JP5381215B2 - Cellulosic fiber structure and method for producing the same - Google Patents

Description

  The present invention relates to a fiber structure including a cellulose ester fiber that has both good texture and friction fastness, and a method for producing the same.

  Conventionally, as cellulose ester fibers, acetates such as cellulose diacetate and cellulose triacetate have been industrialized for a long time, and their value has been recognized as beautiful fibers with high coloring ability. Cellulose diacetate refers to cellulose acetate in which about two of the three hydroxyl groups on the glucose ring constituting the cellulose skeleton are substituted with acetyl groups. Cellulose triacetate refers to one in which almost all hydroxyl groups are substituted with acetyl groups, and is characterized by higher hydrophobicity than diacetate and improved heat resistance. However, these cellulose acetates are low in thermoplasticity and cannot be melt-spun because they are close to the melting temperature and decomposition temperature, and are produced only by a dry spinning method using a harmful organic solvent, resulting in low productivity. Above all, it was a material that had a great negative impact on the environment.

  As cellulose-based polymers having high thermoplasticity, cellulose derivatives that are partially substituted with acyl groups derived from fatty acids that are longer than acetic acid are known every time they are cellulose acetate propionate or cellulose acetate butyrate. These are conventionally industrialized as plastic molded articles and the like, and it is known that melt-spun fibers can be obtained by adding an appropriate plasticizer.

  However, even in these melt-spinnable polymers, the characteristics as cellulose ester are not lost, and the friction fastness decreases due to the decrease in the strength of the fiber itself when the treatment temperature is high in the heat setting process, dyeing process, etc. There was a problem of being seen. On the other hand, as a method for improving the fastness to friction of a cellulosic fiber dyed product, for example, JP-A-60-209080 (Patent Document 1) discloses a method using a water-soluble polymer such as polyvinyl alcohol. ing. Japanese Patent Application Laid-Open No. 62-78288 (Patent Document 2) discloses a method using an amino-modified silicone and a compound having a phenolic hydroxyl group, and Japanese Patent Application Laid-Open No. 7-70937 (Patent Document 3) includes a polyorgano A method using siloxane and water-soluble cellulose ether or polyvinyl alcohol is disclosed. Japanese Patent Laid-Open No. 10-168768 (Patent Document 4) discloses a method using a vinyl polymer obtained by copolymerizing a vinyl monomer containing a tertiary amino group or a quaternary ammonium base in the molecule. Is disclosed. However, these methods have problems in rough texture hardening, processing stability, and the like, and the effect of improving friction fastness is not always sufficient.

JP 60-209080 A JP-A-62-78288 JP-A-7-70937 Japanese Patent Laid-Open No. 10-168768 40

  The present invention relates to a fiber structure including a cellulose ester fiber having both good texture and friction fastness. More specifically, the present invention relates to a fiber structure having improved friction fastness containing cellulose acetate propionate which is a cellulosic fiber.

The cellulose fiber structure of the present invention has the following configuration in order to solve the above problems.
(1) A fiber structure comprising at least a part of a cellulose fiber mainly composed of cellulose acetate propionate, wherein the hydrolysis rate of the cellulose ester portion of the cellulose fiber is 7.8 % or more and 10% or less. The cellulose fiber surface layer has a resin film using a polysiloxane compound and / or a polyisocyanate compound having a plurality of functional groups on the surface, and at least a part of the functional groups is the cellulose. A cellulosic fiber structure characterized by reacting with a hydroxyl group of a fiber.
(2) A liquid containing a polysiloxane-based compound and / or a polyisocyanate-based compound is a cellulose-based resin mainly composed of cellulose acetate propionate having a cellulose ester portion hydrolysis rate of 7.8% to 10%. A cellulosic fiber structure characterized by being subjected to dry heat at 100 ° C. or more and 160 ° C. or less, or wet heat treatment at 90 ° C. or more and 160 ° C. or less after being applied to a fiber structure containing at least a part of fibers. Manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the cellulosic fiber structure provided with the tearing strength of the level which has a smooth feel and the friction fastness was improved, and there is no problem in wearing can be provided, and it is used suitably especially in the clothing field.

