JP2012192623A - Absorption sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an absorption sheet that has percolation control power to the gassy harmful substance and the liquid harmful substance, has superior peel strength and durability of a gas adsorbing layer (gas adsorbent such as activated carbon sheet)and is extremely suitable to be used for a protection material such as protective clothing in which both sides of the gas adsorbing layer are laminated with protective layers.SOLUTION: In the absorption sheet, both sides of the gas adsorbing layer 4 are laminated with protective layers 3 and 5 that are carried out quilting processing with quilting thread 6, and further the surface of either of protective layer is laminated with the cloth 1 that comprises the thermoplastic fibers by a partial adhesion layer 2 of the solventless system adhesive.

Description

  The present invention can effectively protect gaseous harmful substances and liquid harmful substances that are absorbed from the skin, such as organic phosphorus compounds, and adversely affect the human body, and can improve the peel strength and durability of the gas adsorption layer (gas adsorption material). It relates to an improved adsorption sheet. The adsorbing sheet of the present invention is particularly suitably used for protective materials such as shelters, clothes, gloves, socks, shoes, helmets, and covers.

  Various adsorbing sheets that protect the human body from harmful substances have been proposed. For example, an activated carbon sheet is proposed in which the activated carbon sheet is sandwiched or wrapped by a woven fabric or a nonwoven fabric in order to prevent the activated carbon sheet from falling off or scattered, but the lamination method has not been sufficiently studied, Adhesion sheets that have excellent peel strength and durability of the gas adsorbing layer (gas adsorbing material) while maintaining permeation suppressing ability against gaseous harmful substances and liquid harmful substances have not been sufficiently studied.

  For example, in Patent Document 1, an adsorption layer is inserted between two carrier layers, and adhesion between the adsorption layer and the carrier layer is achieved by intermittently applying an adhesive in the form of adhesive dots that do not adhere to each other. Adsorption filter materials have been proposed. This adsorbing filter material has an excellent protection function against biological and chemical harmful substances and poisonous substances, but is inferior in flexibility, breathability, and peel strength, and has a problem in wearing feeling when used in protective clothing.

  In Patent Document 2, a protective layer is laminated on both surfaces of a fibrous activated carbon sheet, and after quilting, it is immersed in a water-dispersed binder resin processing bath, and dried and fixed. There has been proposed an adsorbent sheet that prevents activated carbon dust from falling off or scattering from fiber breakage or powdering due to mechanical force applied to the fibrous activated carbon sheet. Although this adsorbing sheet is excellent in flexibility and air permeability, there is a problem that the permeation suppression ability of the liquid harmful substance is weak due to a through hole formed by a sewing needle by quilting.

  In Patent Document 3, a protective layer is laminated on one surface of the gas adsorption layer, and after quilting, the protective layer is laminated by partial adhesion in which a solvent-free adhesive is applied to the other surface of the gas adsorption layer. Adsorption sheets with laminated layers have been proposed. Although this adsorbing sheet is excellent in flexibility and air permeability, there is a possibility that the protective layer and the gas adsorbing layer (gas adsorbing material) are peeled off and the gas adsorbing layer is damaged.

JP-A-2005-324025 JP 2003-10679 A Japanese Patent Application No. 2009-189649

  The present invention was devised in view of the problems of the prior art, and its purpose is to have a permeation suppressing ability for gaseous harmful substances and liquid harmful substances, and to have a peel strength and a gas adsorbing layer (gas adsorbing material). It is to provide an adsorbing sheet in which protective layers are laminated on both sides of a gas adsorbing layer, which is excellent in durability.

  As a result of earnestly examining the method of laminating the protective layers on both sides of the gas adsorption layer in order to achieve the above object, the present inventor has laminated the protective layers on both sides of the gas adsorption layer by quilting, and any one of the protective layers. Adhering and laminating a fabric made of thermoplastic fibers with a solvent-free adhesive on the surface of the surface, effective protection from gaseous harmful substances and liquid harmful substances, excellent peel strength and durability of the gas adsorption layer The present invention has been found, and the present invention has been completed.

