JPH03213569A - Finished sheet material and its production - Google Patents

Abstract

PURPOSE:To obtain the title material excellent in initial performance and durability by treating a sheet material composed of conjugate fiber made up of an ethylene-vinyl acetate copolymer saponified product and a thermoplastic polyester in a water bath containing a finishing agent and a specified concentration of inorganic salt. CONSTITUTION:(A) An ethylene-vinyl acetate copolymer saponified product with an ethylene content of 30-70mol% and (B) a thermoplastic polyester polymer (e.g. polyethylene terephthalate) are combined at the weight ratio A/B=(5:95) to (60:40) followed by delivery through a spinning nozzle of a sheath- core-type conjugate spinning machine into conjugate fiber. This fiber is brought into contact with a hot plate followed by drawing and then weaving into a plain weave fabric, from which a sheet material is produced. This sheet material is treated in a water bath at 60-125 deg.C containing a finishing agent and an inorganic salt at a concentration of >=10mg/l for a residence time of 5-120min, thus obtaining the objective finished sheet material.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a sheet containing at least a portion of fibers made of a saponified polymer of ethylene vinyl acetate copolymer with excellent functionality and a thermoplastic resin mixed or composited. The present invention relates to a sheet material characterized in that a finishing agent has penetrated into the interior of the ethylene-vinyl acetate copolymer saponified polymer, and a method for manufacturing the same, which improves initial performance and durability. The aim is to provide an excellent sheet material.

(Conventional technology) Synthetic fibers originally have excellent general-purpose properties that are not found in natural fibers, such as strength, elasticity, and abrasion resistance. Since it has drawbacks such as being easily stained and easily melted by heat, it is commercialized with various finishing treatments (for example, sweat-absorbing finishing, antistatic finishing, antifouling finishing, anti-melting finishing, etc.).

(Problem to be solved by the invention) 2- However, with the conventional finishing method of treating fibers with a finishing agent, although the desired initial performance is imparted, there are problems in terms of durability. there were.

That is, since the finishing agent added simply adheres to the surface of the fiber and forms a surface film and is fixed, it is likely to fall off due to washing, friction, etc., and its durability is limited. Therefore, it has been desired to develop a fiber material or a finishing technique that has a permanent finishing effect.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors conducted extensive research and arrived at the present invention.

That is, in the present invention, a saponified polymer (A) of an ethylene vinyl acetate copolymer having an ethylene content of 30 to 70 moles and a thermoplastic polyester polymer (B) are (A):
(B) = s: A sheet material containing fibers mixed or composited at a weight ratio of 95 to 60:40, characterized in that the finishing agent has penetrated into the interior of the polymer (A). II) A saponified polymer (A) of a terene-vinyl acetate copolymer and a thermoplastic polyester polymer (B) having an ethylene content of 30 to 70 molar are (A)= (B)
= 5: When finishing a sheet material containing Q#a mixed or composited at a weight ratio of 95 to 60:40, the finishing agent should be added at a bath temperature of 1 to 1 and the inorganic salt concentration should be 10/L or higher. This is a method for producing a finished sheet material, characterized in that the sheet material is treated in a water bath at a temperature of 60 to 125° C. for a residence time of 5 to 120 minutes.

In this way, by using fibers that are a mixture or composite of a hydrophobic polyester resin and a saponified polymer of ethylene-vinyl acetate copolymer that has hydrophilic hydroxyl groups, it is possible to achieve a highly durable finish. In other words, ・11! When a sheet material containing at least a portion of fibers is finished in a water bath, the highly hydrophilic ethylene vinyl acetate copolymer saponified polymer hydrates and swells, so the finishing agent added becomes more resistant to fibers. It penetrates into the interior and forms a surface film to adhere. Therefore, it is possible to easily apply a highly durable finish without damaging the texture or appearance.

