JP2001001452A - Waterproof sheet for tent and hood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a waterproof sheet for a tent and a hood, which is excellent in durability and has both flexibility and waterproofness and, in addition, can be easily recycled. SOLUTION: This waterproof sheet is formed by covering at least one side of a base fabric made of polyester fibers with polyester-based elastomer under the state that the 50 wt.% or more of the weight of the base fabric is occupied by hollow polyester fibers having a hollowness of 20 to 50%. Or, as the polyester-based elastomer, the polyester-based elastomer containing a hard segment H consisting of a polybutylene terephthalate-based polyester unit, in which 40 mol% or less of total dicarboxylic acid component is occupied by the copolymer component except terephthalic component and tetramethylene glycol component, and a soft segment S consisting of a polyester unit, which is mainly made of an aromatic dicarboxylic acid component and a long chain diol component with 5 to 15 carbon atoms in a main chain between hydroxyl groups and which has a melting point below 100 deg.C or is amorphous, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof sheet which has excellent durability, can be recycled and is environmentally friendly, and can be suitably used for applications such as tents and hoods.

[0002]

2. Description of the Related Art Hitherto, there have been known tents and hood waterproof sheets in which a base fabric is coated with a vinyl chloride resin, a urethane resin, or the like. However, these coating resins have inadequate properties for preventing migration of compounded chemicals, light resistance, hydrolysis resistance and the like, and are problematic in the above-mentioned applications used under conditions of exposure to outside air. That is, although a large amount of plasticizer is blended in the vinyl chloride resin to exhibit flexibility, the plasticizer bleeds out with the passage of time, and not only the vinyl chloride resin hardens but also becomes brittle and cracks. There is a problem that waterproofness is reduced. On the other hand, the urethane resin has sufficient flexibility without using a plasticizer, but the durability, particularly the weather resistance is insufficient, so that the embrittlement and hardening of the resin layer progress with time. There is a similar problem.

Further, vinyl chloride resin and urethane resin are
Recycling is difficult because the material is different from the fiber constituting the base fabric. On the other hand, there is also a problem that harmful substances such as dioxin and nitric oxide are easily generated by incineration.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and an object of the present invention is to provide a combination of excellent durability, flexibility and waterproofness, and to facilitate recycling. An object of the present invention is to provide a waterproofing sheet for tents and hoods. Another purpose is lightweight and flexible,
An object of the present invention is to provide a tent / hood waterproof sheet which has good handleability and does not easily wrinkle during use. Yet another purpose is:
An object of the present invention is to provide a waterproof sheet for tents and hoods having excellent light resistance and hydrolysis resistance.

[0005]

According to the study of the present inventors, the first object is to provide a method in which at least one surface of a base fabric composed of polyester fibers is coated with a polyester elastomer. It has been found that this can be achieved by a tent / hood waterproof sheet characterized by the following.

Another object of the present invention is to form a hollow polyester fiber having a hollow ratio of 20 to 50% at least 50% by weight based on the weight of the base fabric, or a terephthalic acid component and tetramethylene as a polyester elastomer. A hard segment (H) comprising a polybutylene terephthalate-based polyester unit in which the copolymer component other than the glycol component is 40 mol% or less based on the total dicarboxylic acid component; 5 to 15 carbon atoms in the main chain
Mainly composed of a long-chain diol component having a melting point of 10
Use a polyester-based elastomer containing a soft segment (S) composed of a polyester unit that is less than 0 ° C. or amorphous and has a composition weight ratio (H: S) of 20:80 to 70:30. ” Has been found to be achievable.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The base fabric used in the present invention needs to be substantially composed of polyester fibers in order to make the entire waterproof sheet recyclable.

[0008] The polymer constituting the polyester fiber is not particularly limited as long as it is a polyester-based polymer. A copolymer in which the third component is copolymerized with carboxylate and these polyesters in a range that does not impair the object of the present invention, usually in a range of 10 mol% or less, preferably 5 mol% or less based on all acid components. Any of polymerized polymers can be used.
Among them, polyethylene terephthalate or a copolymer thereof is preferable. These polymers may be mixed with various well-known functional agents in a range that does not impair the object of the present invention, usually in a range of 20% by weight or less, and preferably in a range of 10% by weight or less.

Regarding the form of this polyester fiber,
Either a multifilament or a short fiber may be used, or a spun yarn containing the short fiber may be used. The preferred form is
Multifilaments having relatively high strength, and among them, multifilaments subjected to bulky processing such as Taslan processing are preferable because the adhesive strength of the polyester-based elastomer coating layer is improved.

