JP2000192371A - Cellulosic fiber-containing fabric - Google Patents

Abstract

(57) [Problem] To provide a fiber cloth having both durable water repellency, excellent wrinkle resistance and flexibility. A cloth containing at least a part of a crosslinked-modified cellulose-based fiber, wherein the cloth has a cross-linking index defined by the following formula of 1 to 4, and a polyfluoroalkyl on the fiber surface. A cellulosic fiber-containing fabric to which a group-containing acrylic copolymer, an aminosilicone resin, and an aminoplast resin and / or a polyfunctional blocked isocyanate group-containing urethane resin are adhered. Crosslinking index = 100 × (AB) / A where: A: moisture absorption (%) of the cellulose-based fiber after crosslinking modification in an atmosphere of 30 ° C. and 90% RH, B: 20 ° C. Moisture absorption rate (%) of cellulosic fiber after cross-linking modification under 65% RH atmosphere

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a durable cellulosic fiber fabric having water repellency, flexibility and anti-wrinkle properties.

[0002]

2. Description of the Related Art Conventionally, fabrics containing cellulosic fibers have been widely used in various fields such as clothing. However, in fields requiring water repellency such as outer garments, there is a problem that water repellency having sufficient durability cannot be obtained due to the influence of the hydrophilic group of the cellulose fiber. In addition, fiber fabrics containing cellulosic fibers also have drawbacks such as easy wrinkling and shrinkage during washing.

For the purpose of resolving these problems, cross-linking modification is carried out with a cross-linking agent such as formaldehyde or a cellulose-reactive resin, and a water-repellent effect is imparted by using a water-repellent agent in combination. ing. However, there are problems such as insufficient durability of water repellency and a decrease in tear strength of the fabric due to lack of flexibility.

Further, a method has been proposed in which a cellulose fiber is subjected to a water repellent treatment for the purpose of achieving both water repellency and anti-wrinkle properties, and then formaldehyde is adsorbed by a gas phase treatment to block a hydrophilic group. A two-step process is required, and a special device for gas phase processing is required, and there is a problem that the operation is very complicated.

Furthermore, in the modification of these cellulose-reactive resins or formaldehyde by gas phase treatment, the hydrophilic groups of the cellulosic fibers are blocked, so that the combination with a water repellent slightly improves the water repellency. However, this is not a great effect, but there is a problem that the flexibility is reduced and the strength of the fabric is reduced, and the value is extremely low as a commercial product.

[0006]

SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide a durable water-repellent fiber fabric having excellent wrinkle resistance and flexibility.

[0007]

The present invention has the following arrangement to solve the above-mentioned problems.

That is, a cloth containing at least a part of a cellulosic fiber which has been cross-linked and modified, wherein the cloth has a cross-linking index defined by the following formula of 1 to 4, and has a surface of polyfluoro A cellulose fiber-containing fabric to which an alkyl group-containing acrylic copolymer, an amino silicone resin, and / or an aminoplast resin and / or a polyfunctional blocked isocyanate group-containing urethane resin are adhered.

Crosslinking index = 100 × (AB) / A where: A: moisture absorption (%) of the cellulosic fiber after crosslinking modification in a 30 ° C., 90% RH atmosphere. 20
° C, 65% relative humidity RH atmosphere after cross-linking modification of cellulose-based fibers (%) Further, another embodiment of the present invention relates to a shirt, a uniform, and a coat using the above-mentioned cellulosic fiber-containing cloth. Or sports clothing.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The cellulosic fiber fabric in the present invention includes natural cellulose fibers such as cotton, hemp, and pulp.
It is a fabric containing regenerated cellulose fibers such as viscose rayon, polyester fibers such as polyethylene terephthalate and polybutylene terephthalate, polyamide fibers such as nylon 6 and nylon 66, polyolefin fibers such as polyethylene and polypropylene, Mixed with vinylon fiber, acetate fiber, etc.
Also included are those that are mixed in blending, weaving, and knitting. In addition, from the viewpoint of the obtained effect, when mixed with other fibers, those containing 10% by weight or more of cellulosic fibers are preferable.