The present invention is described in detail below.
In the present invention, a cellulose-based fiber mainly composed of cellulose acetate propionate (hereinafter referred to as “cellulose acetate propionate fiber”) has a part or all of hydroxyl groups of cellulose ester-bonded with acetic acid and propionic acid. The average substitution degree of the acetyl group and the acyl group (propionyl group) preferably satisfies the following formula. The average degree of substitution refers to the number of chemically bonded acyl groups among the three hydroxyl groups present per glucose unit of cellulose.
2.0 ≦ (average degree of substitution of acetyl group + average degree of substitution of acyl group) ≦ 3.0
1.5 ≦ (average degree of substitution of acetyl group) ≦ 2.5
0.5 ≦ (Average substitution degree of acyl group) ≦ 1.5
Cellulose acetate propionate fiber satisfying the above formula is preferable because it has a high heat softening temperature, moderate hygroscopicity, and good dimensional stability when used as a fabric.

  The composition containing cellulose acetate propionate for producing the cellulose acetate propionate fiber of the present invention (hereinafter referred to as cellulose acetate propionate composition) may contain a plasticizer. As the plasticizer, a polyhydric alcohol compound is preferable. Specifically, polyalkylene glycols, glycerin compounds, caprolactone compounds, etc., which have good compatibility with cellulose acetate propionate and have a remarkable thermoplastic effect that can be melt-spun, are polyalkylenes. Glycol is preferred. Specific examples of the polyalkylene glycol include, but are not limited to, polyethylene glycol, polypropylene glycol, and polybutylene glycol having a weight average molecular weight of 200 to 4000, and these may be used alone or in combination. Can do.

  The cellulose acetate propionate content in the cellulose acetate propionate composition is preferably 75 to 95% by weight. By setting the content to 95% by weight or less, a plasticizer or the like can be added, and melt moldability is improved. By setting the content to 75% by weight or more, the strength characteristic of cellulose acetate propionate is increased, and a fiber structure having excellent mechanical properties can be obtained.

  In the cellulose acetate propionate composition, the plasticizer content is preferably 5 to 25% by weight. By setting the plasticizer content to 5 to 25% by weight, the heat flow characteristics of cellulose acetate propionate are improved, enabling production by the melt spinning method with high production efficiency, and precise and arbitrary fiber cross section. And the obtained fiber characteristics are also good. The plasticizer content is more preferably 8 to 22% by weight, and most preferably 10 to 20% by weight.

  The cellulose acetate propionate composition in the present invention preferably contains a phosphorus antioxidant, and particularly preferably a pentaerythritol compound. When a phosphorus-based antioxidant is contained, the thermal decomposition prevention effect is very remarkable even in the high spinning temperature range and the low discharge region, the deterioration of the mechanical properties of the fiber is suppressed, and the color tone of the resulting fiber Will be better. The blending amount of the phosphorus-based antioxidant is preferably 0.005 wt% to 0.500 wt% with respect to the cellulose acetate propionate composition for melt spinning.

  Cellulose acetate propionate has higher heat fluidity than cellulose acetate, and is therefore used in plastic molded products. In the present invention, a cellulose acetate propionate is used as a fiber. .

  The fiberizing method is not particularly limited, but the dry spinning method used in the current cellulose acetate and the wet spinning method such as rayon may be adopted, and the thermal fluidity of cellulose acetate propionate. It is also possible to make a fiber by a melt spinning method.

  In addition, if necessary, it may contain inorganic fine particles or organic compounds for various purposes such as anti-thermal deterioration agents, anti-coloring agents, lubricants, antistatic agents, matting agents, lubricants, flame retardants, and coloring pigments. good.

  Further, the cross-sectional shape of the cellulose acetate propionate fiber of the present invention is not particularly limited, and in addition to a commonly used round cross section, a triangular cross section, a multi-leaf shape, a flat shape, a W shape, an S shape, a C shape, an H shape, and a hollow shape. It may be a modified cross-section fiber such as a shape.