The cross section of the fiber in the longitudinal direction may be a solid or hollow cross section, and may be a circular or irregular shape. Above all, fibers having a hollow portion, particularly hollow fibers having a hollow ratio of 20 to 50%,
When 50% by weight or more of the base fabric constituent fiber is obtained, the obtained waterproof sheet not only exhibits excellent lightness, but also hardly generates wrinkles. It is preferable because crack generation is suppressed and use durability is improved.

The fineness of the polyester fiber is from 1 to 2 from the viewpoint of the strength of a waterproof sheet for tents and hoods and the ease of handling in the process of manufacturing the base fabric.
The range of 0 denier is preferable, and the range of 2 to 10 denier is particularly preferable. Further, for the same reason as the single fiber fineness, the total fineness when the polyester fiber is a multifilament or spun yarn is preferably in the range of 30 to 2,000 denier, particularly preferably 50 to 1200 denier.

Next, as the form of the base fabric, any fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric can be adopted as long as it is made of the polyester fiber as described above. This is preferable because the constituent multifilaments or the spun yarns are firmly entangled with each other, so that pull-out hardly occurs. Such a waterproof sheet is not easily frayed even when cut to be sewn on a tent or a hood, so that sewing is very easy and complicated sewing is possible. In addition, the fray herein refers to a phenomenon in which, when the sheet is cut, the yarn constituting the base cloth existing on the end face falls off the sheet.

The basis weight of the base fabric is preferably 100 g / m ² or more from the viewpoint of maintaining the strength of the base fabric, and is preferably 500 g / m ² or less from the viewpoint of maintaining the flexibility of the base fabric.

Next, the polyester-based elastomer used in the present invention is composed of a high-melting crystalline polyester unit (hard segment) and a low-melting or non-crystalline polymer unit comprising a polyether unit and / or a polyester unit (soft segment). ) May be used as long as it is a polyester block copolymer having the following main components.

Preferred hard segments include dicarboxylic acids such as terephthalic acid and naphthalene-2,6-dicarboxylic acid, or ester-forming derivatives thereof, aliphatic diols having 2 to 4 carbon atoms in the main chain, and 1,4. -High melting point crystalline polyester units formed from diols such as alicyclic diols such as dicyclohexanedimethanol, aromatic diols such as xylylene glycol and bis (p-hydroxy) diphenyl, or ester-forming derivatives thereof. And polyester units obtained by copolymerizing copolymer components such as isophthalic acid, phthalic acid, and hexamethylene glycol in an amount of 40 mol% or less based on the total acid components. Among them, polybutylene terephthalate is particularly preferred.

On the other hand, preferred soft segments include aliphatic polyether units such as polyethylene glycol units and polytetramethylene glycol units having a molecular weight of 1,000 or more, aliphatic diols having 2 to 15 carbon atoms in the main chain, and ester-forming compounds thereof. Examples thereof include low melting point or amorphous polyester units having a derivative and a dicarboxylic acid having 2 to 15 carbon atoms in the main chain or an ester-forming derivative thereof as main constituent components.

Among such polyester-based elastomers, in particular, a polybutylene terephthalate-based polyester unit in which a copolymer component other than the terephthalic acid component and the tetramethylene glycol component is 40 mol% or less based on the total dicarboxylic acid component is a hard segment. (H)
The soft segment (S) is mainly composed of an aromatic dicarboxylic acid component and a long-chain diol having 5 to 15 carbon atoms between hydroxyl groups and having a melting point of less than 100 ° C or an amorphous polyester unit. And the weight ratio (H: S) of both is in the range of 20:80 to 70:30, the elastomer itself has excellent stain resistance and durability such as weather resistance and hydrolysis resistance, In addition, the recyclability of the waterproof sheet is improved, which is the most preferable.

In the production of such an elastomer, first, a polyester constituting each of the soft segment (S) and the hard segment (H) is prepared, and then both are melt-mixed. What is necessary is just to adjust so that it may become lower than the melting point of the polyester which comprises.

Since the melting point varies depending on the mixing temperature and time, a method is also employed in which a catalyst deactivator such as phosphorus oxyacid is added to deactivate the catalyst when the desired melting point is reached. For example, phosphoric acid, phosphorous acid, and organic phosphonic acid having a molar number equal to or greater than, preferably 1.2 to 3.0 times, the number of metal atoms of the titanium or tin compound added as a polymerization catalyst for the polyester for the hard segment and the soft segment. An acid or the like is added.

The finally obtained elastomer has a temperature of 35 ° C.
It is preferred that the intrinsic viscosity measured in orthochlorophenol is at least 0.6, especially in the range 0.8 to 1.5.

Incidentally, various functional agents such as a stabilizer, a pigment, a dye, a nucleating agent, a lubricant and a flame retardant may be added to such an elastomer.

