JP2000226774A - Resin-finished fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin-finished fabric excellent in performances including flexibility, bending resistance, high-frequency exothermic effect, antifouling effect, waterproofness, durability and wear resistance over the wide range of temperatures covering low to high temperatures. SOLUTION: This resin-finished fabric is such one that at least one side of a fabric layer is integrated with a coating layer; wherein the coating layer is made from a resin mixture comprising 100 pts.wt. of a resin component composed of (A) 20-85 wt.% of an ethylene-vinyl acetate copolymer containing 10-25 wt.% of vinyl acetate and (B) 15-80 wt.% of a 2nd ethylene-vinyl acetate copolymer containing 40-85 wt.% of vinyl acetate and 10-300 pts.wt. of granules.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to not only a low halogen content but also substantially no generation of toxic gas such as dioxin in incineration (environmentally friendly) and a low halogen content. The present invention relates to a resin processed cloth suitable for a waterproof cloth excellent in various properties such as high-frequency heat generation and abrasion resistance, a resin mixture suitable as a component of the resin processed cloth, and a sheet made of the mixture.

[0002]

2. Description of the Related Art Conventionally, as a resin-treated cloth used for various applications such as a waterproof cloth, a vinyl chloride resin (PVC) sol is coated on an organic fiber cloth represented by polyester fiber, or a PVC film is used. The fabric is integrated (laminated, topped, laminated, etc.). Such a waterproof cloth is not only relatively flexible and high in handling and workability, but also excellent in various properties such as water resistance, light resistance, abrasion resistance, and durability. In addition, since PVC contains a chlorine element, antimony oxide and the like are used. The flame retardant performance is easily ensured by blending the flame retardant aid. In addition, since the sheet is excellent in high-frequency heat generation and easily fused, the sheets can be joined efficiently, and the sheet is excellent in handleability, workability, and maintainability.

[0003]

SUMMARY OF THE INVENTION As described above, PVC
Although the waterproof cloth provided with is excellent in various performances, it is an environmental problem because toxic dioxin and hydrochloric acid gas that damages the incinerator are generated during incineration. Therefore, P
There is a strong demand for the development of an earth-friendly resin processed cloth that replaces the resin-coated cloth provided with VC.

In view of the above, various resin-treated cloths using non-halogen resins such as polyethylene and ethylene-vinyl acetate copolymer (EVA) instead of PVC have been proposed. For example, JP-A-1-301247 discloses that EVA having a vinyl acetate content of 10 to 20% by weight is 60 to 90% by weight.
And EVA having a vinyl acetate content of 22 to 35% by weight.
It has been proposed to coat a fiber substrate with an EVA composition consisting of 40% by weight. According to the invention, a vinyl acetate content of 22 to 3 is used to enhance flexibility and high frequency weldability.
5% by weight of EVA and an EV having a vinyl acetate content of 10 to 20% by weight to obtain heat creep resistance.
A is used.

[0005] According to this method, a resin-treated cloth excellent in various performances can be obtained, but if granules are blended for the purpose of imparting flame retardancy, reinforcement, etc., various performances such as flexibility and bending resistance are impaired. In particular, there is a problem that the performance at low temperatures is remarkably reduced. In particular, in order to obtain a high level of flame retardancy, it is necessary to mix a large amount of inorganic fine particles. In view of the above problems, the object of the present invention is excellent in various properties such as flexibility, bending resistance, and high-frequency heat generation even when various particles are blended in the coating layer,
It is an object of the present invention to provide a resin processed cloth which exhibits excellent performance in an environment ranging from a low temperature to a high temperature and is suitable as an earth-friendly waterproof cloth, and a resin mixture and a sheet which are suitable as constituent components of the resin processed cloth.

