JP2014217600A - Protective garment material and protective garment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective garment material and a protective garment having heat protection properties for protecting the body from heat and flame, especially a function of high heat shielding properties added thereto, in the protective garment material and the protective garment for protecting the body from gaseous- and liquid-phase toxic chemicals.SOLUTION: The protective garment material comprises a laminated body including: an outer layer cloth formed of a fabric including 50 wt.% or more non-hot-melt fibers and having char length by a vertical strategy of JIS L1091 (1999) of 15 cm or less; and an inner layer cloth with a mass of 250-400 g/mincluding an activated carbon fiber sheet in a form of a fabric, a textile, or a non-woven fabric with absolute dry mass of 50-150 g/m. The heat protection property thereof is 45°C/15 s or less.

Description

  The protective clothing material and protective clothing of the present invention relate to protective clothing material and protective clothing for protecting workers handling toxic chemicals, especially when a fire occurs due to an accident or disaster, etc. The purpose is to reduce. The present invention relates to a protective garment for preventing the clothing material from being melted by a flame or high heat and opening a hole to reduce the protection against toxic chemicals or to prevent the inside of the garment from becoming hot due to heat conduction.

  The heat-resistant protective clothing worn by firefighters during firefighting operations includes radiant heat applied to fabric made of flame-retardant organic fibers such as aramid fiber, polyphenylene sulfide, polyimide, polybenzimidazole, and polybenzoxazole. For the purpose of prevention, aluminum foil is laminated or aluminum is surface-treated by coating or vapor deposition. When an operator who handles toxic chemicals normally wears this heat-resistant protective clothing, the load of heat stress is heavy due to its heavy weight and low breathability.

  As protective clothing and materials for protecting the body from gaseous and liquid toxic chemicals, there are highly breathable clothing materials as shown in Patent Document 1, but in the case of protective clothing made of this material, In the event of a fire accident or the like, there is a risk that the wearer may be burned due to a loss such as ignition by a flame or a perforated melt. In addition, if a defect occurs, the protection against toxic chemicals is impaired.

  As a technique for protecting a wearer of protective materials and protective clothing for protecting workers handling organic chemical substances from high heat and flame, Patent Document 2 discloses that an outer layer material is disposed outside a toxic chemical substance adsorption layer. A technique for protecting from flame by having flame retardancy is disclosed. However, this technique cannot prevent radiant heat through the clothing material, and exposure to heat for a certain period of time has a high possibility of causing damage such as a burn to the body surface of the wearer.

JP-A-8-308945 JP 2008-30449 A

  The present invention has been made against the background of the above-described prior art. The purpose of the present invention is to provide a protective clothing material for protecting the body from gaseous and liquid toxic chemicals and a protective clothing for protecting the body from heat and flame. An object of the present invention is to provide a protective clothing material and a protective clothing to which a function of excellent protective properties, in particular, heat shielding properties, is further added.

In order to solve the above problems, the present inventors have intensively studied to arrive at the present invention. That is, the present invention is as follows.
1. An outer-layer fabric comprising 50% by weight or more of non-heat-meltable fibers and having a carbonization length of 15 cm or less according to the vertical method of JIS L1091 (1999), and a fabric, knitted fabric or knitted fabric having an absolutely dry mass of 50 to 150 g / m ² A protective clothing material comprising a laminate of an inner layer fabric having a mass of 250 to 400 g / m ^{2 including} an activated carbon fiber sheet in the form of a nonwoven fabric and having a thermal protection of 45 ° C./15 seconds or less.
2. 2. The protective clothing material according to 1 above, wherein the outer layer fabric is a woven fabric containing 50 to 99% by weight of cotton.
3. Protective clothing using the protective clothing material according to 1 or 2 above

In the protective clothing material composed of the outer layer fabric and the inner layer fabric, a material having a short melting and carbonization length is used for the outer layer fabric, and a material having a predetermined mass or more including a woven or knitted fabric or a nonwoven fabric composed of activated carbon fiber is used for the inner layer fabric, It is possible to obtain a protective clothing material that has both high thermal protection and protection against toxic chemicals.
In the present invention, the outer layer fabric has a function of preventing the spread of fire even in contact with a flame, and the inner layer fabric has a function of shielding heat. In the heat shielding of the inner layer fabric, the mass is effective, and the active carbon fiber woven or knitted fabric or non-woven fabric has an infusibility, a heat insulating property, and a high moisture content, and thus exhibits an effect.