4- (Function) The finishing agent used for finishing in the present invention is attached to or bonded to fibers and has water absorption, hygroscopicity, antistatic property, water repellency/waterproof property, oil repellency, and SR property. , refers to agents that provide effects such as flame retardancy, disaster prevention, anti-melting, antibacterial, antifungal, and insect repellent properties, such as water absorption, hygroscopicity, antistatic properties,
11. Hydrophilic agents (polyethylene glycol derivatives, treatment agents containing various hydrophilic polymers, etc.) that provide water repellency, etc.
Oil repellents (higher aliphatic compounds, silicone-based, fluorine-based, etc.), mildew-proofing agents (phenol-based, etc.), softening agents (silicone-based, anionic, cationic, etc.), melt-proofing agents (silicone-based, polyamide-based, etc.) etc.), flame retardant processing agents (aliphatic bosphates, etc.), hard finishing agents (melamine-based, urethane-based)
Examples include, but are not limited to. Among these, polyethylene glycol derivative-based hydrophilic agents that provide water absorption, hygroscopicity, and SR properties are particularly effective. Preferred hydrophilizing agents based on polyethylene glycol derivatives include compounds represented by 5- (where m and R are numbers from 3 to 20, and n is a number from 5 to 500), and these are particularly preferred; Examples include ethylene oxide adducts of alcohols, ethylene oxide adducts of higher fatty acids, and phosphoric acid and sulfuric acid esters of these compounds. Among the compounds represented by the above chemical formula, in the case of a compound having ethylenically unsaturated bonds, these unsaturated bonds usually react to become saturated bonds after finishing treatment.

6- As processing conditions for the finishing process of the present invention, the saponified ethylene vinyl acetate copolymer is swollen in an aqueous medium bath,
Any conditions may be used as long as the finishing agent penetrates into the inside of the fibers, but preferably the treatment is carried out at a bath temperature of 60 to 125°C, an inorganic salt concentration of XO + 2v/β or more, and a residence time of 5 to 120 minutes. .

If the bath temperature is less than 60°C, the saponified ethylene vinyl acetate copolymer will not swell sufficiently and the desired durability will not be achieved; if the bath temperature exceeds 125°C, the saponified ethylene vinyl acetate copolymer will not swell. Hard adhesion: 12, which is not preferable because the texture is impaired.

In addition, the inorganic group concentration was 10/I1. When finishing treatment is performed in an aqueous medium bath containing the above, the added inorganic salts are hydrated,
The finishing agent dispersed in the water bath sufficiently penetrates into the fibers of the swollen saponified ethylene-vinyl acetate copolymer in the aqueous bath, and at the same time, the finishing agent also forms a film on the fiber surface.

Therefore, it is possible to easily apply a highly durable finish without damaging the texture or appearance.

If the inorganic salt concentration in the aqueous medium bath is less than 10+v/J, it is not preferable because sufficient water availability is not obtained to allow the dispersed finishing agent to penetrate into the inside of the swollen fibers.

Examples of inorganic salts include, but are not limited to, sodium salts, potassium salts, calcium salts, etc., but sodium salts are preferred, and sodium sulfate is more preferred. If the residence time is less than 5 minutes, the finishing agent will not sufficiently penetrate into the fibers, which is not preferable. Residence time 12
Even if the time is longer than 0 minutes, the extent to which the finishing agent permeates into the fibers remains the same and is of no industrial significance.

Furthermore, the processing method includes, for example, a dip-nip method, a batch method, a pad method, and a treatment performed simultaneously with dyeing, but is not limited thereto.

The sheet material referred to in the present invention has an ethylene content of 30 to 70
Morti's saponified polymer of ethylene vinyl acetate copolymer (A) and thermoplastic polyester resin (B) have a weight ratio of A
:B = 5:95 to 60:40, any structure may be used as long as it contains at least a portion of mixed or composite fibers, such as woven fabrics, knitted fabrics, nonwoven fabrics, carpets, or combinations thereof; Furthermore, the sheet materials of the present invention include sheet materials that have been subjected to needle punching or water jet punching, napping with cloth, puffing with sandpaper, or combinations of these treatments.

Next, the saponification polymerized or composite fiber of the ethylene vinyl acetate copolymer having an ethylene content of 30 to 70 moles as used in the present invention will be explained in detail.

The thermoplastic polyester resin referred to in the present invention is, for example,
Terephthalic acid, inphthalic acid, naphthalene 2,6-
Aromatic dicarboxylic acids such as dicarboxylic acid, phthalic acid, α, β-(4-carboxyphenoxy)ethane, 4,4'-dicarboxydiphenyl, 5-sodium sulfonephthalic acid, or esters thereof and ethylene glycol, Diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,
4-Si9- A fiber-forming polyester synthesized from diol compounds such as methanol, polyethylene glycol, and polytetramethylene glycol, in which 80 or more moles of the constituent units, especially 90 moles or more, are ethylene terephthalate units or butylene terephthalate units. Preferably, the polyester is

The polyester may also contain small amounts of additives, fluorescent whitening agents, stabilizers, ultraviolet absorbers, and the like.

As a method for obtaining the desired sheet material, in particular, a polyester resin containing polyethylene terephthalate or polybutylene terephthalate as a main component and an ethylene content of 30% is used.
It is important that the two components of the saponified polymer of the ethylene vinyl acetate copolymer of ~70 molti are mixed or combined to form fibers to such an extent that the two-component polymers remain in an aggregated state.