  The cellulose acetate propionate fiber of the present invention may be a composite fiber such as a core-sheath type, a side-by-side type, a split fiber type, or a sea-island type, in which at least one component is mainly composed of cellulose acetate propionate. Yarn processing such as twisting and taslan processing may be performed.

  In the present invention, the hydrolysis rate of the cellulose ester portion means that the portion of each single fiber cellulose ester that has been hydrolyzed is dyed with a reactive dye, and the dyed portion occupies the single fiber cross-sectional area. Refers to the area ratio. In the present invention, the hydrolysis rate is 0% or more and 10% or less. Since hydrolysis in the present invention usually proceeds from the surface of a single fiber, if the hydrolysis rate exceeds 10%, the cellulose component ratio of the fiber surface increases and fibrillation may occur.

  In the present invention, the hydrolysis rate is obtained by dyeing a fiber with a reactive dye, and among the dyed fibers, a cross section of 100 arbitrarily selected single fibers (cross section cut perpendicularly to the length direction of the fibers). ) Was taken with an optical microscope at a magnification of 500 times, and it was calculated as [(W0−W1) / W0] × 100, with the total area W0 of the single fiber and the area W1 of the cellulose ester portion not dyed with the reactive dye. And the average value.

  In the present invention, the hydroxyl group of the cellulose fiber surface layer reacts with the functional group of the polysiloxane compound and / or polyisocyanate compound having a plurality of functional groups, and is substantially chemically crosslinked.

  Examples of the polysiloxane here include dimethylpolysiloxane, methylhydrogenpolysiloxane, and those having a phenyl group or an alkoxyl group in the side chain. The plurality of functional groups may be the same functional group or different functional groups. The functional group is not particularly limited as long as it can chemically bond with the hydroxyl group on the fiber surface layer, and examples thereof include an epoxy group, a vinyl group, a carboxy group, an isocyanate group, a silanol group, a methylol group, and an oxazoline group. However, an epoxy group is particularly preferable. Furthermore, a high degree of polymerization epoxy-modified polysiloxane is particularly preferred because of its excellent reactivity and durability with the fiber surface hydroxyl group.

  As the high-polymerization degree epoxy-modified polysiloxane, a silicone oil having a viscosity polymerized to 5000 Cs or more and having an ether finger type epoxy group in a side chain is preferable. For example, “High Softer K-355” manufactured by Meisei Chemical Industry Co., Ltd. Is mentioned.

  The amount of the polysiloxane compound attached to the fiber structure is preferably 0.1 to 5% by weight, more preferably 0.2 to 2% by weight. If the amount of adhesion to the fiber structure is too small, it is difficult to obtain the effect of improving the fastness to friction. If the amount is too large, the misalignment, cracking, and sliminess of the fiber structure may become strong. In order to make the adhesion amount of the polysiloxane compound to a specific range with respect to the fiber structure, it can be set to 0.1 to 5% by weight by adjusting the solid content of the drug and the pickup rate. . Although depending on the solid content of the drug, the concentration of the liquid used is preferably about 5 to 50 g / l.

  In the present invention, since a polysiloxane compound having a reactive group that reacts with a hydroxyl group is used, it is excellent in terms of durability even when used alone, but further durability can be obtained by using a polyisocyanate compound in combination. Can do.

  The reason why a synergistic effect can be obtained by the combination with the polyisocyanate compound is not certain, but, for example, in the combination with the epoxy group, the fiber surface hydroxyl group and the epoxy group of the polysiloxane compound are chemically crosslinked, Isocyanate and hydroxyl groups on the surface of the fiber, and furthermore, a chemical crosslink between the hydroxyl group that is the decomposition terminal of the epoxy group of the polysiloxane and the isocyanate, and a chemical crosslink between the amino group that is the decomposition terminal of the isocyanate and the epoxy group of the polysiloxane. It is estimated that the durability is further improved by the formation of chemical crosslinks.