  Hereinafter, the present invention will be described in detail.

  The protective clothing material of the present invention comprises a laminate of an outer layer fabric and an inner layer fabric. The outer layer fabric is made of a woven fabric containing 50% by weight or more of non-heat-meltable fibers and having a carbonization length of 15 cm or less according to the vertical method of JIS L1091 (1999). Non-heat-meltable fibers include flame retardant synthetic fibers such as aramid fibers, polyphenylene sulfide, polyimide, polybenzimidazole and polybenzoxazole, cellulosic fibers and animal fibers subjected to flame retardant treatment. Here, the cellulosic fibers include natural celluloses such as cotton, hemp, jute, flax, kenaf, and cocoon, and regenerated cellulose fibers such as viscose rayon, copper ammonia rayon, polynosic, lyocell, and melt spinning type. Animal hair refers to animal (natural keratinous) fibers obtained from wool, goats, alpaca, rabbits, camels, minks, seals, etc.

  In the case of cellulosic fibers, it is necessary to perform a flame retardant treatment. Flame retardant processing includes a method of applying a flame retardant such as ammonium phosphate, ammonium sulfamate, ammonium alkyl phosphate, inorganic brominated compound, borax, boric acid and the like. Of these, inorganic phosphate, polyphosphate, polyphosphate amide, polyphosphate carbamate, N phosphate nitrile chloride, organic phosphate ester, thiophosphate ester, phosphite type, phosphate type are preferable as flame retardant processing agents. Phosphorus flame retardant compounds such as phosphine type (phosphonium salt), phosphine oxide type, phosphoric acid amide type, and organic condensate. Exemplary flame retarding agent THPC (Tetrakis Hydroxy Methyl Phosphonium Chloride), THPS (Tetrakis Hydroxy Methyl Phosphonium Sulfite), THPOH (Tetrakis Hydroxy Methyl Phosphonium Hydroxide), Dialkyl Phoshon-Carbonic Acid Amid N-Metylol, N-Metylol Dimethyl There is Phosphopropionamide, which forms a methylol group during the reaction and reacts with the hydroxyl group (—OH) of the cellulosic fiber to impart high washing durability and the like.

  In the case of animal fiber, it is a weak flame retardant fiber, but it does not reach self-extinguishing properties. Therefore, it is preferable to apply flame retardant treatment in the same way as cellulosic fibers, and titanium or zirconium salts are chemically treated. Zaporo processing to be bonded to is a typical processing method.

  The above non-heat-melting fibers, that is, flame-retardant synthetic fibers and flame-retardant processed cellulose fibers and animal hair fibers may be used alone, but may be mixed with other fibers by blending, knitting or knitting. Is possible. In the case of mixing, these non-thermomelt fibers need to be contained in an amount of 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. When the mixing ratio is less than 50% by weight, the dough melts and a hole is formed, or self-extinguishing takes time, and the wearer's body may be burned.

  The outer layer fabric is preferably a woven fabric in order to suppress the penetration of toxic chemicals and to prevent the heat and flame radiant heat as much as possible. The woven structure is not particularly limited, and plain woven fabric, oblique woven fabric, satin weaving fabric And is woven using a known loom such as an air jet room, a water jet room, a rapier room, or a projector room.

The mass of the woven fabric used for the outer layer fabric of the present invention is preferably 100 g / m ² or more and 280 g / m ² or less, more preferably 120 g / m ² or more and 200 g / m ² or less. When the mass exceeds 280 g / m ² , the texture becomes hard and bending wear decreases, and the weight of the protective clothing increases and the physiological burden on the wearer increases. On the other hand, if the mass is less than 100 g / m ² , the flat wear resistance and the bending wear resistance are lowered, and sufficient flame retardancy and thermal protection cannot be obtained. It is also possible to make a ripstop fabric in which thick yarns are woven at regular intervals in order to increase the strength.