In the present invention, a cellulose fiber in which at least a part thereof is crosslinked and modified by a crosslinking agent or the like is used. The cross-linking agent referred to here is a compound capable of forming a cross-link between and within cellulose molecules by reacting with a hydroxyl group in a cellulose molecule constituting the cellulosic fiber, particularly a hydroxyl group in an amorphous region. That is, specifically, formaldehyde and dimethylol ethylene urea, dimethylol triazone, dimethylol uron, dimethylol glyoxal monourein, dimethylol propylene urea, methoxylation of some or all of these methylol groups, Examples include cellulose-reactive resins such as ethoxylated resins, polycarboxylic acids, and isocyanates. Among these crosslinking agents, formaldehyde or a compound represented by the following general formula [I] is preferably used in order to more efficiently and effectively perform the crosslinking modification of the cellulosic fiber.

[0012]

Embedded image

Here, R ₁ and R ₂ are each —H, 1 to 4 carbon atoms.
R ₃ , R ₄ , R ₅ , and R ₆ are the same or different groups represented by any one of —CH ₂ OR _{7 and} —CH ₂ OR ₇
Or the same or different groups is either -OR _8, shows that R _7, R ₈ is -H or a group of the same or different or an alkyl group having 1 to 4 carbon atoms .

In order to obtain a crosslinked-modified cellulosic fiber, a catalyst may be used in combination for the purpose of accelerating the reaction of a crosslinking agent, and specific examples thereof include organic acids, organic amines, magnesium chloride and zinc nitrate. And metal salts such as zinc borofluoride, magnesium nitrate, and zinc chloride.

[0015] The polyfluoroalkyl group-containing acrylic copolymer referred to in the present invention is not particularly limited. For example, homopolymerization of a vinyl monomer having a polyfluoroalkenyl group having 3 to 20 carbon atoms or a polyfluoroalkyl group alone is carried out. And those obtained by copolymerization of such a vinyl monomer with another vinyl monomer having no polyfluoroalkenyl group or polyfluoroalkyl group.

Examples of the vinyl monomer having a polyfluoroalkenyl group or a polyfluoroalkyl group include CH ₂ ＣC
HCOOCH ₂ C ₇ F ₁₅ , CH ₂ ＣC (CH ₃ ) COOCH
₂ C ₆ F ₁₂ CF ₃ (CF ₃ ), CH ₂ ＣＨCHCOO (CH ₂ )
₂ N (C ₃ H ₇ ) SO ₂ C ₈ F ₁₇ , C ₆ F ₁₃ CH ₂ OH, C ₈ F
₁₇ SO ₂ (C ₃ H ₇ ) CH ₂ CH ₂ OH, C ₈ F ₁₇ SO ₂ (C ₃
H ₇ ) CH ₂ COOCNH (CH ₂ ) ₆ NH (CH ₂ CN
₂ O) ₁₁ CH _{3 and the} like can be used.

Other vinyl monomers having no polyfluoroalkenyl group or polyfluoroalkyl group include, for example, ethylene, vinyl chloride, vinylidene chloride, acrylamide, styrene, benzyl acrylate, vinyl alkyl ketone, maleic anhydride, isoprene , Siloxane,
A vinyl monomer of a blocked isocyanate is used.
Among them, those containing a copolymer containing a blocked isocyanate vinyl monomer as a main component are preferred. When the polyfluoroalkyl group acrylic copolymer is used in an amount of 0.1% to the fiber fabric.
01 to 10% owf, particularly preferably 0.03 to 5%
owf is preferably contained.

In the present invention, an amino silicone resin is used. Since such a silicone resin adheres to the fiber surface, the flexibility is reduced by cross-linking and modification, so that not only the flexibility can be imparted to the cellulosic fiber fabric having reduced strength, but also a polyfluoroalkyl group-containing acrylic. It also helps the water repellency of the copolymer. Such an amino silicone resin is not preferable because it has a hydrophilic property and impairs water repellency. That is, those which do not contain a hydrophilic component such as ethylene oxide or propylene oxide and those whose amino group is not modified with a hydrophilic component such as carboxylic acid are preferable.

The aminosilicone resin preferably has an amino equivalent of 500 geq / mol or more from the viewpoint of securing flexibility and washing durability, and has an amino equivalent of 12000 geq / mol or less so as not to increase the hydrophilicity. It is preferred that

In order to impart sufficient flexibility and water repellency to the fabric, the aminosilicone resin should be 0.06% owf or more with respect to the fiber fabric, and should not be reduced in water repellency. It is preferably 1% owf or less so as not to cause a defect such as displacement.

As the aminoplast resin, for example, melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylol propylene urea, dimethylol ethylene urea and dimethylol hydroxyurea, and uronic resins such as dimethylol uron are used. Can be. Among them, hexamethylolmelamine is preferred. The amount of the aminoplast resin is preferably from 0.01 to 2% by weight, and particularly preferably from 0.02 to 1% by weight, in terms of solid content, based on the fiber cloth.