That is, the present invention has the following configurations (1) to (5).
(1) A protective layer is laminated on both sides of the gas adsorption layer by quilting, and a fabric made of thermoplastic fiber is adhered to the surface of any of the protective layers with a solventless adhesive and laminated. Adsorption sheet.
(2) Adhesion sheet according to (1), wherein the adhesion by the solventless adhesive is partial adhesion, and the mass of the solventless adhesive is from 5 g / m ^{2 to} 50 g / m ² .
(3) The gas adsorbing layer has any form of a woven fabric, a knitted fabric, a nonwoven fabric, or a felt, and the solventless adhesive is a urethane adhesive or a silicone adhesive (1) or The adsorption sheet according to (2).
(4) A protective material using the adsorption sheet according to any one of (1) to (3).
(5) The protective material according to (4), wherein the protective material is protective clothing.

  In the adsorbing sheet of the present invention, a protective layer is laminated on both sides of the gas adsorbing layer by quilting, and a fabric made of thermoplastic fibers is adhered to the surface of any protective layer with a solventless adhesive. Therefore, it has a permeation suppressing ability not only for gaseous harmful substances but also for liquid harmful substances, and has excellent peel strength and excellent durability of the gas adsorption layer (activated carbon sheet). Therefore, it is extremely suitable for use in protective materials such as protective clothing.

It is the schematic of the cross-section of the adsorption sheet of this invention. It is the schematic which showed the gas-penetration resistance test method. It is the schematic which showed the liquid-penetration resistance test method.

Hereinafter, the suction sheet of the present invention will be described in detail.
As the adsorption sheet in the present invention, as shown in FIG. 1, a protective layer 3 and a protective layer 5 are laminated on each side of a gas adsorption layer 4 with a quilting thread 6, and either the protective layer 3 or the protective layer 5 is laminated. A fabric 1 made of thermoplastic fibers is laminated on a surface (the surface of the protective layer 3 in FIG. 1) via a partial adhesive layer 2 made of a solventless adhesive.

  The gas adsorbing layer used in the adsorbing sheet of the present invention includes a carbon adsorbing material such as activated carbon and carbon black, or a gas adsorbing material comprising an inorganic adsorbing material such as silica gel, zeolite adsorbing material, silicon carbide, activated alumina, etc. However, it can be appropriately selected depending on the target adsorbed substance. Among them, activated carbon that can deal with a wide range of gases is preferable, and fibrous activated carbon that has an adsorptivity with respect to gaseous harmful substances that have a large adsorption rate and adsorption capacity and are effective when used in a small amount is more preferable.

  The gas of the substance to be adsorbed includes a gaseous compound having one or more carbon elements. For example, the gaseous compound includes a gaseous harmful substance having a relatively large molecular weight of 50 or more and capable of being adsorbed by a gas adsorption layer such as activated carbon. Specific examples include organic phosphorus compounds used for agricultural chemicals, insecticides and herbicides, and general organic solvents such as toluene, methylene chloride and chloroform used for painting work and the like.

When fibrous activated carbon is used for the gas adsorption layer, the BET specific surface area is preferably 700 m ² / g or more and 3000 m ² / g or less, and more preferably 1000 m ² / g or more and 2500 m ² / g or less. If the BET specific surface area is less than the above range, a large amount of activated carbon is required to obtain sufficient protection, the material becomes heavy, and there is a concern that the flexibility is inferior. On the other hand, if the above range is exceeded, a problem of desorbing the adsorbed gaseous harmful substance may occur.

The mass of the fibrous activated carbon is preferably 10 g / m ² or more and 300 g / m ² or less, more preferably 20 g / m ² or more and 200 g / m ² or less. When the mass is less than the above range, the capacity that can be adsorbed is reduced, and the use time is limited. On the other hand, when the above range is exceeded, there is a concern that the flexibility of the sheet material is inferior.