  In order for the protective clothing material of the present invention to have excellent thermal protection properties, the outer layer fabric has a combustion length (carbonization length) according to “Vertical Flammability Test Method—Vertical Burner Method” described in JIS L1091 (1999) Annex 8. ) Must be 15 cm or less. It is said that when the carbonized length is 25 cm or more in a textile product, it is considered to be flammable, more than 15 cm and less than 25 cm, and less than 15 cm to have flame retardancy. Is shown.

  The outer layer fabric of the present invention is flexible processing, shape stabilization processing, waterproof processing, water repellency oil processing, antistatic processing, antibacterial / deodorant processing, mite processing, water absorption / sweat absorption processing, antifouling processing, Functional processing such as visible light camouflage processing, near-infrared camouflage processing, and far-infrared shielding processing can be performed. In order to prevent the liquid toxic chemical substance from adhering to the surface of the outer layer fabric and penetrating into the interior, it is preferable to apply water repellency.

  The inner layer fabric of the present invention is a fiber material containing a woven or knitted fabric or nonwoven fabric of activated carbon fibers (hereinafter referred to as “activated carbon fiber sheet”), and the woven or knitted fabric or nonwoven fabric of activated carbon fibers may be used alone. Is provided with a protective layer on one side, more preferably on both sides.

  The protective clothing material of the present invention is a laminate in which an inner layer fabric and an outer layer fabric are overlapped and the thermal protection by the measurement method shown in the examples is 45 ° C./15 seconds or less. Since the cellular tissue of the human body is caused to coagulate by heat at about 65 ° C., it must be kept at 65 ° C. or lower on the body surface inside the protective clothing. In measuring the thermal protection, when the ambient temperature is 20 ± 2 ° C., the temperature rise after exposure to the flame needs to be 45 ° C. or less. In addition, when the user is exposed to a flame during an actual activity work, it is possible to take measures such as evacuation or extinguishing within a predetermined time. If it is 45 degrees C or less, damage can be suppressed to the minimum.

  The activated carbon fiber used in the present invention is obtained by subjecting the precursor fiber to carbonization / activation heat treatment. Examples of the precursor fiber include viscose rayon, copper ammonia rayon, polynosic, lyocell, and melt spinning type. Examples include regenerated cellulose fiber, acrylonitrile fiber, phenol fiber, pitch fiber, polyvinyl alcohol fiber, and lignin fiber. Of these materials, viscose rayon and polynosic regenerated cellulosic fibers, phenolic fibers or acrylonitrile fibers are preferred as materials for protective clothing. Is more preferable.

  After forming the above-mentioned precursor fibers into a knitted or non-woven fabric, carbonizing at 300 to 800 ° C. in an inert gas atmosphere, and then activating in an atmosphere containing an active gas at 600 to 1100 ° C., an activated carbon fiber sheet is obtained. can get. Carbonization and activation may be processed batchwise or continuously.

The present invention relates to a protective clothing material for protecting the body from toxic chemicals, wherein the toxic chemicals are adsorbed and filtered by activated carbon fibers to prevent penetration into the protective clothing. Therefore, the characteristics of obtaining the adsorption performance of activated carbon fiber in the present invention, preferably the specific surface area by the BET method is 1000 to 2000 ² / g, more preferably 1300~1700m ² / g. Moreover, as an adsorption | suction characteristic with respect to an organic solvent, it is an activated carbon fiber sheet whose equilibrium adsorption amount in the toluene adsorption performance as described in JIS K1477 (2008) is 30% or more.

In the present invention, the activated carbon fiber sheet has a function of adsorbing and filtering the above-mentioned toxic chemical substances and also serves as a shield against heat and flame. That is, most of the activated carbon fiber sheet is made of carbonaceous material, so that it does not melt and does not open even when exposed to high temperatures, and becomes a heat insulating layer because the moisture content in the standard state is high. In order to satisfy these two roles, the dry mass of the activated carbon fiber sheet is preferably 50 to 150 g / m ² , and the moisture content in the standard state is preferably 15% or more.