When using an aminoplast resin, a commonly used catalyst may be used. For example, phosphoric acid, sulfuric acid,
Examples include salts of inorganic acids such as nitric acid such as ammonium, aluminum, and zinc, and salts of organic acids such as formic acid, acetic acid, acrylic acid, and succinic acid.

The polyfunctional blocked isocyanate group-containing urethane resin is not particularly limited as long as it is an organic compound having two or more blocked isocyanate functional groups in a molecule, and dissociates upon heating to regenerate active isocyanate groups. Phenol, malonic acid diethyl ester, methyl ethyl ketone oxime, sodium bisulfite,
Any polyfunctional blocked isocyanate urethane resin obtained by reacting the above may be used. Particularly preferably, methyl ethyl methoxime of diphenylmethane diisocyanate,
An aqueous dispersion of methyl ethyl ketoxime of the trimethylolpropane tolylene diisocyanate adduct is preferred.

The amount of the polyfunctional blocked isocyanate urethane resin is preferably from 0.01 to 4% by weight, more preferably from 0.03 to 1% by weight in terms of solid content, based on the fiber cloth.

Further, a catalyst may be used to accelerate the lowering of the dissociation temperature of the urethane resin containing a polyfunctional blocked isocyanate group, and dibutyltindiolate, dibutyltinstearate, stearylzinc and organic amine compounds are preferred.

Next, a method for producing the cellulosic fiber fabric of the present invention will be described.

A treating solution containing a polyfluoroalkyl group-containing acrylic copolymer, an aminosilicone resin, and / or an aminoplast resin and / or a polyfunctional blocked isocyanate group-containing urethane resin is padded onto a cloth containing cellulosic fibers. Method, spray method, dipping method,
It is applied by a printing method, a coating method, a gravure method, a foam processing, or the like. In particular, when the crosslinking agent used for modifying the cellulosic fiber is a fibrin-reactive resin, a polycarboxylic acid, or an isocyanate, the padding method is preferable.
Next, the cellulosic fiber-containing fabric containing the treatment liquid was treated with 8
Heat treatment at 0-220 ° C.

Alternatively, after immersing the cellulosic fiber-containing cloth in a treatment liquid containing a crosslinker for cellulosic fibers, squeezing with a mangle and heat-treating at 80 to 220 ° C.
Further, a polyfluoroalkyl group-containing acrylic copolymer,
After being immersed in a treatment liquid containing an aminosilicone resin and / or an aminoplast resin and / or a urethane resin containing a polyfunctional blocked isocyanate group, it may be squeezed with a mangle and heat-treated at 80 to 220 ° C.

The cellulosic fiber fabric of the present invention contains a crosslinked modified cellulose fiber. The degree of the modification is such that the crosslinking index defined by the above formula is in the range of 1 to 4, preferably 2 to 4. Must be within 3.5. Such a crosslinking index is obtained by subtracting the value of the moisture absorption at a temperature of 20 ° C. and a relative humidity of 65% RH from the value of the moisture absorption at a temperature of 30 ° C. and a relative humidity of 90% RH of the cellulosic fiber after the crosslinking modification. It is calculated by
It is an index for knowing how much the cellulosic fiber has been cross-linked and modified. That is, this utilizes the fact that the hydroxyl group in the cellulose molecule is blocked by the crosslinking modification, and as a result, the value of the moisture absorption rate decreases. The smaller the index, the greater the degree of crosslinking modification, and the larger the index, the smaller the degree of crosslinking modification. Generally raw cotton,
Hemp is about 4-5.

When the crosslinking index is less than 1, the crosslinking is excessively formed and the form stability is good, but the strength of the fabric is maintained even when the aminosilicone resin adheres to the surface of the cellulosic fiber. Cannot be performed, and it is not practical. On the other hand, if the crosslinking index is greater than 4, the crosslinking modification of the cellulosic fiber is not sufficient, and the required level of wrinkle-proof form stability cannot be obtained. The cross-linking index is preferably in the range of 2 to 3.5 in consideration of the balance between the strength of the fabric and the form stability such as wrinkle resistance.

A textile product using the cellulosic fiber-containing fabric of the present invention has both morphological stability such as wrinkle resistance and shrink resistance, as well as soft texture and water repellency that is excellent in durability. Ideal for school children, school shirts, uniforms, coats, sports clothing, etc.