[0006]

According to the present invention, there is provided (1) a resin-processed cloth in which a coating layer is integrated on at least one surface of a cloth layer, wherein the coating layer has a vinyl acetate content of 10 to 2;
100 parts by weight of a resin component consisting of 20 to 85% by weight of EVA (A) of 5% by weight, 15 to 80% by weight of EVA (B) having a vinyl acetate content of 40 to 85% by weight, and granules 10 to 30
(2) at least one part of the granular material has a maximum endothermic temperature of 1 part by weight;
The resin processed cloth according to (1), which is an inorganic fine particle having a temperature of 50 to 500 ° C. and a maximum heat absorption of 250 cal / g or more, (3)
(1) A waterproof cloth comprising the resin-treated cloth according to any of (2) and (4) a vinyl acetate content of 10 to 25% by weight.
A resin composition containing 20 to 85% by weight of EVA (A) and 15 to 80% by weight of EVA (B) having a vinyl acetate content of 40 to 85% by weight; (5) a coating layer integrally formed on at least one surface of the fabric layer; A resin-treated cloth, wherein the coating layer has a vinyl acetate content of 10 to 25% by weight.
20-85% by weight, vinyl acetate content 40-85% by weight
Resin component 10 comprising 15 to 80% by weight of EVA (B)
(6) A sheet comprising the resin mixture according to (5), which comprises 0 parts by weight and 10 to 200 parts by weight of the granules.

The present invention is excellent in various properties such as flexibility, bending resistance and abrasion resistance even when particles which easily deteriorate flexibility, abrasion resistance and bending durability are added to the coating layer. , A wide temperature range from low to high, specifically at least-
An object of the present invention is to obtain a resin processed cloth exhibiting excellent performance in a wide range of practical temperatures from 20 ° C to 70 ° C. In the present invention, as a resin component constituting the coating layer, low vinyl acetate-containing EVA (A) having a vinyl acetate content of 10 to 25% by weight.
It is necessary to use a resin component containing high vinyl acetate-containing EVA (B) having a vinyl acetate content of 40 to 85% by weight,
The use of this component produces the above effects.

Further, in the present invention, EVA (A) and EVA (B) are used in combination, and EVA (A) is 20 to 85% by weight and EVA (B) is 15% by weight in the resin component.
８０80% by weight, preferably 30 to 60% by weight of EVA (A) and 40 to 70% by weight of EVA (B). If the content of EVA (A) is too large or the content of EVA (B) is too small in the resin component, the flexibility of the resin component is deteriorated, and the cold resistance and bending resistance become insufficient and cracks are easily formed. This also impairs the high-frequency heat generation. Conversely, if the content of EVA (A) is too low or EV
If the content of A (B) is too large, for example, the surface sticks under a temperature condition of 40 ° C. or higher, so that the antifouling property is impaired, and the abrasion resistance becomes insufficient, which causes a problem in high-temperature characteristics.

Further, the vinyl acetate content of EVA (A) must be 10 to 25% by weight, preferably 15% by weight or more. If the vinyl acetate content of the EVA (A) is too small, the flexibility, flex resistance and high-frequency heat generation of the resin component become insufficient, and the performance degradation particularly at low temperatures becomes remarkable. Conversely, if the content is too large, the abrasion resistance and antifouling properties are impaired, and the high temperature properties become insufficient. For the same reason, the (MFI) of EVA (A) is 1 to 10 g / 10 min, particularly 1 to 3 g / min.
It is preferably 10 minutes. EVA (A) may be further copolymerized with units other than ethylene or vinyl acetate as long as the effects of the present invention are not impaired. From the viewpoint of efficiently obtaining the effects of the present invention, the content of other units is preferably 30% by weight or less, more preferably 10% by weight or less.

The vinyl acetate content of EVA (B) is 40 to
It is necessary to be 85% by weight, preferably 50% by weight or more and 70% by weight or less. If the vinyl acetate content is too low or too high, the crystallinity of the polymer increases and the flexibility becomes insufficient, and the properties particularly at low temperatures are greatly reduced. In addition, when the vinyl acetate content is too low, there is a problem that high-frequency heat generation is impaired. In general, when high vinyl acetate-containing EVA having a vinyl acetate content of 40% by weight or more, particularly 50% by weight or more, is blended, the abrasion resistance of the resin component becomes insufficient and the high-temperature characteristics are easily reduced. Is added and mixed, the high vinyl acetate-containing EV
A remarkable effect can be obtained by blending A.