  As raw materials for fibrous activated carbon, in addition to natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as rayon, polynosic and solvent spinning methods, polyvinyl alcohol fibers, acrylic fibers, aromatic polyamide fibers, lignin fibers, phenols Synthetic fibers such as system fibers and petroleum pitch fibers can be mentioned, but regenerated cellulose fibers, phenol fibers, and acrylic fibers are preferred from the physical properties (strength etc.) and adsorption performance of the obtained fibrous activated carbon. Fibrous activated carbon can be produced by a conventionally known method. For example, a fabric that has been woven, knitted, or non-woven using short fibers or long fibers of these raw material fibers can be appropriately flame-resistant as necessary. After containing an agent, it can be produced by applying a flameproofing treatment at a temperature of 450 ° C. or lower, and then carbonizing at a temperature of 500 ° C. or higher and 1000 ° C. or lower.

  As a method for forming the gas adsorption layer, a conventionally known method can be employed. For example, a method of adhering a gas adsorbent to a sheet base material with a binder, or a gas adsorbent made into a slurry including an appropriate pulp and binder. A method of making paper by a wet paper machine, or a method of carbonizing and activating the raw material fibers of the gas adsorbent material in advance by weaving, knitting, or non-woven fabric, and flame-resistant treatment as necessary can be employed.

  The gas adsorbing layer preferably has any form of woven fabric, knitted fabric, non-woven fabric, or felt. Among these, the form of the woven fabric or the knitted fabric is preferable from the viewpoints of air permeability, ease of lamination, flexibility, and the like.

  Examples of the protective layer used in the adsorption sheet of the present invention include a woven fabric, a knitted fabric, a nonwoven fabric, a porous film, an apertured film, a membrane material, or a composite material thereof, and may be appropriately selected depending on the purpose of use. it can. The purpose of the protective layer is to protect the adsorbing sheet from mechanical force applied from the outside, to supplement the mechanical strength of the adsorbing sheet, to ensure adsorbability to liquid harmful substances, and the like.

  The fabric made of thermoplastic fibers used in the adsorption sheet of the present invention preferably has any form of a woven fabric, a knitted fabric, and a nonwoven fabric.

  As thermoplastic fibers, polyethylene, polypropylene, polystyrene, acrylotolyl / butanediene / styrene resin, polyvinyl chloride, acrylonitrile / styrene resin, methacrylic resin, vinyl chloride, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, GF reinforced Examples include polyethylene terephthalate, ultrahigh molecular weight polyethylene, polyphenylene sulfite, polyimide, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyetheretherketone, liquid crystal polymer, and polytetrafluoroethylene. It can be selected as appropriate and is not particularly limited.

The mass of the fabric made of thermoplastic fibers is preferably 5 g / m ² or more and 100 g / m ² or less. More preferably, the 10 g / ^{m 2} or more 50 g / ^{m 2} or less. If the mass is less than the above range, a problem of reduction in mechanical strength (tensile strength) occurs. On the other hand, if the mass exceeds the above range, flexibility (comfort) is reduced.

  The thickness of the fabric made of thermoplastic fibers is preferably 1.0 mm or less, and more preferably 0.8 mm or less. If the thickness exceeds 1.0 mm, the laminate becomes stiff and the workability of the suction sheet is deteriorated. The lower limit of the thickness is not particularly defined, but is actually 0.5 mm.

  The adsorbing sheet of the present invention has protective layers on both sides of the gas adsorbing layer, and they are integrated and laminated by quilting, and a cloth made of thermoplastic fibers is bonded to any of the protective layers without solvent. It is characterized by being laminated by bonding with an agent. If the protective layer is bonded to the gas adsorption layer with an adhesive, the gas adsorbent in the gas adsorption layer may be clogged with pores, and the protective layer and the gas adsorption layer may be peeled off during use. There is a risk that the gas adsorption performance will be degraded. On the other hand, if the protective layers are merely laminated on both sides of the gas adsorption layer by quilting, there is a possibility that liquid material may permeate through the through holes of the sewing needle. The adsorbing sheet of the present invention has an improved peel strength and a gas adsorbing layer (not only a gaseous harmful substance but also a liquid harmful substance by the method for laminating the protective layer and the fabric as described above, while suppressing permeation. The durability of the gas adsorbent) can be achieved.