Next, a method for coating the above-mentioned polyester-based elastomer on the above-mentioned base cloth will be described. The waterproof sheet for tents and hoods of the present invention can be obtained by laminating and impregnating the above-mentioned polyester-based elastomer on the base fabric made of the above-mentioned polyester fibers and covering the same. For the method of lamination and impregnation, a means well known in the art may be employed.For example, a molten polyester-based elastomer is extruded on the surface of the base fabric, and the elastomer is pressed into the base fabric while being pressed against the base fabric. A method in which at least a part is pressed and bonded (so-called melt lamination method), a method in which an elastomer sheet formed into a sheet by a T-die or calendering method is joined using a suitable anchoring agent (so-called dry lamination method), Examples include a method of dipping a cloth in an elastomer solution (so-called dip method), and a method of applying an elastomer solution to one side of a base cloth (so-called knife coater method). Among these, a melt lamination method and a dry lamination method, which have relatively simple manufacturing steps, are preferred.

The amount of the elastomer applied to the base cloth slightly varies depending on whether the applying means is lamination or impregnation. For example, in the case of lamination, the thickness of the elastomer is an important factor. That is, the thickness of the elastomer layer is preferably 250 μm or less from the viewpoint of flexibility of the obtained sheet, and is preferably 10 μm or more from the viewpoint of waterproofness. Here, the thickness of the elastomer layer is a linear distance from the surface of the base fabric to the outer surface of the elastomer layer on one side of the sheet, and in the case of both sides, if each side is within this range, Good. On the other hand, in the impregnation mode, the weight ratio of the elastomer to the base fabric is an important factor. For the same reason as the thickness described above, the preferred weight ratio of the two is preferably in the range of 1: 0.2 to 3.0, particularly preferably 1: 0.3 to 2.0.

The tent and hood waterproofing sheet of the present invention obtained as described above does not suffer from deterioration in flexibility and waterproofness over time and becomes dirty when compared with a conventional sheet using a vinyl chloride resin. It will be difficult. In addition, the matrix polymer of the fibers constituting the base fabric is polyester,
Since the coating resin is a polyester-based elastomer, it can be easily recycled.

[0025]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. In addition, each characteristic value in an Example followed the following measuring method.

<Fasting resistance> 10 (weft) through waterproof sheet
A rectangular sample was cut by cutting to 5 cm x 5 mm (longitudinal), and a 5 cm long side portion was gripped by a chuck, and then the chuck was fixed at a position 3 cm above a horizontally placed iron plate. The chuck was moved horizontally by 5 cm each before and after in the thickness direction of the sample, and this was repeated 300 times / 10 minutes in a reciprocating manner.

<Weather Resistance> Using a sunshine weather meter according to JIS K7102, the surface condition of the resin surface of the sample after a lapse of 1500 hours without rain at 63 ° C. was evaluated.

<Wrinkle resistance> The cloth was cut into a width of 5 cm, folded in ^two, a load of 500 g / 25 cm ² was applied for 10 minutes, and after 30 minutes of deloading, the state of the folds was visually observed to see the state of wrinkles.

Reference Example 1 Dimethyl terephthalate 180
Part, 20 parts of dimethyl sebacate, 140 parts of tetraethylene glycol and 30 parts of diethylene glycol are subjected to a transesterification reaction with a dibutyltin diacetate catalyst, followed by polycondensation under reduced pressure to give a polyester (S) having an intrinsic viscosity of 1.01.
I got This polyester (S) has an intrinsic viscosity of 0.98
Of polybutylene terephthalate (H) was dried, 170 parts were added, and the mixture was further reacted at 240 ° C. for 45 minutes. Then, 0.1 part of phenylphosphonic acid was added to stop the reaction. This polyester-based elastomer (A)
Had a melting point of 192 ° C. and an intrinsic viscosity of 1.02.

Reference Example 2 Dimethyl isophthalate 180
Parts, 20 parts of dimethyl sebacate and 170 parts of hexamethylene glycol were subjected to a transesterification reaction with a dibutyltin diacetate catalyst, followed by polycondensation under reduced pressure to obtain a polyester (S) having an intrinsic viscosity of 1.06. This polyester (S)
Then, chips of polybutylene terephthalate (H) having an intrinsic viscosity of 0.98 were dried, and 107 parts were added thereto.
After further reaction for 45 minutes, 0.1 part of phenylphosphonic acid was added to stop the reaction. This polyester-based elastomer (B) had a melting point of 204 ° C. and an intrinsic viscosity of 1.07.