[0032]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

The scouring and mercerizing were carried out by a conventional method.
A broad woven fabric having a basis weight of 112 g / m ^{2 and} consisting of a blend yarn of 45% polyester 45% and cotton 55% was used. After immersing such a woven fabric in a processing liquid and padding at a squeezing ratio of 80%,
Preliminary drying was performed at 100 ° C. for 2 minutes, followed by heat treatment at 180 ° C. for 1 minute to obtain a sample.

In the examples, the crosslinking agent and its catalyst, polyfluoroalkyl group-containing acrylic copolymer, silicone resin A, aminoplast resin and its catalyst, polyfunctional blocked isocyanate group-containing urethane resin and its catalyst include The following were used. [Cross-linking agent] Aqueous solution of dimethylol dihydroxyethylene urea resin (solid content: 20%) [Catalyst of cross-linking agent] Magnesium chloride [Polyfluoroalkyl group-containing acrylic copolymer] Copolymerization reaction of the following amount of compound with distilled water Stiffened copolymer (solid content 30%) C ₁₂ F ₂₅ (CH ₂ ) ₂ OCOCH = CH ₂ 88 g CH ₃ (C ₂ H ₅ ) CNONCH (C ₆ H ₄ ) CH ₂ (C ₆ H ₄ ) NHCOO ( CH ₂ ) CH = CH ₂ 1 g Stearyl acrylate 9 g Vinyl chloride 4 g Stearyl methyl ammonium chloride 2 g C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₂ H 2.4 g Acetone 60 g Distilled water 415 g Amine-based catalyst 0.8 g [Silicone-based Resin A] Amino silicone resin having an amino equivalent of 3000 gram equivalent / mol (solid content: 20%) [Aminoplast resin Hexamethylol melamine resin (solid content 80%) [Catalyst of aminoplast resin] Organic amine compound [Polyfunctional isocyanate group-containing urethane resin] Water-dispersed liquid of methyl ethyl ketoxime of diphenylmethane diisocyanate (solid content 30%) [Polyfunctional Catalyst for Blocked Isocyanate Group-Containing Urethane Resin] Dibutyltindiolate The following silicone resins B and C in Comparative Examples were used. [Silicone Resin B] Amino silicone resin having an amino equivalent of 300 gram equivalent / mol (solid content: 30%) [Silicone resin C] Amino silicone resin having an amino equivalent of 20,000 gram equivalent / mol (solid content: 30%) Sample obtained Was evaluated by the following method. [Cross-linking index] Cross-linking index = 100 × (AB) / A Here, A: moisture absorption (%) of the cellulosic fiber after cross-linking modification at a temperature of 30 ° C. and a relative humidity of 90% RH. Moisture absorption (%) of the cellulosic fiber after cross-linking modification in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH [Wrinkle resistance] AATCC-124-1984 Judgment was made based on a five-step replied method.

Grade 5 (good) to Grade 1 (poor) [Washing Shrinkage] JIS L-1042 G Method The shrinkage in the vertical and horizontal directions of the fabric was measured by the household washing method. After washing, it was sandwiched between dry filter papers without being squeezed by a dehydrator, dehydrated by lightly pressing, and dried on a horizontally placed wire mesh. (Flexibility) The handling was evaluated according to the following criteria.

：: A texture rich in flexibility Δ: A texture that is slightly rough and has a core remaining X: A texture that is coarse and has no flexibility (tear strength) JIS L-1096 D method Pendulum method The tear strength in the warp yarn cutting direction and the weft yarn cutting direction was measured. (Water repellency) Evaluated according to JIS L1092 (spray method).

100: no adhesion wet on the surface 90: slight adhesion wet on the surface 80: drop point of water on the surface indicates wet 70: partial wet across the surface 50: wet all over the surface 0: Surface is completely wet Durability was evaluated by flexibility and water repellency after 10 washes. The washing conditions were in accordance with JIS L0217 (1) washing method 103 method.

Examples 1 to 3 Using a working fluid having the composition shown in Table 1, the crosslinking index was 1 to 4
Was prepared. Table 1 shows the results. In each case, a fabric having both excellent morphological stability, flexibility and durability and water repellency was able to be obtained.

