evaluation: After repeating the above steps once for 20 times, measuring the length (Lcm) Shrinkage rate (%) = (10.00
-L) /10.00 x 100

Tensile strength: JIS L-1096 6 1
2. Test piece 2.5 cm by 1A method (strip method),
The strength at the time of wave break was measured at a grip interval of 10 cm. As for the direction of the test piece, the tensile strength in the weft direction was measured. Retention rate: The ratio of the tensile strength after processing to the tensile strength before processing was shown in percentage.

Measurement of Pore Volume: The pore volume was measured by the solute exclusion method described in the literature shown in paragraph 0010.・ A sample of known dry weight is swollen with water, surface-free water is centrifugally dehydrated, and then immersed in an aqueous saccharide solution of known semi-particle diameter of a certain concentration, and the decrease in saccharide concentration is determined by the degree of illuminance.
Inaccessible Water (pore volume) was calculated. δ = q / p−W (Ci−Cf) / pCf δ: Inaccesible Water g water / g fiber p: sample dry weight g W: weight of solute aqueous solution g Ci: standard solute concentration g / dl Cf: solute concentration after treatment g / dl ・ Solute sugar used and its particle size Maltose 1.0 nm Raffinose 1.2 nm Dextran 4000-8000 3.6 nm Dextran 19600 6.0 nm Dextran T-40 9.0 nm Dextran 208000 17 nm Dextran T-500 27 nm

Example 1 Cotton fabric mercerized (50 × 50/144 × 81,
110 g / m ² ) was irradiated with 3 Mrad electron beam as shown in Table 1 and then over-fed by 4% using a sanforizing machine to finish. The results of the shrinkage ratio in the vertical direction and the tensile strength retention ratio in the horizontal direction of the woven fabric are shown in Table 3, showing excellent repeated washing shrinkage resistance and tensile strength retention. In addition,
The pore volume of the cotton single fiber was 0.23 ml / g.

Example 2 Cotton fabric mercerized up (50 × 50/144 × 81,
110 g / m ² ) as shown in Table 1
After squeezing so as to obtain a pickup of 3% and irradiating with an electron beam of 3 Mrad, it was dried with a pin tenter at 120 ° C. for 2.5 minutes. Then, it was over-fed by 4% using a sanforizing machine to finish. The results of the shrinkage ratio in the vertical direction and the tensile strength retention ratio in the horizontal direction of the woven fabric are shown in Table 3, showing excellent repeated washing shrinkage resistance and tensile strength retention. The pore volume of the cotton single fiber was 0.14 ml / g, and the swelling degree S (%) with water was 1.0% or less.

EXAMPLE 3 Cotton fabric mercerized ascent (50 × 50/144 × 81,
110 g / m ² ) was dipped in the processing agent bath shown in Table 1 to obtain 70
% Squeeze to pick up, 12 with a pin tenter
After drying at 0 ° C. for 2.5 minutes, it was irradiated with an electron beam of 3 Mrad. Then, it was over-fed by 2% using a sanforizing machine to finish. The results of the shrinkage ratio in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 3, showing excellent wash shrinkage resistance and tensile strength retention. The pore volume of the cotton single fiber was 0.15 ml / g, and the swelling degree S (%) was 1.0% or less.

Example 4 Cotton fabric mercerized (50 × 50/144 × 81,
110 g / m ² ) was dipped in the processing agent bath shown in Table 1 to obtain 70
% Squeeze to pick up, 12 with a pin tenter
After drying at 0 ° C. for 2.5 minutes, it was irradiated with an electron beam of 3 Mrad. Then, it was over-fed by 2% using a sanforizing machine to finish. The results of the shrinkage ratio in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 3, showing excellent wash shrinkage resistance and tensile strength retention. The pore volume of the cotton single fiber was 0.14 ml / g, and the swelling degree S (%) was 1.0% or less.

Examples 5 and 6 Example 3 except that the processing agent bath shown in Table 1 was used.
It carried out similarly to. The results of the shrinkage rate in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 3, showing excellent wash shrinkage resistance and tensile strength retention. The pore volume of cotton monofilament is 0.
15 ml / g, and the swelling degree S (%) was 1.0% or less.

Example 7 The same procedure as in Example 3 was carried out except that the electron beam irradiation was 1 Mrad. The results of the shrinkage ratio in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 3, showing excellent wash shrinkage resistance and tensile strength retention. The pore volume of the cotton single fiber was 0.14 ml / g, and the swelling degree S (%) was 1.0% or less.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the irradiation of the electron beam of 3 Mrad was omitted. The results of the shrinkage rate in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 4, and although the tensile strength retention rate was satisfied, the wash shrinkage resistance was large and poor.
The pore volume of cotton plain was 0.31 ml / g.

Comparative Example 2 All were carried out in the same manner as in Example 1 except that the step of overfeeding 4% using a sanforizing machine was omitted. Although the shrinkage rate in the vertical direction and the tensile strength retention rate in the horizontal direction of the woven fabric were almost satisfied, the shrinkage resistance to washing was large and poor.

Comparative Example 3 All were carried out in the same manner as in Example 2 except that the step of overfeeding 4% using a sanforizing machine was omitted. The results of the shrinkage rate in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 4, and although the tensile strength retention rate was satisfied, the wash shrinkage resistance was large and poor.

Comparative Examples 4, 7 and 8 The same procedure as in Example 4 was carried out except that the step of 2% overfeed was omitted by using a sanforizing machine and the corresponding processing agent baths shown in Table 3 were used. . The results of the shrinkage ratio in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 4, and although the tensile strength retention ratios were satisfied, the shrinkage resistance against washing was large and poor.

Comparative Examples 5, 7, and 9 The same procedure as in Example 5 was performed except that the electron beam irradiation of 3 Mrad was omitted and the corresponding processing agent baths shown in Table 2 were used. The results of the shrinkage ratio in the vertical direction and the tensile strength in the horizontal direction of the woven fabric are shown in Table 4, and although the tensile strength retention ratios were satisfied, the shrinkage resistance against washing was large and poor.

Comparative Examples 10, 11 and 12 Cotton woven mercerized cloth (50 × 50/144 × 81,
110 g / m ² ) is dipped in each corresponding processing agent bath shown in Table 2, squeezed to 70% pickup, dried with a pin tenter at 120 ° C for 2.5 minutes, and then further dried with a pin tenter at 155 ° C for 3 minutes. did. Then, it was finished with 0% overfeed using a sanforizing machine.
The results of shrinkage in the vertical direction and tensile strength in the horizontal direction of the fabric are shown in Table 4, and the shrinkage resistance to washing was small and excellent.
The tensile strength retention was extremely low and unsatisfactory.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

EFFECTS OF THE INVENTION Cellulose monofilaments in which the pore volume inside the cellulose monofilament is reduced by filling with only a radiation or a polymerizable monomer, a prepolymer water-soluble polymer and the like and irradiating the cellulose monofilament are suppressed. The cellulose fiber-containing fiber structure containing the cellulose single fiber containing the cellulose single fiber and subjected to the relaxation treatment has a small dimensional shrinkage ratio during repeated selection, and can suppress a decrease in strength such as tensile strength.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // D06M 101: 06

Claims (1)

[Claims] 1. A method for producing a low-shrinkage cellulose fiber-containing fiber structure, which comprises subjecting a cellulose fiber-containing fiber structure to radiation treatment and then performing a relaxation treatment.