From the viewpoint of suppressing sticking at a high temperature and increasing abrasion resistance, the melt flow index (MFI) of EVA (B) is 20 g / 10 min or less, particularly 5 g / min.
It is preferably 10 min or less, more preferably 0.1 to 2 g / 10 min. EVA (B) may be further copolymerized with units other than ethylene and vinyl acetate as long as the effects of the present invention are not impaired. In order to obtain the effect of the present invention efficiently, the other units are 30% by weight.
Hereinafter, the content is more preferably 10% by weight or less.

From the viewpoint of enhancing flexibility, bending resistance and abrasion resistance in a wider temperature range and obtaining excellent high-frequency heat generation, the weight average vinyl acetate content of the resin component should be 25% by weight or more, especially 30% by weight. % By weight or more.
It is preferably 0% by weight or less, more preferably 50% by weight or less. In addition, from the viewpoint of processability, adhesiveness to fabric, mechanical performance, and the like, the melt flow index (MF
I) is 20 g / 10 min or less, especially 0.5 g / 10 m
in to 10 g / 10 min or less, further 1 g / 10 m
It is preferable that the content be in the range from in to 2.5 g / 10 min.

The resin component in the present invention is mainly composed of an EVA composition comprising EVA (A) and EVA (B), but other resins are included as long as the effects of the present invention are not impaired. EVA (A) and EVA (A)
EVA other than VA (B) may be included.
The type of the resin is not particularly limited, for example, a rubber component,
Examples include olefin-based resins, acrylates, copolymerized polyamide-based resins, and urethane-based resins. EVA
Resins other than (A) and EVA (B) are 40% by weight or less,
Further, it is preferably at most 30% by weight, particularly preferably at most 10% by weight.

The granules used in the present invention are not particularly limited as long as they are solids, and any granules can be used. For example, particles having an average diameter of 10 mm or less can be used, and particles having an average diameter of 5 mm or less, more preferably 1 mm or less, and further preferably 100 μm or less are preferable from the viewpoint of uniform dispersibility, and the average diameter is 0.01 μm or more and 10 μm or less. , Especially 1
Fine particles of not more than μm can be particularly preferably used. The shape of the granules that can be used in the present invention is not particularly limited, and may be a fibrous material, a beaten material, or the like, including a spherical shape or a shape similar thereto. It is preferably substantially spherical from the viewpoint of uniform dispersibility.

In the present invention, various granules can be used for any purpose. For example, a flame retardant such as antimony oxide and a flame retardant auxiliary, a filler for improving mechanical performance, a filler for cost reduction, a pigment for coloring, various ultraviolet rays such as benzophenone and benzotriazole. Examples include an absorbent, an antioxidant such as an amine and a phenol diameter, and a lubricant such as an octadecyl phosphate-based or ethylene bisamide-based lubricant. Of course these are 2
More than one species may be used in combination. The blending amount of the granules may be appropriately determined. However, in order to effectively obtain the effects of the present invention and not to impair the mechanical performance of the resin mixture, the resin component 1
10 to 300 parts by weight, especially 50 to 20 parts by weight
It is preferably 0 parts by weight, more preferably 80 to 150 parts by weight.

In the present invention, more remarkable effects can be obtained by imparting flame retardancy to the resin mixture. In particular, it is preferable to impart flame retardancy to the extent that it passes the Ministry of Home Affairs Ordinance flame prevention test. When blending a flame-retardant powder, it is preferable to use particles having a maximum endothermic temperature of 150 to 500 ° C., particularly 200 to 350 ° C., and inorganic fine particles having an average particle size of 10 μm or less (especially 1 μm or less), The endothermic amount at the maximum endothermic temperature (maximum endothermic amount) is 250 kcal / g or more,
More than 300 kcal / g, especially 400 kcal / g
g or more.

By mixing such granules, EVA
Since the composition absorbs heat in an appropriate temperature range until the composition undergoes thermal decomposition, an excellent flame retardant effect is achieved. In particular, granules having a large maximum heat absorption can provide sufficient flame retardant effects without being blended in a large amount into the resin component, so that various problems such as weakening of the resin mixture, deterioration of mechanical performance, and deterioration of durability are caused. A more excellent effect is obtained which is less likely to occur. Suitable endothermic inorganic fine particles include aluminum hydroxide and magnesium hydroxide. Such heat-absorbing inorganic fine particles are composed of resin component 1
10 to 300 parts by weight, especially 50 to 2 parts by weight, per 100 parts by weight.
00 parts by weight, more preferably 80 to 150 parts by weight.