  The adsorbing sheet of the present invention includes, for example, a gas adsorbing layer and two protective layers integrated by quilting and laminating protective layers on both sides of the gas adsorbing layer, and then preliminarily existing on the protective layer side of the gas adsorbing layer. It is created by partially applying a solvent adhesive, laminating a fabric made of thermoplastic fibers on the adhesive surface, laminating the laminate with a roll, and then curing the adhesive.

  As the quilting process, a conventionally known method can be adopted, and a sewing thread such as polyester, nylon, cotton or the like is preferably used. In consideration of protection against liquid harmful substances, it is particularly preferable to use an oil-repellent sewing thread.

  The solventless adhesive is not particularly limited, but a urethane-based or silicone-based hot-melt type insoluble adhesive is preferable in terms of flexibility, peel strength after bonding, air permeability, and adsorptivity.

  The method of partial adhesion is not particularly limited, but in consideration of flexibility, air permeability, etc., the adhesive is uniformly applied to a non-whole dot, lattice, spiral, or rod shape by a gravure method or a screen method. The method of adhering is preferable. The adhesive can be applied to either the protective layer surface or the gas adsorption layer surface, but it is preferable to apply the adhesive to the protective layer surface in consideration of gas adsorption performance.

The application amount of the adhesive is preferably 5 g / m ² or more and 50 g / m ² or less. Still more preferably 10 g / ^{m 2} or more 40 g / ^{m 2} or less. If the coating amount is less than the above range, there will be a problem of a decrease in adhesive strength. On the other hand, if it exceeds the above range, flexibility and air permeability will be reduced.

  The ratio of the adhesion area at the time of partial adhesion (the ratio of the adhesive application area to the area of the protective layer) is preferably 5% or more and 50% or less, more preferably 10% or more and 40% or less. If the ratio is less than the above range, there is a problem that the adhesive strength is lowered. On the other hand, if the ratio is more than the above range, the amount of adhesive applied becomes large, partial adhesion hardly occurs, and flexibility and breathability are reduced. A problem that degrades occurs.

  In the case of partial adhesion by the gravure method or the screen method, the gravure roll or screen to be used can be appropriately selected according to the adhesion area and the adhesive application amount. In the case of the gravure method, these can be arbitrarily set by the number of gravure lines, and in the case of the screen method, these can be arbitrarily set by the thickness of the mesh and the aperture ratio.

  In the adsorption sheet of the present invention, the peel strength at the adhesion interface through the adhesive between the protective layer and the fabric made of thermoplastic fibers is both the length direction (vertical direction) and the width direction (width direction) of the material. Is preferably 5.0 N or more, more preferably 6.0 N or more, and particularly preferably 10.0 N or more. If the peel strength is low, the fabric composed of the protective layer and the thermoplastic fiber is peeled off, which causes a problem that the protection by the fabric does not function. The upper limit of the peel strength is not particularly defined, but is practically about 50.0N.

As mass of the laminated body which consists of a gas adsorption layer and two protective layers, 500 g / m < ² > or less is preferable, More preferably, it is 450 g / m < ² > or less. When the mass of a laminated body exceeds 500 g / m < ² >, mass will become large and it will become easy to become a material lacking in a softness | flexibility. The lower limit of the mass is not particularly defined, but is practically about 30 g / m ² .

  As thickness of the laminated body which consists of a gas adsorption layer and two protective layers, 5.0 mm or less is preferable, More preferably, it is 4.0 mm or less. When the thickness exceeds 5.0 mm, the laminate becomes stiff and the workability of the suction sheet is deteriorated. The lower limit of the thickness is not particularly defined, but is practically about 1.5 mm.

  The stiffness of the laminate composed of the gas adsorption layer and the two protective layers is preferably 0.05 N · cm or less in both the length direction (vertical direction) and the width direction (width direction) of the material, More preferably, it is 0.03 N · cm or less. If the bending resistance exceeds the above range, the material becomes stiff and it becomes difficult to process as an adsorption sheet. The lower limit of the bending resistance is not particularly defined, but is practically about 0.005 N · cm.