Various polymers are known as resins that are hygroscopic and have fiber-forming ability, but among these polymers, ethylene-vinyl acetate copolymer 10-saponified product has a particularly high Young's modulus when absorbing moisture. It is excellent in that it does not feel sticky even when wet.

As a saponified polymer of ethylene vinyl acetate copolymer (hereinafter abbreviated as EVAL), the degree of saponification is 95q6
EVAL containing 30 to 70 moles of ethylene component having a high degree of saponification is optimal. If the ethylene component content in EVAL increases, the hydroxyl groups (OH) naturally decrease, which makes it impossible to achieve the desired swelling in a water bath and penetration of processing agents, which is undesirable.

In addition, if the ethylene component content is too low, the melt formability will decrease, and when it is mixed with polyester immediately before spinning and then turned into fibers, the spinnability will be poor and single yarn breakage and yarn breakage will increase, so it is not preferable. do not have. Further, it is not suitable because the heat resistance at 250° C. or higher, which is the spinning temperature of polyester, is insufficient. Therefore, it can be said that EVAL with a high degree of saponification and an ethylene component content of 30 to 70 moles is suitable for obtaining the desired fiber. The hydroxyl group of EVAL may be acetalized with an aldehyde compound, more preferably with a dialdehyde compound such as glutaraldehyde or glyoxal.

In the present invention, the weight ratio of EVAL and polyester is 5.
:95 to 60:40. If the weight ratio of EVAL is less than 5% by weight, the amount of impregnation of the processing agent due to swelling of the EVAL of the present invention will be reduced, and the desired durability will not be obtained, which is not preferable.

On the other hand, if the weight exceeds 60%, it is not preferable because the properties of the spinning process and the drawing process deteriorate, and also the properties of the original polyester in the fiber properties deteriorate and the strength becomes low, which is not preferable. Also, the degree of polymerization of EVAL used! If the value is too low, the difference in melt viscosity between the polyester and the polyester during spinning becomes too large, resulting in poor balance of the mixed or composite polymer, resulting in a decrease in spinnability, which is not preferable. JIS-ni-67
It is preferable from the viewpoint of spinnability that the melt index under a load of 2160 r at 190° C. in accordance with Japanese Patent No. 30-1977 is 20 or less.

Furthermore, mixing in the present invention means, for example, melt-extruding the (A) side polymer and the (B) side polymer separately,
Before reaching the spinning nozzle, the ratio of (A) to (B) is mixed in a static mixer to a predetermined weight ratio, and after being mixed uniformly or non-uniformly, the fibers are extruded from the spinning nozzle. It is to become In addition, composite typically means that the (A) side polymer and the (B) side polymer are melt-extruded separately, and the ratio of (A) to CB is adjusted to a predetermined weight ratio before reaching the spinning nozzle. After compounding, the fibers are made into fibers by extruding them through a spinning nozzle. For example, the cross-sectional shape of the fibers is core-sheath type (Figure 1), bimetallic type (Figure 4), multilayer lamination type (Figure 4), etc. Figure 5).

Furthermore, the present invention may combine such a mixture and such a composite to form a fiber, for example, in a core-sheath type fiber,
A composite fiber may be used in which the core component is the CB) polymer and the sheath component is a mixture of the (A) polymer and (B) polymer.

Furthermore, the present invention provides for the mixed or composite fibers to have a fiber cross-sectional shape resembling a pentagonal or hexagonal cross-section through high-order processing such as false twisting and crimp processing, or to have a fiber cross-sectional shape similar to a pentagonal or hexagonal cross-section during spinning. Leaf-shaped, T-shaped, 4-lobed, 5-lobed, 7-lobed,
Even if the sheet material has a multilobal shape such as an eight-lobed shape or various cross-sectional shapes, it is possible to obtain a sheet material with excellent durability, which is the object of the present invention.

In the present invention, penetrating into the inside of the edge line means that approximately 0.1 μm of the surface of fiber #1 is dissolved and removed using a saponified ethylene-vinyl acetate copolymer polymer solvent (e.g., ethanol). This can be confirmed by evaluating the performance.

EXAMPLES Hereinafter, the sheet materials of the present invention will be specifically explained using examples, but the present invention is not limited in any way, and the hydrophilicity (water absorption) in the examples , SR, property, water repellency, and durability were evaluated using the following methods.