  Examples of the polyisocyanate-based compound include polydienes mainly composed of tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate. Isocyanate compounds can be preferably used. Among these, a block type aqueous polyisocyanate compound in which a functional group capable of reacting with a terminal functional group having crosslinkability is blocked is preferable.

  Next, the manufacturing method of the present invention will be described.

  In the method for producing a fiber structure of the present invention, a liquid containing a polysiloxane compound and / or a polyisocyanate compound is applied to a fiber structure containing at least part of cellulose acetate propionate fiber, and then 100 to 160. A heat treatment is carried out at a dry temperature of 96 ° C. or a wet heat of 96 ° C. or higher, and heat-set at 120 to 150 ° C.

  Particularly preferably, the polysiloxane compound and the polyisocyanate compound are applied to a fiber structure containing at least part of cellulose acetate propionate fiber by a pad method, a spray method, or the like, and a range of 100 ° C. or more and 160 ° C. or less. Heat treatment for 10 seconds to 10 minutes at a temperature of 90 ° C. or higher and 160 ° C. or lower in a saturated steam atmosphere for 0.5 to 10 minutes, Heat set for a minute.

  An electrostatic agent, a water repellent, a softening agent, a deodorant, and the like may be appropriately added to the treatment liquid.

  The present invention prevents or delays the fibrillation of the fiber itself due to frictional resistance by forming a film with a resin having excellent smoothness on the surface of the fiber having low wear properties. By improving the abrasion resistance, fastness to dry friction, whitening caused by threading, frictional heat meltability, fusion during sewing, and the like are improved.

  The fiber structure of the present invention is suitably used for applications such as coats, blousons, windbreakers, blouses, shirts, skirts, slacks, bedding on a futon side, interior equipment such as curtains, and the like.

Hereinafter, the present invention will be described in detail by way of examples. Moreover, the measured value in an Example and a comparative example was obtained with the following method.
(1) Hydrolysis rate The hydrolysis rate was obtained by dyeing a fiber with a reactive dye and cutting the cross section of 100 single fibers arbitrarily selected from the dyed fibers (cut perpendicularly to the length direction of the fiber). (Cross section) was photographed with an optical microscope at a magnification of 500 times, and was calculated as [(W0−W1) / W0] × 100 with the total area W0 of the single fiber and the area W1 of the cellulose ester portion not dyed with the reactive dye. And the average value.
(1) Fastness to dry friction JIS L 0849 type II (Gakushin type) was measured by grade determination of dry friction.
(2) Tear strength Measured by the JIS L 1096: 99-8.15.5D method (penjuram method).
(3) Washing durability As the fastness to dry friction and tear strength, the performance after washing was the data after the following treatment. Dissolve weak alkaline synthetic detergent specified in JISK 337 to a concentration of 0.2% in an automatic inversion swirl electric washing machine, and wash for 10 minutes under strong conditions at a bath ratio of 1:50, 40 ± 2 ° C. Then, after draining and dewatering, washing with water was carried out for 5 minutes.
(4) Hardness evaluation by sensory test: Ten test subjects evaluated the hardness of the fabric in three stages, and set the average value. (○ soft △ somewhat hard × hard)
Reference example 1
Biaxial extruder with 80% by weight of cellulose acetate propionate (ester substitution degree 2.5 (acetyl substitution degree 2.0, propionyl substitution degree 0.5)) and 20% by weight of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd., PEG 600) And kneaded to obtain pellets. After the pellets were vacuum dried, melt spinning was performed at a spinning temperature of 240 ° C. and a spinning speed of 750 m / min to obtain 100 dtex and 36 filament fibers. A plain woven fabric was woven using the obtained cellulose ester fibers as warp and weft yarns.

  Next, the obtained raw machine is treated with water at 40 ° C., scoured at 80 ° C., dried at 110 ° C., dyed black at 98 ° C. using a disperse dye, and reduced and washed with sodium carbonate at 60 ° C. for 20 minutes. And dried.