The air permeability of the laminate composed of the gas adsorption layer and the two protective layers is preferably 50 cm ³ / cm ² · s to 300 cm ³ / cm ² · s, and more preferably 100 cm ³ / cm ² · s. Above 250 cm ³ / cm ² · s. If the air permeability is less than the above range, the air permeability is inferior, and if the air permeability exceeds the above range, the material becomes insufficiently bonded, which may cause a problem of peeling.

The toluene adsorption performance (toluene gas equilibrium adsorption amount) of the laminate composed of the gas adsorption layer and the two protective layers is preferably 20 g / m ² or more. More preferably, it is 25 g / m ² or more. When the toluene adsorption performance is less than the above range, the adsorptivity is poor and the protection against gas is poor. The upper limit of the toluene adsorption performance is not particularly defined, but is practically about 200 g / m ² .

  As for the number of gas adsorbing layers and protective layers laminated on them, at least one layer is required on each side of the gas adsorbing layers, but for the purpose of significantly improving the mechanical strength or when there are multiple target gases. It is effective to use the gas adsorbing layer and the protective layer in a superposed manner.

  Furthermore, in order to further improve the protection of the adsorbent sheet against liquid harmful substances, use a material that has been subjected to water / oil repellent treatment in advance on at least one of the layers constituting the adsorbent sheet before lamination processing. It is preferable that the adsorbent sheet after lamination is subjected to water / oil repellent treatment by post-processing. The water / oil repellent finish may be any conventionally known method and is not particularly limited. It is preferable that at least one layer of the material constituting the adsorbing sheet has a water repellent performance grade 2 or higher and an oil repellency performance grade 2 or higher.

  Next, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods described in the examples are as follows.

(1) Gas permeation resistance test: An explanatory diagram of this test is shown in FIG. The test article 10 is sandwiched between two glass cells (upper cell 7 and lower cell 12) having an internal volume of 350 cc, and the periphery is sealed with paraffin 11. From the upper cell 7 of this test container, 20 μL of 3-methoxybutyl acetate is dropped onto the test product 10. This is put in a constant temperature box set at 25 ± 2 ° C., the gas concentration on the lower cell 12 side is sampled from the sampling port 8 after 24 hours, and the gas concentration permeated through the test article 10 is measured by gas chromatography. When the gas concentration was below the detection limit (0.1 ppm), it was indicated by ◯, and when the gas concentration was confirmed to exceed the detection limit, it was indicated by x.

(2) Liquid penetration resistance test: An explanatory diagram of this test is shown in FIG. The filter paper 16 was placed on the glass plate 17, and the test product 15 was further placed thereon, and 20 μL of the test solution 14 (methyl salicylate in which the red dye was dissolved) was dropped. Then, pressurize the weights 13 of the bottom area 1 cm ² under a load 1 kg / cm ^2, to determine the permeability of the liquid by the degree of filter paper coloration after 24 hours. No coloration was indicated by ○, slight coloration was indicated by Δ, and coloration was indicated by ×.

(3) Ratio of application area of adhesive (adhesive area ratio): After applying the adhesive to the protective layer and pasting it once onto the gas adsorption layer, peeling both off and then using an image processor The surface of the fabric was observed. The total area of the areas where the adhesive was applied was divided by the total area of the area where the protective layer and the gas adsorption layer were laminated to obtain the ratio of the area where the adhesive was applied.

(4) Mass: Measured according to JIS-L-10968.3.

(5) Thickness: Measured according to JIS-L-10968.4.

(6) Breathability: Measured according to JIS-L-10968.26.

(7) Specific surface area: A nitrogen adsorption isotherm was determined and calculated by the BET method based on this.

(8) Gas equilibrium adsorption amount: measured in accordance with JIS-K-1477.

(9) Peel strength 1: Based on JIS-L-1089.7.10, the peel strength between the fabric composed of the thermoplastic fibers of the adsorption sheets of Examples 1 to 4 and the protective layer was measured. When it exceeded 10.0 N, the measurement of peeling strength was stopped and it displayed as (circle) as no peeling.