  The activated carbon fiber sheet may be used alone as the inner layer fabric, but the activated carbon fiber is brittle and may be worn by friction or compression when used as clothes. In order to prevent this, it is preferable to arrange a protective layer on one side or both sides of the activated carbon fiber sheet. As the protective layer, a woven or knitted fabric and a nonwoven fabric that are flexible and breathable are suitable, and can be bonded to both the front and back surfaces of the activated carbon fiber sheet.

The inner layer fabric preferably has a configuration in which a protective layer is disposed on one or both sides of an activated carbon fiber sheet. The mass of the inner layer fabric is 250 to 400 g / m ² . If the mass is less than 250 g / m ² , heat / flame shielding is insufficient, so that heat protection cannot be obtained, and if the mass exceeds 400 g / m ² , it is bulky and fit when used as clothes. It is inferior and hinders work activities.

The inner layer fabric is a laminate of an activated carbon fiber sheet and a protective layer, and the method of laminating is known, such as a quilting method for sewing with sewing thread, a laminating method using an aqueous binder, or a laminating method using a thermoplastic adhesive sheet. However, it is necessary to avoid an adhesive medium containing an organic solvent that interferes with the adsorption ability of the activated carbon fiber sheet.

Protective clothing made using an outer layer fabric and an inner layer fabric is included in the present invention. That is, an outer layer fabric made of a woven fabric containing 50% by weight or more of non-heat-meltable fibers and having a carbonization length of 15 cm or less according to the vertical method of JIS L1091 (1999), and a woven or knitted fabric having an absolutely dry mass of 50 to 150 g / m ² Alternatively, a protective clothing material having a thermal protection property of 45 ° C./15 seconds or less, comprising a laminate with an inner layer fabric having a mass of 250 to 400 g / m ^{2 including} an activated carbon fiber sheet in the form of a nonwoven fabric, is used. It was a protective suit. Here, the outer layer fabric and the inner layer fabric may be joined by a quilting method or a laminating method, but may be sewn into the shape of a garment simply by overlapping without joining.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not restrict | limited by these Examples. The evaluation methods described in the examples are based on the methods described below.

<Thermal protection test>
Based on the test apparatus of ASTM D4108-1987, it measured by the following method. From the bottom, the outer layer cloth and the inner layer cloth, which are test specimens, are sequentially stacked and attached to the gripper, and the sample is placed so as to be 5 cm above the mouth of the propane gas burner. At this time, the outer layer fabric is on the burner side, and the inner layer fabric on the body side when the protective clothing is produced is on the upper side. A thermocouple thermometer is installed 1 cm above the sample and the temperature (A) before flame contact is measured. Remove the burner, send propane gas to ignite the flame, and adjust the flame length to 4 cm. After the flame has stabilized, the burner is quickly moved under the sample, and the thermocouple thermometer display temperature (B) after 15 seconds is measured. The thermal protection according to the present invention is according to the following equation. The thermal protection test was performed in an atmosphere of 20 ± 2 ° C.
Thermal protection (° C) = B (° C)-A (° C)

<Toluene equilibrium adsorption amount>
Of the toluene adsorption performance described in JIS K1477 (2007), it depends on the equilibrium adsorption amount.

<BET specific surface area>
About 30 mg of a sample was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, and measured using a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics). The adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) was measured in the range of relative pressure of 0.02 to 0.95, and the adsorption isotherm of the sample was created. Based on the results in the relative pressure range of 0.02 to 0.15, the BET specific surface area (unit: m ² / g) per weight was determined by the BET method.

<Mass>
The mass was measured by the A method out of the mass per unit area in the standard state described in JIS L1096 (2010).

<Absolute mass>
The absolute dry mass was determined by measuring the mass per unit area after the sample was heated in a constant temperature dryer at 115 ± 5 ° C. for about 3 hours, then sealed and cooled to room temperature in a desiccator.

<Carbonation length>
The carbonization length was measured by “Vertical Flammability Test Method—Vertical Burner Method” described in JIS L1091 (1999) Annex 8.

