JP2008104556A - Laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet which shows an excellent deodorizing performance, antibacterial properties, and rigidity. <P>SOLUTION: The laminated sheet includes a layer containing a substance having an absorption action of odorous substances and an air-permeable sheet layer containing a photocatalyst degrading the odorous substance, which are integrally laminated. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate sheet in which an adsorption layer and a decomposition layer of an odorous substance are laminated and integrated, and more specifically, relates to a laminate sheet excellent in deodorizing and antibacterial properties, in which adsorption and decomposition are sequentially performed.

  Conventionally, as a material used for a deodorizing filter, a filter containing an adsorbent such as a photocatalyst and activated carbon has been used. For example, as a filter for an air purifier, Patent Documents 1 to 3 include an activated carbon filter and In addition, a photocatalytic filter and a combination of filters arranged in units of filters or a stack of filters are disclosed. Since such a filter is a combination of filters or a stack of filters, there is a problem that the filter becomes bulky and the structure becomes large as a whole. In addition, there are problems such as inferior molding processability such as pleating and inferior form retention to a pleated shape.

Patent Document 4 proposes a deodorant fiber containing both an adsorbent and a photocatalyst in the same fiber. This deodorant fiber provides deodorant performance regardless of whether or not light is irradiated, but since both the adsorbent and the photocatalyst are contained in the same fiber, the mixing ratio of the adsorbent and the photocatalyst depends on the application. However, there is a problem that the preparation and processing methods of both are likely to be complicated, the functions of both are not sufficiently exhibited, and the cleaning durability tends to be reduced.
Therefore, there has been a demand for a filter capable of maximizing the functions of both the adsorbent and the photocatalyst, that is, a filter capable of efficiently demonstrating the performance of both in one sheet.
JP-A-63-315138 Japanese Patent Laid-Open No. 10-85558 JP 2003-53116 A Japanese Patent No. 3215318

  The problem of the present invention is that, in contrast to the conventional problems described above, the functions of both adsorption ability and resolution can be fully exerted, have a synergistic excellent effect, and are excellent in washing durability and deodorant antibacterial performance. It is to provide a laminated sheet.

  In view of the above-mentioned problems of the prior art, the inventor is a laminate sheet in which a layer containing an adsorption agent and a layer containing a decomposition agent are laminated and integrated, and the laminate sheet is adsorbed. The so-called deodorizing substance in the gas passing through the sheet is temporarily adsorbed and stored in the adsorbent by providing the layer and the decomposition layer as separate layers and forming a laminate having moderate air permeability as a whole. The pocket action and the odorous substance are adsorbed by the adsorbent layer, thereby concentrating the odorous component, and then the rapid decomposition by the decomposing agent is performed efficiently, and these effects are combined. The present inventors have found that it has excellent deodorizing and antibacterial performance and have reached the present invention.

That is, the present invention is as follows.
(1) A laminate sheet in which a layer containing an odorous substance-adsorbing substance and a breathable sheet layer containing a photocatalyst for decomposing the odorous substance are laminated and integrated.
(2) The laminate sheet according to (1), wherein the laminate has an air permeability of 1 to 350 cc / cm ² / sec.
(3) The laminate sheet according to (1), wherein a weight ratio between the adsorption agent and the photocatalyst is in a range of 5 to 300.
(4) The layered sheet according to any one of (1) to (3), wherein the layer containing the adsorptive substance is made of an adsorbent and a hot melt resin.
(5) The laminate sheet according to any one of (1) to (4), wherein the breathable sheet is a thermoplastic synthetic fiber nonwoven fabric layer.
(6) The laminate sheet according to (4), wherein the breathable sheet layer containing a photocatalyst is a nonwoven fabric sheet in which the photocatalyst is supported by a binder.
(7) The laminate sheet according to any one of (1) to (5), wherein the layer containing the adsorptive substance and the breathable sheet layer containing the photocatalyst are alternately arranged in multiple layers. .
(8) The laminate sheet according to (7), wherein the adsorption agent and / or the photocatalyst has a concentration gradient for each layer unit and is arranged in multiple layers.
(9) The laminate sheet according to (1), wherein a photocatalyst is applied to the breathable sheet in a range of 0.1 to 10 g / m ² .
(10) The laminate sheet according to (4), wherein a mixing ratio of the adsorbent and the hot melt resin is 0.3 to 2.
(11) The laminate sheet according to (5), wherein the thermoplastic synthetic fiber nonwoven fabric is a long fiber nonwoven fabric or a needle punched long fiber nonwoven fabric.