1. Hydrophilicity (water absorption) Compliant with JIS L-1096A method, 20X
Attach a 20 ann test piece to a mold frame with a diameter of 15 mm without causing wrinkles, and use a dropper that can divide distilled water at 20 ± 2 °C into 25 to 28 drops of water at 14 mm. Then, place one drop of water so that the tip of the dropper is approximately 1 crn from the surface of the horizontal test piece, and measure the time until the water drop on the test piece stops exhibiting any special reflection.

It can be said that the shorter the water absorption time, the easier it is to get wet with water.

2. SR property (stain repellency) A 6 x 6 α test piece was placed horizontally on a polyethylene sheet, and 0.1 d of contaminating solution (0.1% carbon black added to motor oil, stirred, After dropping the mixture) using a measuring pipette, place a polyethylene sheet over the contaminated area for 50 minutes. Apply a load of After removing the main polyethylene sheet and leaving it for about 1 hour, use a household washing machine to mix 22/2 neutral detergent into a 40°C washing solution, wash for 10 minutes, and dry.

The degree of contamination is determined in accordance with JIS-L-0803-74, and the judgment values are divided into grades 1 to 5, with grade 1 being SR, the lowest grade, and grade 5 being SR, and the highest grade.

3. Water repellency Compliant with JIS L 1092 spray test, attach a 20 x 20 crn test piece to a 15 crn diameter mold without wrinkles, insert it into a spray nozzle, and spray it with 250 ml of room temperature water at a fixed angle. After spraying 1 ~
After removing excess water droplets, the wet state of the test piece is evaluated by comparing and contrasting it with a standard sample.

The criteria for determining the water repellency score and the wet state of the fabric surface are as follows.

4.Durability Using a household washing machine, add 22% neutral detergent to the washing liquid at 40℃.
/2 was washed and the washing durability was examined.

QHL is for no washing, and I is for washing for 100 minutes continuously.
The above performance was evaluated using QHL and 3QHL when washing for 300 minutes continuously.

Example 1 Saponified ethylene vinyl acetate copolymer (A) with an ethylene content of 48 mol and saponification degree of 99 mol and polyethylene terephthalate CB with an intrinsic viscosity of 0.70)
Melt extrusion using separate extruders using
After compounding (A) and (B) at a composite ratio of 50:50% by weight, the fibers are discharged using a spinning nozzle so that the cross section becomes a core-sheath type composite fiber as shown in Figure 1. Amount 18f/min.

Melt spinning was carried out at a spinning winding speed of 1000 m/min. The obtained spun yarn was stretched using a normal roller plate type stretching machine under the conditions of a hot roller of 75°C, a hot plate of 120°C, and a stretching ratio of 3.3 times,
A multifilament of 50d/24f was obtained. The spinnability and stretchability were good and there were no problems. The obtained multifilaments were used as warp and weft yarns to weave a 1/l plain woven fabric. The weaving process was also particularly problematic. This plain fabric is called Actenol R.
After desizing in a bath at 80°C containing -1001f/λ, glutaraldehyde 51/L1 sulfuric acid 152/bu,
It was immersed in a bath containing a composition solution containing 10 f/l of sulfuric acid, treated at 90°C, and then immersed in H2O25C.
It was treated at 80°C with a composition solution containing C/n. After heat setting at 160° C., finishing treatment was performed at the same time as dyeing according to the following conditions. In order to examine the effect of the finishing agent, the same treatment was carried out under conditions in which the finishing agent was not used.

The obtained plain woven fabric has a very good texture and has a high hydrophilicity (water absorbency),
SR properties and durability were evaluated.

Example 2 Saponified ethylene-vinyl acetate copolymer polymer (A) with an ethylene content of 48 molar and 99 molar and polyethylene terephthalate 1- with an intrinsic viscosity of 0.70.
(B) is melt-extruded using separate extruders, and the composite ratio of (A) and (B) is 30 nia 0% by weight.
After compositing the fibers so that the cross-section becomes a multilayer composite fiber as shown in FIG. 5, the spinning nozzle discharges the fibers at a rate of 30 f/min.

Melt spinning was performed at a spinning take-up speed of 1200 m/min. The obtained spun yarn was stretched using a normal roller plate type drawing machine under the conditions of a hot roller of 75°C, a hot plate of 120°C, and a stretching ratio of 2.9 times.
A multifilament of d/24f was obtained. The spinnability and stretchability were good and there were no problems. A milled fabric was knitted using the obtained multifilament. The silk fabric was desized, subjected to 20% alkali weight loss and heat set at 180°C, and then dyed in the same manner as in Example 1. After that, PEG-based hydrophilic agent 10% owf
.