[Outer layer fabric 1]
A 40th blend yarn was prepared from nylon 66 filament yarn and cotton at a blending ratio of 5/95 by an electric opening method. Subsequently, weaving was performed by an ordinary method using an air jet loom to prepare a 2/1 twill fabric having a warp density of 140 yarns / 2.54 cm and a weft yarn density of 108 yarns / 2.54 cm. Subsequently, hair sinter, paste removal, scouring, bleaching, mercerization, dyeing, and soaping were performed by conventional methods. Further, this dyed fabric was dipped in an aqueous solution containing 40% Pyrobatex CP containing 0.5% N-methyloldimethylphosphonopropionic acid amide and 0.5% ammonium chloride, squeezed so that the pickup became 65%, and dried. -An outer layer fabric 1 was obtained by heat treatment. The mass of the outer layer fabric 1 was 175 g / m ² .

[Outer fabric 2]
Cotton 40-th spun yarn was woven by an air jet loom by a conventional method to prepare a 2/1 twill fabric having a warp yarn density of 90 / 2.54 cm and a weft yarn density of 80 / 2.54 cm. Further, the outer layer cloth 2 was obtained by subjecting to the same under-bleaching, dyeing and processing as the outer layer cloth 1. The mass of the outer layer fabric 2 was 121 g / m ² .

[Outer fabric 3]
A 40th blend yarn was prepared from nylon 66 filament yarn and cotton at a blending ratio of 5/95 by an electric opening method. Subsequently, weaving was performed by an ordinary method using an air jet loom to prepare a 2/1 twill fabric having a warp density of 140 yarns / 2.54 cm and a weft yarn density of 108 yarns / 2.54 cm. Subsequently, hair sinter, paste removal, scouring, bleaching, mercerization, dyeing, and soaping were performed by a conventional method to obtain an outer layer fabric 3. The mass of the outer layer fabric 3 was 160 g / m ² .

[Activated carbon fiber sheet 1]
A 20th spun yarn was obtained using a phenol fiber (Kinol) staple having a single yarn fineness of 2.2 dtex. The spun yarn was knitted into a milled knitted fabric having a mass of 190 g / m ² using a 22 gauge double-sided circular knitting machine.
This knitted fabric was carbonized from normal temperature to 890 ° C. for 30 minutes in an inert gas using a firing furnace, and then activated at a temperature of 890 ° C. for 90 minutes in an active gas containing 12 wt% of water vapor. The activated carbon fiber knitted fabric obtained had an absolutely dry mass of 110 g / m ² and a mass of 150 g / m ² . This activated carbon fiber knitted fabric had a toluene adsorption amount of 48% and a BET specific surface area of 1390 m ² / g and had very high adsorption performance.

[Activated carbon fiber sheet 2]
A plain fabric with a basis weight of 135 g / m ² was prepared using the spun yarn of the phenolic fiber used for the production of the activated carbon fiber sheet 1, and the carbonization and activation treatment was similarly performed to prepare an activated carbon fiber fabric. The obtained activated carbon fiber fabric had an absolutely dry mass of 81 g / m ² and a mass of 111 g / m ² . The activated carbon fiber knitted fabric had a toluene adsorption amount of 50% and a BET specific surface area of 1400 m ² / g.

[Activated carbon fiber sheet 3]
A plain woven fabric having a basis weight of 85 g / m ² was prepared using the spun yarn of the phenolic fiber used for the production of the activated carbon fiber sheet 1, and the activated carbon fiber woven fabric was prepared by performing carbonization / activation treatment in the same manner. The obtained activated carbon fiber fabric had an absolutely dry mass of 50 g / m ² and a mass of 70 g / m ² . The activated carbon fiber knitted fabric had a toluene adsorption amount of 50% and a BET specific surface area of 1400 m ² / g.

[Protective layer 1]
After knitting warp knitted fabric with a 22 gauge 6 sheet double rasile machine using 84 dtex-24fil nylon 66 filament yarn as ground yarn and 176 dtex nylon 66 monofilament yarn as pile yarn, scouring and dyeing by regular method did. This knitted fabric was cut in half, and then placed on a cut pile, and then the tip of the pile was melted hot to form a spherical product. The knitted fabric thus obtained had a mass of 150 g / m ² .

[Protective layer 2]
20 g / m ² polyester non-woven thermoplastic adhesive between a 30 g / m ² spunbond nonwoven and a 40 g / m ² spunlace nonwoven (Kinha Tech Dynac (registered trademark), melting point 115 ° C.) And a protective layer 2 was obtained by laminating with a heating roller. The mass of the obtained nonwoven fabric laminate was 89 g / m ² .