It is preferable to use a flame retardant together with the flame retardant from the viewpoint that the flame retardant effect can be enhanced and the amount of the flame retardant added can be reduced. When using the above-mentioned endothermic inorganic particles,
In particular, a remarkable effect can be obtained by using a melamine cyanurate compound in combination. As the melamine cyanurate compound, for example, fine powder having a high melting point obtained by mixing and reacting an aqueous solution of melamine and an aqueous solution of cyanuric acid can be suitably used. The amount of the melamine cyanurate compound is 1 to 5 with respect to 100 parts by weight of the resin component.
It is preferably 0 parts by weight, particularly preferably 5 to 20 parts by weight.

As other flame retardant aids, phosphate compounds such as octadecyl phosphate and zinc compounds of octadecyl phosphate can be suitably used. Even when a small amount of the phosphoric ester compound is blended, the flame retardant effect of the endothermic inorganic particles is synergistically enhanced, and since the compound is a liquid, the effect on the resin mixture is small and more excellent. The effect is obtained. It is preferable to add about 0.01 to 5 parts by weight, especially about 0.1 to 1 part by weight, based on 100 parts by weight of the resin component, and it is more preferable to use it together with the melamine cyanurate compound.

From the viewpoint of high-frequency heat generation, granules having a water content of 5% by weight or more, particularly 10% by weight or more, and more preferably 20 to 50% by weight, are preferably blended. By blending granules having a high water content, the high-frequency heat generation of the resin mixture can be significantly increased. The water content in the present invention refers to the weight ratio of OH groups in the granules, and can be measured by the method described in Examples. In particular, the maximum weight reduction temperature of the granules is preferably 200 ° C. or more, more preferably 250 ° C. or more. Those having a high maximum weight loss temperature are less likely to release water molecules in a processing step and the like, and water molecules are released at the time of high-frequency bonding, so that high-frequency heat generation can be sufficiently enhanced.

It is preferable to use an inorganic hydrate as such a high water content granule, and an inorganic material containing water of crystallization (coordinating water, anion water, lattice water, zeolite water) or the like can be suitably used. Specifically, aluminum hydroxide, magnesium hydroxide, hydrotalcite compounds and the like are preferably mentioned, and these can be used alone or in combination of two or more. From the viewpoint of high-frequency heat generation and the like, it is preferable to use magnesium hydroxide. Of these, endothermic inorganic substances such as aluminum hydroxide and magnesium hydroxide are also excellent in the flame retardant effect, and therefore can be most preferably used in the present invention.

The resin mixture containing the resin component and the granular material is suitable as a coating layer of a fabric, but can be used without being integrated with the fabric. For example, the resin mixture may be formed into a molded product (for example, a sheet such as a film) or may be laminated on a layer other than the fabric layer (for example, a metal layer or a film layer) to form a laminate. The resin mixture and the molded product obtained from the mixture exhibit excellent flexibility, bending resistance, abrasion resistance and mechanical performance in a wide temperature range from low temperature to high temperature, and are also excellent in high-frequency heat generation. Therefore, it can be easily joined. Such a resin mixture can be molded into any form, but it can be applied more widely when it is formed into a sheet. The method of forming the sheet is not particularly limited, but after kneading by a known means such as an extruder, a Beverly mixer, and a two-roll, if it is formed into a sheet by a known means such as a calender roll, a T-die or an inflation extruder, Good.

When the resin mixture is integrated with the cloth, a sheet made of the resin mixture may be laminated or topped on the cloth. Further, after dissolving the resin mixture in an organic solvent or the like, the resin mixture can be integrated with the fabric by a dipping method, a coating method, a roll coat method, a knife coat method, or the like. From the viewpoint of waterproofness and the like, it is preferable to adopt a method of laminating with a cloth after forming the resin mixture into a sheet or simultaneously with forming the sheet. The thickness of the sheet made of the resin mixture is set at 0.1 from the viewpoint of waterproofness, flexibility, antifouling property and the like.
It is preferably 1 to 5 mm, particularly preferably 1 mm or less, more preferably 0.5 mm or less. The amount of the resin component adhering to the fabric in the resin-treated cloth is preferably 50 to 1000% by weight / fabric, and particularly preferably 200 to 500% by weight / fabric from the viewpoint of waterproofness, handleability and the like.