(10) Peel strength 2: Based on JIS-L-1089.7.10, peel strength between the gas adsorption layer and the protective layer of the adsorption sheets of Examples 1 to 4 and Comparative Examples 1 and 2 (Comparative Example 1) About the part which is not quilted stitching was measured. When it exceeded 10.0 N, the measurement of peeling strength was stopped and it displayed as (circle) as no peeling.

(11) Durability of gas adsorption layer: After measuring peel strength 2, visually check the appearance of the peeled surface of the gas adsorption layer, and indicate that the gas adsorption layer is not broken and has excellent durability. Then, the gas adsorbed layer was confirmed to be broken and the durability was inferior.

Production of gas adsorption layer As the gas adsorption layer, fibrous activated carbon in the form of a knitted fabric was produced by the following method. A circular knitted fabric with a single yarn fineness of 2.2 dtex and a 20th novolak phenol resin fiber spun yarn having a mass of 220 g / m ² is heated in an inert atmosphere at 410 ° C. for 30 minutes, and then in an inert atmosphere at 880 ° C. Was heated for 20 minutes until carbonization proceeded, and then activated for 2 hours at a temperature of 890 ° C. in an atmosphere containing 12% by volume of water vapor. The obtained gas adsorption layer has a mass of 125 g / m ² , a specific surface area of 1400 m ² / g, a thickness of 0.80 mm, and a gas permeability of 200 cm ³ / cm ² · s with a water level gauge of 1.27 cm. The toluene adsorption performance (toluene gas equilibrium adsorption amount) was 53 g / m ² .

Production of protective layer As a protective layer, a tricot knitted fabric was produced by the following method. Using a 28 gauge two-sheet tricot machine, set polyester filaments (82.5 dtex, 36 filaments) on the front cage and polyester filaments (22 dtex, monofilament) on the back cage, respectively. After knitting a warp knitted fabric with a back 1-0 / 2-3 structure, it was refined by a conventional method and further dyed with a disperse dye. The obtained protective layer had a thickness of 0.28 mm, a mass of 80 g / m ² , and a gas permeability of 500 cm ³ / cm ² · s with a pressure difference of 1.27 cm in water level.

Preparation of oil-repellent sewing thread Upper thread is polyester filament sewing thread # 50 (83.3 dtex / 1 × 3), 7.0 wt% fluorine-based water repellent (Asahi Glass Co., Ltd., Asahi Guard AG970), 0.7 wt. % Urethane-based cross-linked resin (Meisei Chemical Industry Co., Ltd., Meikanate WEB) after being immersed in water, dehydrated, dried, fixed at 180 ° C., and 0.35 wt% adhered to the resin solids, A silicon-based oil was prepared by adhering 1.1 wt% by a dipping method. On the other hand, the lower yarn is polyester spun yarn # 130 (80 s / 1 × 2), 7.0 wt% fluorine-based water repellent (Asahi Glass Co., Ltd., Asahi Guard AG970), 0.7 wt% urethane-based cross-linked resin. (Meisei Chemical Industry Co., Ltd., Meikanate WEB) after being immersed in a processing bath, dehydrated, dried, fixed at 180 ° C. and deposited with 0.48 wt% resin solids, and then paraffin wax was immersed by the immersion method. It was prepared by attaching 0.83 wt%.

Example 1
The above protective layers were overlaid on both sides of the gas adsorbing layer, and then quilted and sewn into a diamond pattern at a 2-inch pitch using an oil-repellent sewing thread to obtain a laminate having a three-layer structure. On the other hand, 10 g / m ² of urethane-based reactive hot melt (manufactured by DIC Corporation, Tyforce H-1041) is applied to the protective layer on one side of this laminate by a gravure method so that the adhesive area ratio becomes 7%. Then, the adhesive layer of the protective layer was overlaid on a fabric made of thermoplastic fibers (Toyobo Co., Ltd., Ecule 3201A, polyester long fiber nonwoven fabric, mass 20 g / m ² , thickness 0.15 mm). The material was pressed with a roll. Thereafter, the laminate having a four-layer structure was left in a constant temperature and humidity chamber at 30 ° C. and 65% RH for 24 hours to perform a curing treatment. Further, the laminate was dipped in a processing bath of 3 wt% fluorine-based water repellent (Aseihigaku AG970, Meisei Chemical Industry Co., Ltd.) and dried, and then subjected to fixing treatment at 170 ° C., and the water repellent was used as a binder resin. The solid content was 0.5 wt%. Table 1 shows the gas permeation resistance test result, the liquid permeation resistance test result, the peel strength 1, the peel strength 2 and the evaluation results of the durability of the gas adsorption layer of the obtained adsorption sheet.