[Protective layer 3]
A warp knitted fabric was formed by a tricot knitting machine using a polyester filament yarn of 83 dtex-36 fil as a front yarn and a polyester monofilament yarn of 22 dtex as a back yarn, and scoured and dyed by a conventional method to obtain a protective layer 3 . The mass of the obtained tricot knitted fabric was 50 g / m ² .

[Inner layer laminating method 1]
Using a polyester filament yarn 50th sewing thread as the upper yarn and a polyester spun yarn 130th sewing yarn as the lower yarn, an activated carbon fiber sheet is sandwiched between the protective layers, and the number of driven yarns / 2.54cm Quilted with diamond pattern.

[Inner layer lamination method 2]
A polyamide-based nonwoven fabric thermoplastic adhesive having a mass of 10 g / m ² (Dyac (registered trademark) manufactured by Kureha Tech, melting point: 115 ° C.) having a mass of 10 g / m ² was laminated between the protective layer and the activated carbon fiber sheet by a heating roller.

Example 1
The protective layer 1 / activated carbon fiber sheet 1 / protective layer 3 were laminated in this order and laminated by the inner layer cloth laminating method 1. The mass at that time is shown in Table 1. Table 1 also shows the thermal protection when the outer fabric 1 is placed on the protective layer 1 side and stacked. This protective clothing material has excellent thermal protection.

(Example 2)
The protective layer 2 / activated carbon fiber sheet 2 / protective layer 3 were laminated in this order and laminated by the inner layer fabric lamination method 2. The mass at that time is shown in Table 1. Table 1 also shows the thermal protection when the outer fabric 2 is arranged on the protective layer 2 side and stacked. This protective clothing material has excellent thermal protection.

Example 3
Protective layer 1 / activated carbon fiber sheet 3 / protective layer 3 were laminated in this order and laminated according to inner layer fabric laminating method 1. The mass at that time is shown in Table 1. Table 1 also shows the thermal protection when the outer fabric 1 is placed on the protective layer 1 side and stacked. This protective clothing material has excellent thermal protection.

(Comparative Example 1)
Protective layer 2 / activated carbon fiber sheet 3 / protective layer 3 were laminated in this order and laminated according to inner layer fabric lamination method 2. The mass at that time is shown in Table 1. Table 1 also shows the thermal protection when the outer fabric 2 is arranged on the protective layer 2 side and stacked. This protective clothing material is inferior in thermal protection.

(Comparative Example 2)
Protective layer 3 / activated carbon fiber sheet 2 / protective layer 3 were laminated in this order and laminated by inner layer fabric lamination method 2. The mass at that time is shown in Table 1. Table 1 also shows the thermal protective properties when the outer layer fabrics 2 are stacked. This protective clothing material is inferior in thermal protection.

(Comparative Example 3)
The protective layer 1 / activated carbon fiber sheet 1 / protective layer 3 were laminated in this order and laminated by the inner layer cloth laminating method 1. The mass at that time is shown in Table 1. Table 1 also shows the thermal protection when the outer fabric 3 is arranged on the protective layer 1 side and stacked. This protective clothing material is inferior in thermal protection.

The protective clothing material and protective clothing of the present invention are a protective clothing material and protective clothing that protects the body from gaseous and liquid toxic chemicals. It is intended to provide a protective clothing material and protective clothing to which a function of superiority is further added, and contributes greatly to the industrial world.

Claims (3)

An outer-layer fabric comprising 50% by weight or more of non-heat-meltable fibers and having a carbonization length of 15 cm or less according to the vertical method of JIS L1091 (1999), and a fabric, knitted fabric or knitted fabric having an absolutely dry mass of 50 to 150 g / m ² A protective clothing material comprising a laminate of an inner carbon cloth having a mass of 250 to 400 g / m ^{2 including} an activated carbon fiber sheet in the form of a nonwoven fabric, and having a thermal protection of 45 ° C./15 seconds or less.   The protective clothing material according to claim 1, wherein the outer layer fabric is a woven fabric containing 50 to 99% by weight of cotton.   Protective clothing using the protective clothing material according to claim 1.