(12) The laminate sheet according to (5) or (11), wherein at least one of the thermoplastic synthetic fiber nonwoven fabrics is composed of a composite fiber having a core-sheath structure.
(13) A deodorized antibacterial molded article obtained by molding the laminate sheet according to any one of (1) to (12).

The laminate sheet of the present invention comprises a layer containing an odorous substance adsorbing substance (hereinafter sometimes simply referred to as an adsorption layer) and a breathable sheet layer containing a photocatalyst that decomposes the odorous substance (hereinafter simply referred to as decomposition). (Sometimes referred to as “layers”) are arranged independently and laminated and integrated. Thus, for example, deodorant components are first adsorbed in the adsorption layer, temporarily stored at a high concentration, and then rapidly decomposed in the decomposition layer. Adsorption and decomposition proceed in two stages in parallel. Therefore, the synergistic effect of both is exhibited, and an excellent deodorizing effect is obtained. In the present invention, since adsorption and decomposition proceed simultaneously, the adsorption seat is less likely to be saturated, a constant deodorization is possible, and a semi-permanent, continuous deodorization effect can be expected.
Further, since the rate of adsorption and decomposition of odorous substances is synergistically increased, high-concentration deodorizing components can be deodorized and decomposed in a short time, and long-life deodorization can be expected.

In the present invention, the balance between the amount of adsorbent and the amount of decomposing agent can be changed in accordance with the required application and characteristics, so an efficient laminate sheet is designed in consideration of the balance between adsorption and decomposition rate. be able to. Further, by arranging the adsorption layer and the decomposition layer in multiple layers, it is expected that the deodorizing ability is improved and the life is extended. Furthermore, by providing a concentration gradient for each layer of the adsorption layer and / or the decomposition layer, a more efficient operation effect is exhibited. Moreover, the combination of nonwoven fabric sheets can be changed to greatly control the range of breathability.
In addition, the laminated sheet of the present invention can also exhibit excellent antibacterial properties by using a decomposition layer that also has antibacterial effects, and further has less deterioration in performance in cleaning and also has excellent cleaning durability. .
Therefore, the laminated sheet of the present invention is suitable for various uses that require deodorization and antibacterial properties, such as sanitary materials, living materials, interior interiors, building materials, and other various filter materials.

The effects of the present invention are summarized as follows.
(1) Odorous components are first adsorbed in the adsorption layer, and then decomposed in the decomposition layer. Since the adsorption and decomposition proceed in two stages in parallel, the synergistic effect of both is demonstrated and excellent. Deodorizing effect is obtained.
(2) In the present invention, since adsorption and decomposition proceed in parallel, the adsorption seat is less likely to be saturated, a constant deodorization is possible, and a semi-permanent, continuous deodorization effect can be expected.
(3) By increasing the speed of adsorption and decomposition, high-concentration deodorant components can be deodorized and decomposed in a short time, and long-life deodorization can be expected.
(4) Since the amount of adsorbent and decomposing agent can be changed according to the required application characteristics, the rate balance between adsorption and decomposition can be easily changed, and efficient deodorization, Decomposition can be expected.
(5) The adsorption layer and the decomposition layer can be easily arranged in multiple layers, and a more effective deodorization and antibacterial effect can be achieved by providing a concentration gradient for each layer of the adsorption layer and / or the decomposition layer. And can have a long life.
(6) By using a decomposition layer having an antibacterial effect, excellent antibacterial properties can also be exhibited. Furthermore, by using a method for supporting a decomposed substance using a binder, there is little degradation in performance during cleaning, and excellent cleaning durability is achieved.