(Example 2)
The above protective layers were overlaid on both sides of the gas adsorbing layer, and then quilted and sewn into a diamond pattern at a 2-inch pitch using an oil-repellent sewing thread to obtain a laminate having a three-layer structure. On the other hand, 10 g / m ² of urethane-based reactive hot melt (manufactured by DIC Corporation, Tyforce H-1041) is applied to the protective layer on one side of this laminate by a gravure method so that the adhesive area ratio becomes 7%. Then, the adhesive layer of the protective layer was overlaid on a fabric made of thermoplastic fibers (Toyobo Co., Ltd., Ecule 3401A, polyester long fiber nonwoven fabric, mass 40 g / m ² , thickness 0.24 mm). The material was pressed with a roll. Thereafter, the laminate having a four-layer structure was left in a constant temperature and humidity chamber at 30 ° C. and 65% RH for 24 hours to perform a curing treatment. Further, the laminate was dipped in a processing bath of 3 wt% fluorine-based water repellent (Aseihigaku AG970, Meisei Chemical Industry Co., Ltd.) and dried, and then subjected to fixing treatment at 170 ° C., and the water repellent was used as a binder resin. The solid content was 0.5 wt%. Table 1 shows the gas permeation resistance test result, the liquid permeation resistance test result, the peel strength 1, the peel strength 2 and the evaluation results of the durability of the gas adsorption layer of the obtained adsorption sheet.

(Example 3)
The above protective layers were overlaid on both sides of the gas adsorbing layer, and then quilted and sewn into a diamond pattern at a 2-inch pitch using an oil-repellent sewing thread to obtain a laminate having a three-layer structure. On the other hand, 10 g / m ² of urethane-based reactive hot melt (manufactured by DIC Corporation, Tyforce H-1041) is applied to the protective layer on one side of this laminate by a gravure method so that the adhesive area ratio becomes 7%. Then, the adhesive layer of the protective layer was overlaid on a fabric made of thermoplastic fibers (Toyobo Co., Ltd., Ecule 3701A, polyester long fiber nonwoven fabric, mass 70 g / m ² , thickness 0.31 mm). The material was pressed with a roll. Thereafter, the laminate having a four-layer structure was left in a constant temperature and humidity chamber at 30 ° C. and 65% RH for 24 hours to perform a curing treatment. Further, the laminate was dipped in a processing bath of 3 wt% fluorine-based water repellent (Aseihigaku AG970, Meisei Chemical Industry Co., Ltd.) and dried, and then subjected to fixing treatment at 170 ° C., and the water repellent was used as a binder resin. The solid content was 0.5 wt%. Table 1 shows the gas permeation resistance test result, the liquid permeation resistance test result, the peel strength 1, the peel strength 2 and the evaluation results of the durability of the gas adsorption layer of the obtained adsorption sheet.

Example 4
The above protective layers were overlaid on both sides of the gas adsorbing layer, and then quilted and sewn into a diamond pattern at a 2-inch pitch using an oil-repellent sewing thread to obtain a laminate having a three-layer structure. On the other hand, after applying 10 g / m ² of a silicon-based sealing agent (manufactured by Shin-Etsu Chemical Co., Ltd., KE-45) to the protective layer on one side of this laminate so that the adhesive area ratio is 7% by the gravure method. The adhesive layer of the protective layer is overlaid on a fabric made of thermoplastic fibers (Toyobo Co., Ltd., Ecule 3401A, polyester long fiber nonwoven fabric, mass 40 g / m ² , thickness 0.24 mm), Crimped with a roll. Thereafter, the laminate having a four-layer structure was left in a constant temperature and humidity chamber at 30 ° C. and 65% RH for 24 hours to perform a curing treatment. Further, the laminate was dipped in a processing bath of 3 wt% fluorine-based water repellent (Aseihigaku AG970, Meisei Chemical Industry Co., Ltd.) and dried, and then subjected to fixing treatment at 170 ° C., and the water repellent was used as a binder resin. The solid content was 0.5 wt%. Table 1 shows the gas permeation resistance test result, the liquid permeation resistance test result, the peel strength 2 and the evaluation results of the durability of the gas adsorption layer of the obtained adsorption sheet.