As the fabric layer constituting the resin-treated fabric of the present invention, any fabric such as woven fabric, knitted fabric, and non-woven fabric (wet or dry) can be used, but from the viewpoint of mechanical performance, handleability, etc. Preferably, it is knitted. Specifically, plain weave,
A woven fabric such as an entangled weave or a mosaic weave, or a knitted fabric such as an inserted Russell knit may be used. From the viewpoint of mechanical performance and cost, a plain woven fabric is preferably used. The fabric layer preferably has a basis weight of about 100 to 300 g / m ^{2 in} terms of lightness, mechanical performance, and the like. The mesh size of the cloth may be appropriately set according to the purpose. For example, when used as a waterproof cloth, a high-density plain woven fabric may be used. A woven or knitted fabric may be used.

The type of the fiber constituting the fabric layer is not particularly limited, and for example, various inorganic fibers, synthetic fibers, natural fibers and the like can be used. Specifically, glass fibers and carbon fibers as inorganic fibers, polyester fibers such as polyethylene terephthalate fibers (including molten liquid crystalline polyester fibers), polyamide fibers, aramid fibers, polyolefin fibers, and polyvinyl alcohol fibers as organic fibers. Fiber and the like. In the present invention, a plurality of these may be used in combination, and modified cross-section fibers, composite fibers (core-sheath type or the like), sea-island structural fibers, and the like can also be used. The fibers may optionally contain titanium oxide, kaolin, silica, barium sulfate, carbon black, pigments, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, and the like.

From the viewpoints of mechanical performance, handleability, weight, heat resistance and the like, it is preferable to use synthetic fibers, and it is more preferable to use fibers having high adhesiveness to the resin layer. It is preferable to use an olefin fiber, a polyester fiber or a polyvinyl alcohol fiber from the viewpoints of light resistance, abrasion resistance and low-temperature characteristics. The form of the fiber constituting the fabric is a filament yarn (monofilament, multifilament),
A cut fiber, a spun yarn, a tape-shaped split yarn, or the like may be appropriately selected. When the fabric is a woven or knitted fabric,
It is preferable to use a filament yarn from the viewpoint of mechanical performance, and a single fiber denier of 1 to 3000 d, particularly 3 to 20 d is used.
It is preferably set to about 00d. It is preferable to use a spun yarn from the viewpoint of adhesiveness to the coating layer.

The coating layer is integrated on at least one side of the fabric layer, but it is preferable to form the coating layer on both sides of the fabric layer from the viewpoint of waterproofness, stain resistance and the like. Of course, the resin layer specified in the present invention may be integrated only on one side, and an arbitrary layer (a resin layer, a metal layer, a fabric layer, a rubber layer, etc.) may be integrated on the other side as desired. Further, another layer may be laminated. In addition, there may be a portion where no resin component is present as long as the effect of the present invention is not impaired. Preferably, on at least one side of the resin-treated cloth, 80
It is preferable that at least 90% by area, particularly at least 90% by area is covered with the resin layer. In terms of handling, water resistance, etc.
500-3000 g / m ² , especially 10
The thickness is preferably about 00 to 2000 g / m ² , and the thickness is preferably about 0.2 to 10 mm, particularly about 0.5 to 3 mm.

The resin processed cloth of the present invention is excellent in various performances. For example, the softness is 300 mm or less, and 250
mm or less, and a resin-treated cloth judged to be good in the non-adhesion test, cold resistance test, and rub resistance test shown in Examples can be obtained.

Further, when the sheet made of the resin-treated cloth and the resin mixture of the present invention is used for various purposes, it is necessary to use two or more sheets at their ends and to repair broken parts and the like. When the high-frequency heat generation property of the sheet is low, it is difficult to perform bonding between the sheets and a great amount of time and labor is required, but the resin-treated cloth / sheet of the present invention is excellent in the high-frequency heat generation property. Therefore, the adhesive resin is softened by the high-frequency welder, and processing such as connection and repair between the sheets can be easily and efficiently performed. Preferred conditions for the high-frequency welder include a frequency of 40 to 50 MHz.
z General-purpose high-frequency welder, contact pressure 1kgf / m ²
As described above, the anode current value is 100 to 200 A / m ² ,
After welding for 15 seconds, cooling is performed for 2 to 10 seconds under the same contact pressure. It is preferable that the high-frequency heat generation measured by the method described in the examples is 20 seconds or less, particularly 10 seconds or less.