  Next, 10 g / l of an epoxy-modified polysiloxane (“High Softer K-355” manufactured by Meisei Chemical Industries) and 10 g / l of a blocked isocyanate-based cross-linking agent (“Meikanate WEB” manufactured by Meisei Chemical Industry Co., Ltd.) are used. After squeezing with%, it was dried at 110 ° C. and heat-treated at 160 ° C. for 90 seconds.

As shown in Table 1, the obtained work cloth had a smooth texture, excellent friction fastness with excellent durability, and a tear strength at a level causing no problem in wearing.
Example 2
In Reference Example 1, the following treatment was performed before dyeing, and the same treatment as Reference Example 1 was performed except that the amount of epoxy-modified polysiloxane (“Hisofter K-355” manufactured by Meisei Chemical Industry Co., Ltd.) was changed to 20 g / l. The processed cloth was obtained.

  As a treatment method before dyeing, 3% by weight of sodium hydroxide was used, and a steam treatment at 100 ° C. for 10 minutes was performed. After sufficient washing with water, neutralization washing was performed at 1 g / l of acetic acid at 60 ° C. and dried. The hydrolysis rate was 7.8%.

As shown in Table 1, the obtained work cloth had a frictional fastness with a smooth texture and excellent durability and a tear strength at a level causing no problem in wearing.
Reference example 3
Also in Reference Example 1, the same treatment as Reference Example 1 was performed except that “heat treatment of 160 ° C. × 90 seconds after drying at 110 ° C.” was changed to a treatment for 5 minutes in a saturated steam atmosphere at 105 ° C. I got a cloth.

As shown in Table 1, the obtained work cloth had a frictional fastness with a smooth texture and excellent durability and a tear strength at a level causing no problem in wearing.
Comparative Example 1
In Reference Example 1, the treatment with the epoxy-modified polysiloxane and the blocked isocyanate-based crosslinking agent was not performed, and “heat treatment of 160 ° C. × 90 seconds after drying at 110 ° C.” was changed to a heat treatment of 180 ° C. × 90 seconds. Performed the same treatment as in Reference Example 1 to obtain a processed cloth.

As shown in Table 1, the obtained work cloth was rough and inferior in both fastness to friction and tear strength.
Comparative Example 2
Reference Example 1, instead of the epoxy-modified polysiloxane and the block iso Siu sulfonate-based crosslinking agent, an anionic surfactant (manufactured by Meisei Chemical Works, Ltd. "Derekutoru M-3") was used instead 5 g / l only, reference The same treatment as in Example 1 was performed to obtain a work cloth.

As shown in Table 1, the obtained processed fabric had a rough texture and poor friction fastness.
Comparative Example 3
In Example 2, the same treatment as in Example 2 was performed except that the amount of the epoxy-modified polysiloxane (“High Softer K-355” manufactured by Meisei Chemical Industry Co., Ltd.) was changed to 3 g / l to obtain a work cloth.

  As shown in Table 1, the obtained work cloth was inferior in friction fastness.

Claims (2)

It is a fiber structure containing at least a part of cellulose fibers mainly composed of cellulose acetate propionate, and the hydrolysis rate of the cellulose ester portion of the cellulose fibers is 7.8 % or more and 10% or less. The cellulosic fiber surface layer has a resin film using a polysiloxane compound and / or a polyisocyanate compound having a plurality of functional groups on the surface, and at least a part of the functional groups are formed of the cellulosic fibers. A cellulose fiber structure characterized by reacting with a hydroxyl group. A liquid containing a polysiloxane compound and / or a polyisocyanate compound is at least a cellulose-based fiber mainly composed of cellulose acetate propionate having a hydrolysis rate of a cellulose ester portion of 7.8% to 10%. A cellulose-based fiber structure characterized by being subjected to a heat treatment of dry heat at 100 ° C. or higher and 160 ° C. or lower, or wet heat at 90 ° C. or higher and 160 ° C. or lower after being applied to a fiber structure included in part. Method.