Example 1 Polyester high strength yarn BHT
A 500-denier 96 filament is woven in a plain weave structure at a density of 23 filaments / inch in the course of the process, and the base fabric thereof is used as a pretreatment agent as crisvon AH- manufactured by Dainippon Ink and Chemicals, Inc.
420 (polyester-based adhesive) based on the weight of the base cloth
Wt.%, And cured at 120 ° C. for 3 minutes. Then, 100 parts of the polyester elastomer of Reference Example 1 containing 30 parts of ammonium polyphosphate (Terage C60: manufactured by Chisso Corporation) as a flameproofing agent was added to T. The laminate was laminated on a table at 225 ° C. at a thickness of 250 μm on the front surface and 200 μm on the back surface to obtain a recyclable tent and hood sheet having good weather resistance and anti-wrinkle properties.

Example 2 Cationic dyeable polyester hollow fiber 840 denier 192 filament (having a hollow ratio of 32)
%, Strength of 5.1 g / de, elongation of 14.5%) with a weft-inserted Russell to 18 threads / inch through L1 (00/00), 18 threads / inch on the weft-inserted yarn, and L2 (32/21/10) /
12) and L3 (10/12/23/21), after knitting using cationic dyeable polyester solid yarn 75 denier 24 filament, the resulting knitted fabric was treated with Dainippon Ink ( CRISVON AH420
And then cured at 130 ° C. for 3 minutes, and then the polyester elastomer resin of Reference Example 2 was heated at 230 ° C. at 210 ° C. at 210 ° C. and the back surface 200 μm.
It was melt-laminated to a micron thickness to obtain a hood which was not easily frayed from the cut, and had good weather resistance and wrinkle recovery properties. According to the wrinkle test, wrinkles 30 minutes after the removal of the weight were almost invisible.

[Embodiment 3] BHT500-9 of Embodiment 1
A tent / hood sheet was obtained in the same manner as in Example 1 except that the cationic dyeable hollow fiber of Example 2 was used instead of 6. The stain resistance was equivalent to Example 1, while the wrinkle recovery was better than Example 1 and equivalent to Example 2.

[Comparative Example] The base fabric used in Example 1 was calendered with a PVC resin, and the surface was 250 microns and the back surface 2
Finished to a thickness of 00 microns. Although the obtained sheet could be used as a tent, it could not be recycled because it was a PVC resin, and the plasticizer bleed-out and became easily stained with the passage of use time, and wrinkles were easily generated by a wrinkle test Was something.

[0035]

As described above, the waterproof sheet for tents and hoods of the present invention has a sufficient flexibility without incorporating a plasticizer in the coating resin as compared with the conventional sheet using a vinyl chloride resin. It is excellent in durability without deterioration in flexibility and waterproofness, and is hardly stained.
In addition, since the fibers constituting the base fabric are polyester fibers and the coating resin is a polyester-based elastomer, and both are the same type of polymer, recycling is extremely easy. Further, in the present invention, added values such as anti-fraying property, anti-wrinkling property and handling property can be imparted, and it is particularly suitable as a tent / hood waterproof sheet.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08J 5/18 CFD C08J 5/18 CFD C08L 67:02 F term (Reference) 2E141 AA00 EE03 EE04 4F006 AA35 AB35 BA05 4F071 AA44 AH03 BB06 BC01 4F100 AK41A AK41B AK41C AK42B AK42C AL01B AL01C AL09B AL09C BA02 BA03 BA06 BA07 BA10B BA10C DG01A DG11A DG13A EH17 EH172 GB90 JD00 YK00 JL00

Claims (5)

[Claims] 1. A waterproof sheet for tents and hoods, wherein at least one surface of a base fabric made of polyester fibers is coated with a polyester elastomer. 2. The waterproofing sheet for tents and hoods according to claim 1, wherein at least 50% by weight of the weight of the base fabric is a hollow polyester fiber having a hollow ratio of 20 to 50%. 3. The tent / hood waterproof sheet according to claim 1, wherein the base fabric is a warp knit. 4. The tent / hood waterproof sheet according to claim 3, wherein the warp-knitted fabric is a warp-knitted warp-knitted fabric. 5. A hard segment (H) in which the polyester elastomer comprises a polybutylene terephthalate polyester unit in which a copolymer component other than the terephthalic acid component and the tetramethylene glycol component is 40 mol% or less based on all dicarboxylic acid components. And a polyester unit mainly composed of an aromatic dicarboxylic acid component and a long-chain diol component having 5 to 15 carbon atoms in the main chain between hydroxyl groups, and having a melting point of less than 100 ° C or amorphous. And the composition weight ratio (H: S) of both is 20:80 to 7
The waterproof sheet for tents and hoods according to claim 1, wherein the ratio is 0:30.