[0030] The resin-treated cloth of the present invention may have a desired performance by adding particles such as a flame retardant.
Used in all applications because it retains performance such as flexibility, flex resistance, durability, mechanical performance, and water resistance over a wide temperature range from low to high temperatures, and has excellent high-frequency heat generation. it can. For example, it can be widely used for civil engineering and construction applications, covering materials, etc., especially hatch covers, truck hood sheets, nozumi sheets, flexible containers, various liners (pond liners, waste disposal liners, water tank liners, etc.), various tents (Tent warehouses, etc.), sound insulation sheets, architectural sheets (wall sheets, floor coverings, etc.), various water-insulating sheets, etc. Also suitable for embankment reinforcing fiber grids, architectural curing meshes, etc. -Available. Above all, the resin-treated cloth of the present invention is suitable as a waterproof cloth. Further, when the resin-treated cloth of the present invention is provided with flame retardancy, it becomes more suitable for these uses, and more excellent performance is exhibited.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

EXAMPLES [Vinyl acetate content by weight] A resin-treated cloth was treated with a solvent having no C ＝ O group such as carbon tetrachloride to dissolve the resin components, and the obtained resin solution was subjected to liquid chromatography (HLC). EVA treated with different vinyl acetate contents
Are separated from each other. Each of the obtained EVA solutions was set in a cell of an infrared spectrophotometer (IR) and measured, and the vinyl acetate content was calculated from the following equation from the peak of C = O stretching vibration obtained at a wave number of 1740 cm ^-1 . . Note that I
/ I ₀ is the absorbance, A is the amount of the sample (mg / ml solvent), L is the cell thickness (cm), and the half width is the peak width (cm) of a portion showing a half of the peak height. Vinyl acetate content = (0.540 × logI ₀ / I × half-width / AL) × 100 In this example, since EVA with a known vinyl acetate content was used, the value is shown as it is.

[EVA weight ratio] EVA having the same acetic acid content as the vinyl acetate content determined by the above method
Are prepared, and various mixed resin solutions are prepared by changing the mixing ratio of EVA having different vinyl acetate contents. At this time, a solvent having no C ＝ O group such as carbon tetrachloride is used as the solvent. Next, the obtained mixed resin solution was subjected to liquid chromatography (HLC) to collect an HLC peak, and EVA was collected.
A calibration curve is prepared for the ratio of the mixing weight ratio of the above to the ratio of each EVA peak area. Next, EVA was obtained from the peak area ratio of HLC obtained by the measurement of the vinyl acetate content and the above calibration curve.
Find the weight ratio of

[Weight average vinyl acetate content by weight%] {VAc (A) × Wt (A) + VAc (B) × Wt (B)}
/ 100. VAc (A), VAc (B)
Is the vinyl acetate content (% by weight) of EVA (A) or EVA (B), and Wt (A) and Wt (B) are the weight percentage (% by weight) of EVA (A) or EVA (B) in the resin component.
It is.

[Melt Flow Index (MFI)
g / 10 min], determined by applying the condition 4 of “Method for testing flow of thermoplastics” of JIS K7210.
When the MFI of the resin component is obtained, the MFI is obtained after separating the resin from the resin work cloth as necessary. [Maximum endothermic temperature ° C, maximum calorie cal / g] After vacuum-drying the sample at 30 ° C until it becomes weight-equilibrium, collect it in an aluminum cell, measure the mass accurately, and send it to a differential thermal analyzer (DTA). The sample was set and subjected to thermal analysis in a nitrogen stream at 20 ml / min at a heating rate of 5 ° C./min. The temperature showing the maximum endothermic peak was taken as the maximum endothermic temperature, and the calorific value determined from the integrated area of the peak and the sample mass was calculated. Calculate as the maximum heat absorption.