Treatment was carried out for 30 minutes in a water bath at 80°C to which 30 kg/λ of calcium carbonate was added and in an organic solvent at 50°C.

The obtained knitted fabric had a very good feel, and its hydrophilicity (water absorption), SR, property, and durability were evaluated based on the methods described in the text.

Comparative Example 1 Ordinary polyester filament yarn (50d/24f)
A 1/1 plain weave was woven using a 1/1 plain weave fabric, which was then subjected to a process treatment followed by a finishing treatment (a PEG-based hydrophilic agent IQ% owf was added) at the same time as dyeing, as described in the text. Based on the method, hydrophilicity (water absorption), SFL property,
Durability was evaluated.

Table 1 summarizes the evaluation results of the sheet materials shown in Examples 1 and 2 and Comparative Example 1 based on the method described in the text.

As shown in Table 1, in Examples 1 and 2 (water bath treatment), the desired finishing effects (initial performance) of hydrophilicity and SR properties were sufficiently obtained by applying the finishing process.
It can also be seen that it has excellent durability against washing and abrasion. On the other hand, it can be seen that in Example 2 (in an organic solvent bath) and Comparative Example 1, initial performance is imparted by finishing, but durability is poor. In Example 2 above, in which a water bath was used as the treatment bath, it was confirmed that the treatment agent penetrated into the fibers.

21-Example 3 A 1/1 plain woven fabric using the core-sheath type composite fiber shown in Example 1 was subjected to punching, glutaraldehyde treatment, and dyeing treatment under the same conditions as Example 1, and then silicone It was immersed in a water bath containing a water repellent finishing agent 10 Li/J2 and sodium sulfate 20 V/λ at a bath temperature of 80°C for 10 minutes, 50 minutes, and 120 minutes, squeezed uniformly with a mangle, and dried. Water repellency and durability were evaluated based on the method described in .

Furthermore, in order to confirm that the finishing agent had penetrated into the inside of the fiber, the obtained plain fabric was immersed in an ethanol bath to dissolve approximately 1 μm of the saponified ethylene vinyl acetate copolymer on the fiber surface. The water repellency was evaluated by removing the finishing agent adhering to the fiber surface.

Comparative Example 2 1 made of the polyester filament shown in Comparative Example 1
/1 plain fabric was processed and dyed by a general method, and then treated with the same silicone water repellent agent 102/β and sodium sulfate 20 f/1. The samples were immersed in a water 22-bath containing 80° C. for 10 minutes, 50 minutes, and 120 minutes, and water repellency and durability were evaluated based on the method described in the text.

Furthermore, for comparison, the resulting plain woven fabric was immersed in an alkaline bath to dissolve the surface of the polyester fibers, and the finishing agent adhering to the fiber surfaces was completely removed to evaluate water repellency.

The evaluation results of the sheet materials shown in Example 3 and Comparative Example 2 are summarized in Table 2.

From Table 2, it can be seen that in Example 3, even though the finishing agent adhering to the fiber surface was removed, the result was still 1. The effect of water-repellent P treatment is observed, indicating that the finishing agent penetrates into the saponified ethylene-vinyl acetate copolymer polymer [7], improving the durability of the finishing process.

On the other hand, Comparative Example 2 shows that when the finishing agent adhering to the surface of the υ fibers is removed by washing or friction, the finishing effect also disappears.

Table 1: Margin Table (Effects of the Invention) According to the present invention as described above, a sheet material with excellent initial performance and durability can be easily obtained by performing a finishing process.

[Brief explanation of drawings]

Figures 1 to 7 are cross-sectional views of typical fibers used in the present invention. In Figure 1, the north side (B) is the poly sheath part (A)
It is a polymer. In Figures 2 to 7, either (A) polymer or (B) polymer may be used.

Claims (1)

[Claims] 1. A saponified polymer (A) of an ethylene vinyl acetate copolymer having an ethylene content of 30 to 70 mol% and a thermoplastic polyester polymer (B) are (A):(B)=5: 95~
A finished sheet material containing fibers mixed or composited at a weight ratio of 60:40, characterized in that a finishing agent has penetrated into the interior of the polymer (A). 2. Saponified polymer (A) of ethylene vinyl acetate copolymer with ethylene content of 30 to 70 mol% and thermoplastic polyester polymer (B) (A):(B) = 5:95 ~
When finishing a sheet material containing fibers mixed or composited at a weight ratio of 60:40, it contains a finishing agent,
A method for producing a finished sheet material, which comprises treating the sheet material in a water bath with an inorganic salt concentration of 10 mg/l or more and a bath temperature of 60 to 125° C. for a residence time of 5 to 120 minutes.