(Comparative Example 1)
The protective layer was overlaid on one surface of the gas adsorption layer, and then quilted and sewn into a diamond pattern at a 2-inch pitch using an oil-repellent sewing thread to obtain a laminate having a two-layer structure. On the other hand, after applying 10 g / m ² of urethane-based reactive hot melt (manufactured by DIC Corporation, Tyforce H-1041) to the protective layer of this laminate so that the adhesive area ratio is 7% by the gravure method. The adhesive layer of the protective layer was superposed on the other surface of the gas adsorption layer having the above two-layer structure, and all the materials were pressure-bonded with a roll. Thereafter, the laminate having a three-layer structure was left in a constant temperature and humidity chamber at 30 ° C. and 65% RH for 24 hours to perform a curing treatment. Further, the laminate was dipped in a processing bath of 3 wt% fluorine-based water repellent (Asahi Glass Co., Ltd., Asahi Guard AG970), dried, and then subjected to fixing treatment at 170 ° C. To 0.5 wt%. Table 1 shows the gas permeation resistance test result, the liquid permeation resistance test result, the peel strength 2 and the evaluation results of the durability of the gas adsorption layer of the obtained adsorption sheet.

(Comparative Example 2)
After laminating the above-mentioned protective layers on both sides of the above-mentioned gas adsorption layer, a laminated body of a three-layer structure is created by quilting and stitching to a diamond pattern at a 2-inch pitch using an oil-repellent sewing thread. Except not having laminated | stacked, the adsorption sheet was produced by the method similar to Example 1. FIG. Table 1 shows the gas permeation resistance test result, the liquid permeation resistance test result, the peel strength 2 and the evaluation results of the durability of the gas adsorption layer of the obtained adsorption sheet.

  As is apparent from the results in Table 1, the adsorption sheets of Examples 1 to 4 are good in all of gas permeation resistance, liquid permeation resistance, peel strength, and durability of the gas adsorption layer. The adsorption sheet of Comparative Example 1 has a low peel strength and the durability of the gas adsorption layer is inferior. The adsorption sheet of Comparative Example 2 has low liquid permeation resistance. The evaluation item was inferior to that of the example.

  The adsorbing sheet of the present invention is excellent in peel strength and durability of the gas adsorbing layer while maintaining the permeation suppressing ability for not only gaseous harmful substances but also liquid harmful substances. It is important to contribute.

1: Fabric made of thermoplastic fiber 2: Partial adhesive layer 3: Protective layer 4: Gas adsorption layer 5: Protective layer 6: Quilted yarn 7: Upper cell 8: Sampling port 9: Test liquid 10: Test article 11: Paraffin 12 : Lower cell 13: Weight 14: Test solution 15: Test product 16: Filter paper 17: Glass plate

Claims (5)

  A suction sheet comprising: a protective layer laminated on both sides of a gas adsorption layer by quilting; and a fabric made of thermoplastic fibers adhered to the surface of any of the protective layers with a solventless adhesive. The adhering sheet according to claim 1, wherein the adhesion by the solventless adhesive is partial adhesion, and the mass of the solventless adhesive is 5 g / m ² or more and 50 g / m ² or less.   The gas adsorbing layer has any form of woven fabric, knitted fabric, non-woven fabric, or felt, and the solventless adhesive is a urethane-based adhesive or a silicone-based adhesive. Adsorption sheet.   A protective material using the adsorbent sheet according to claim 1.   The protective material according to claim 4, wherein the protective material is protective clothing.