[Maximum weight loss temperature (° C.)] A sample was vacuum dried at 50 ° C. for 24 hours or more, and then dried by a calorimeter.
In a nitrogen gas stream of 0 ml / min, a change in temperature to weight is measured under the condition of a heating rate of 5 ° C./min, and the maximum peak temperature of the differential curve is defined as the maximum weight loss temperature. [Water content%] After the sample was vacuum-dried at 50 ° C. for 24 hours or more, the sample (mass W1 g) was put into a distillation apparatus composed of a heat-resistant container, and was subjected to dry distillation at a temperature of 800 ° C. or more. W2g) is measured, a part thereof is sampled, the water content (c) is quantified by gas chromatography, and calculated by (W2 × C) / W1 × 100.

[Average Particle Diameter μm] Appropriately enlarged by an electron microscope or the like (5,000 if the average particle diameter is 10 μm or less).
The fine particles observed in the cross section of the resin mixture multiplied by a factor of ２０20,000 are measured in diameter when the fine particle shape is a perfect circle or a substantially circular shape, and in the case of a non-circular shape, the major diameter is measured. An average value is obtained, and this is performed in five or more sections, and the average value is obtained. In the state of the granular dispersion liquid, the particle size distribution was measured using a Microtrac particle size distribution analyzer, and the maximum peak point particle size (M
V value) is defined as the average particle size.

[Weight g / m ² , thickness mm, degree of softness mm]
It was measured according to IS L 1096. The bending resistance was measured by the cantilever method. [Flame retardancy] Evaluated according to the Ministry of Home Affairs Ordinance's flame prevention test. [Non-adhesive, cold resistance (cold resistance at -20 ° C)] JI
In accordance with S K 6772, those in which the above did not appear were evaluated as good, and those in which adhesion, cracks, and the like occurred were evaluated as poor.

[Mass resistance] According to JIS M7102 "Scott method", after bending 1000 times with a pressing load of 1 kg, those without cracks and abrasion are good, and those with cracks and abrasion are bad. Was evaluated. [High-frequency heating property seconds] Two resin-treated cloths are overlapped and brought into contact with each other, and a high-frequency bonding machine (manufactured by Pearl Industries, model T-120)
00, frequency 38.6MHz, output 3KW) 20 × 1
An electrode having a size of 50 mm was attached, a joining process was performed under the condition of a contact pressure of 2 kg / cm ² , and a current supply time required for good welding was evaluated as high-frequency heat generation.

Examples 1-3, Comparative Example 1, Comparative Example 2
EVA having a vinyl acetate content of 20% by weight as VA (A)
(Evatate H-2031: Sumitomo Chemical, MFI
EVA (Ebaslen 410-P: 1.5 g / 10 min) having a vinyl acetate content of 60% by weight as EVA (B):
Made by Dainippon Ink and Chemicals, MFI 0.5g / 10mi
n) was uniformly mixed to obtain a resin component. Further, based on 100 parts by weight of the resin component, aluminum hydroxide having a maximum endothermic temperature of 280 ° C., a maximum endothermic amount of 470 cal / g, and an average particle diameter of 1.0 μm or less (Heidilite H42S, a maximum weight loss temperature of 275 ° C., a water content of 34. 6%) 120 parts by weight of a melamine cyanurate compound having an average particle diameter of 10 μm or less (N
F-350: 12 parts by weight of Nissan Chemical Industries, Ltd. and 0.3 parts by weight of a zinc compound of octadecyl acid phosphate (LBT-1830: manufactured by Sakai Chemical Industry) were added and mixed.
After kneading using an inφ2 roll, a sheet having a thickness of 0.4 mm was obtained.

As the fabric, a plain weave fabric (202 g / m ² ) in which 1,500 denier / 192f polyester multifilament yarn was driven in the lengthwise direction at 25 yarns / in and the widthwise direction at 23 yarns / in was used. A sheet made of a resin mixture is laminated on both sides of the fabric, and the temperature is 170 ° C. × 20 k
After pressing for 30 seconds and heating for 3 minutes under the condition of g / cm ² ,
By cooling, a resin processed cloth was produced. Table 1 shows the results
Shown in