Comparative Examples 1 to 7 Samples were prepared using working fluids having the compositions shown in Table 1.
Table 1 shows the results. In Comparative Example 1, although excellent morphological stability, durable water repellency, and flexibility were obtained, slippage was large and misalignment occurred. In Comparative Example 2, although excellent morphological stability was obtained, the flexibility was not sufficient, and the durable water-repellent fabric was inferior. In Comparative Example 3, although excellent morphological stability and durable water repellency were obtained, there was no flexibility at all, the tear strength of the fabric was significantly reduced, and a practically usable fabric could not be obtained. In Comparative Example 4, although excellent morphological stability was obtained, there was no water repellency and the flexibility was low, so that the tear strength of the fabric was significantly reduced, and a fabric that could withstand practical use could not be obtained. Comparative Example 5 had both excellent form stability and flexibility, but was not of sufficient commercial water repellency by using the water repellency of the silicone resin alone, and was low in commercial value.

In Comparative Examples 6 and 7, although durable water repellency was obtained, there was no form stability, wrinkles after washing were very poor, and Comparative Example 6 was not flexible, so that the fabric was torn. The strength was greatly reduced, and a practically usable fabric could not be obtained.

[0041]

[Table 1]

Example 4 Using a processing liquid having the composition shown in Table 2, after pad dry-curing treatment with the first-stage treatment liquid, washing with hot water at 60 ° C. and drying, and then using the second-stage treatment liquid Pad dry curing treatment was performed to prepare samples having a crosslinking index of 1 to 4. Table 2 shows the results. In each case, a fabric having both excellent morphological stability, flexibility and durability and water repellency was able to be obtained.

Comparative Examples 8 and 9 Using a processing liquid having the composition shown in Table 2, pad dry cure treatment with a first-stage treatment liquid, washing with hot water at 60 ° C., and drying, followed by a second-stage treatment A pad was dry-cured with the solution to prepare a sample. Table 2 shows the results. Comparative Example 8
Although excellent morphological stability and durable water repellency were obtained,
Not enough flexibility, the tear strength of the fabric is greatly reduced,
No practically usable fabric could be obtained. Comparative Example 9
Although it has both excellent form stability and flexibility, the water repellency of the silicone resin alone did not provide enough water repellency to withstand sports clothing use, and was of low commercial value.

[0044]

[Table 2]

[0045]

According to the present invention, form stability, flexibility,
A fiber material having excellent durability and water repellency can be obtained, and a fabric suitable for dress shirts, school shirts for school children, sports clothing, uniforms such as white coats and working clothes, coats, and the like can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/18 104 C09K 3/18 104 D06M 13/352 D06M 13/352 15/423 15/423 15/564 15/564 15/643 15/643 // D06M 101: 06 F term (reference) 4H020 BA24 BA32 4L033 AA02 AC01 AC02 AC03 AC15 BA56 BA92 CA22 CA36 CA64 DA02

Claims (8)

[Claims] 1. A fabric containing at least a part of a crosslinked modified cellulose fiber, wherein the fabric has a crosslinking index defined by the following formula of 1 to 4, and a polyfluoropolymer on the fiber surface. A cellulosic fiber-containing cloth to which an alkyl group-containing acrylic copolymer, an aminosilicone resin, and / or an aminoplast resin and / or a polyfunctional blocked isocyanate group-containing urethane resin are adhered. Crosslinking index = 100 × (AB) / A where: A: moisture absorption (%) of the cellulose-based fiber after crosslinking modification in an atmosphere of 30 ° C. and 90% RH, B: 20 ° C. Moisture absorption rate (%) of cellulosic fiber after cross-linking modification under 65% RH atmosphere 2. The composition according to claim 1, wherein the crosslinked modified cellulosic fiber is contained in an amount of at least 10% by weight.
The cellulosic fiber-containing fabric described in the above. 3. A cross-linking agent for cross-linking modification is represented by the following general formula:
2. The compound represented by [I].
Or the cellulosic fiber-containing fabric according to 2. Embedded image Here, R ₁ and R ₂ represent —H, an alkyl group having 1 to 4 carbon atoms or —
CH ₃ OR ₇ is the same or different group, and R ₃ , R ₄ , R ₅ and R ₆ are the same or different group which is any one of —H or —OR ₈ ; ₇ and R ₈ represent the same or different groups of —H or an alkyl group having 1 to 4 carbon atoms. 4. The cellulosic fiber-containing fabric according to claim 1, wherein the amino silicone resin has an amino equivalent of 500 to 12,000 gram equivalent / mol. 5. A shirt comprising the cellulosic fiber-containing fabric according to claim 1. 6. A uniform comprising the cellulosic fiber-containing fabric according to any one of claims 1 to 4. 7. A coat comprising the cellulosic fiber-containing fabric according to any one of claims 1 to 4. 8. A sports garment using the cellulosic fiber-containing fabric according to any one of claims 1 to 4.