Comparative Example 3 Vinyl acetate content: 20% by weight
EVA (Evertate H-2031: manufactured by Sumitomo Chemical Co., Ltd.
EVA (Ultracene UE750) having 70 parts by weight of MFI 1.5 g / 10 min and a vinyl acetate content of 32% by weight.
MFI 30g / 10min, manufactured by Nippon Polychem Co., Ltd.3
Example 1 was repeated except that a resin component obtained by uniformly mixing 0 parts by weight was used. Table 1 shows the results. Comparative Example 4 EVA having a vinyl acetate content of 5% by weight (Evatate D2011: manufactured by Sumitomo Chemical Co., Ltd., MFI 2 g / 10
min) 90 parts by weight, E having a vinyl acetate content of 90% by weight.
The same procedure as in Example 1 was carried out except that a resin component obtained by uniformly mixing 30 parts by weight of a solid obtained by evaporating water from a VA emulsion (OM-6000, manufactured by Kuraray Co., Ltd., MFI 30 g / 10 min) was used. Was. Table 1 shows the results.

Comparative Example 5 Vinyl acetate content: 32% by weight
The procedure was performed in the same manner as in Example 1 except that a resin component consisting only of EVA (Ultrasenon UE750, manufactured by Nippon Polychem, MFI 30 g / 10 min) was used. Table 1 shows the results
Shown in

[0043]

[Table 1]

The resin-treated cloth obtained in the examples had excellent properties such as flexibility, cold resistance, abrasion resistance, and high-frequency heat generation, and was suitable as a waterproof cloth. The resin-treated cloth obtained in Comparative Example 1 had low-temperature properties and low flexibility, and cracks occurred in a retirement test and a rub resistance test. In addition, high-frequency heat generation was low, and it was impossible to perform bonding even after processing for 30 seconds or more. Further, the resin-treated cloth obtained in Comparative Example 2 had low high-temperature characteristics, and not only caused adhesion due to the adhesion treatment, but also had low abrasion resistance and abrasion occurred in the rub resistance test.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) D06M 11/45 D06M 11/00 G F term (reference) 4F072 AA01 AA08 AA09 AB04 AB05 AB06 AB09 AB10 AB28 AB29 AB30 AD04 AD08 AE07 AE09 AE10 AE11 AE21 AF02 AF03 AF04 AF19 AF24 AF25 AF27 AF28 AF29 AF31 AG03 AG20 AH02 AH06 AH25 AH26 AH31 AH46 AK05 AL09 4F100 AA01B AA19 AK22B AK41 AK68B AL05B BA02 DE01B DG04 J03 J03 J04 J04 DE076 DE126 DE146 DE286 EE036 EP026 EU176 EU186 EW046 FD016 FD056 FD076 FD096 FD136 FD176 GF00 GH00 GK02 4L031 AB31 BA11 BA34 BA38 CA08 CA11 DA00 DA16 4L033 AB04 AC03 AC05 AC15 BA39 CA28 DA07

Claims (6)

[Claims] 1. A resin-treated cloth in which a coating layer is integrated on at least one surface of a fabric layer, wherein the coating layer is an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 10 to 25% by weight. 20-85% by weight, vinyl acetate content 40
To 85% by weight of ethylene-vinyl acetate copolymer (B) 1
A resin processed cloth comprising a resin mixture containing 100 parts by weight of a resin component comprising 5 to 80% by weight and 10 to 300 parts by weight of granules. 2. The method according to claim 1, wherein at least a part of the particles has a maximum endothermic temperature of 1
The resin processed cloth according to claim 1, which is an inorganic fine particle having a temperature of 50 to 500C and a maximum heat absorption of 250 cal / g or more. 3. A waterproof cloth made of the resin-treated cloth according to claim 1. 4. An ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 10 to 25% by weight and an ethylene-vinyl acetate copolymer (B) having a vinyl acetate content of 40 to 85% by weight. 15-80% by weight of a resin composition. 5. A resin-treated cloth in which a coating layer is integrated on at least one side of a fabric layer, wherein the coating layer is an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 10 to 25% by weight. 20-85% by weight, vinyl acetate content 40
To 85% by weight of ethylene-vinyl acetate copolymer (B) 1
A resin mixture containing 100 parts by weight of a resin component consisting of 5 to 80% by weight and 10 to 200 parts by weight of granules. 6. A sheet comprising the resin mixture according to claim 5.