  In the present invention, the breathable sheet layer containing a photocatalyst as a decomposition agent may be a porous sheet, but a woven fabric, a knitted fabric, a non-woven fabric, etc. are preferable, and a non-woven fabric is particularly preferable from the viewpoint of strength and air permeability.

  As the nonwoven fabric used in the present invention, a thermoplastic synthetic fiber nonwoven fabric is preferable, and a nonwoven fabric obtained by a spunbond method, a thermal bond method, a needle punch method, water column entanglement method, or the like using fibers having a fiber diameter of 1 to 30 μm is particularly preferable.

  Examples of constituent fibers of the nonwoven fabric include polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and copolyester, nylon fibers such as nylon 6, nylon 66, and copolyamide fibers, and low density polyethylene. Polyolefin fibers such as high density polyethylene, polypropylene, copolymerized polyethylene, and copolymerized polypropylene.

  Polyesters such as aromatic polyester copolymers and aliphatic polyesters obtained by copolymerizing polyethylene terephthalate with one or more compounds of phthalic acid, isophthalic acid, sebacic acid, adipic acid, diethylene glycol, and 1,4-butanediol. There are fibers.

  As the composite fiber, a composite fiber composed of two components having a low melting point component such as a core-sheath structure and side-by-side, for example, a composite fiber having a high melting point in the core part and a low melting point in the sheath part is a thermal adhesive viewpoint. To preferred. For example, the core is a high melting point fiber such as polyethylene terephthalate (PET), polybutylene terephthalate, nylon 6, nylon 66, copolymer polyamide, and the sheath is low density polyethylene, high density polyethylene, polypropylene, copolymer polyethylene, copolymer. Composite fibers, which are low melting point fibers such as polymerized polypropylene, copolymerized polyester (CO-PET), and aliphatic polyester, are used alone or laminated and mixed. In particular, a spunbond polyester long fiber nonwoven fabric is preferred from the viewpoint of strength, rigidity, pleatability, and the like.

  Preferably, at least one of the thermoplastic synthetic fiber nonwoven fabrics is a core-sheath composite fiber nonwoven fabric, a laminated nonwoven fabric of high-melting fibers and low-melting fibers, a laminated nonwoven fabric of high-melting fibers and a core-sheath composite fiber nonwoven fabric, or the like. . The reason is that heating and pressurizing during the production of the laminate can contribute to adhesion by softening or melting from both sides of the low-melting fiber and the hot-melt resin, and adhesion integration can be performed effectively. is there.

Nonwoven basis weight of the present invention is preferably 15~150g / m ^2, more preferably from 20 to 100 g / m ^2, the basis weight is less than 15 g / m ^2, powder leakage, such as adsorbent fiber interstices increases Tends to occur, and the strength decreases. On the other hand, if it exceeds 150 g / m ² , the fiber gap can be reduced, but the thickness is increased and the heat insulation is increased, but the thermal adhesiveness and the bonding processability are lowered.

  In the present invention, the weight ratio of the adsorbent substance and the photocatalyst that is the decomposition agent is in the range of 5 to 300, preferably in the range of 10 to 100. When the weight ratio is within this range, the adsorption / decomposition rate balance is good, and the adsorption pocket effect, concentration effect, and rapid decomposition effect are obtained.

  In the present invention, the layer containing an adsorbent substance is preferably composed of an adsorbent and a hot melt resin, and a mixture of the adsorbent and the hot melt resin is more preferably used. Each particle size range is preferably 100 to 1000 μm, and more preferably mixed and processed so as to have substantially the same particle size range.

  In the integrated processing of the laminated body, from the viewpoint of bonding properties, the adsorbent and hot melt resin have the same particle size range and particle size, so that the adsorbent is not crushed and the resin adheres to the nonwoven fabric layer. The adsorbent can be held in the intermediate layer in a relatively high degree of freedom while maintaining the properties, and the surface activity can be effectively functioned without covering the surface of the adsorbent.

  Further, from the viewpoint of bonding processability, it is preferable to select the meltability and amount of the hot melt resin, and the hot melt resin is preferably softened or has a high viscosity (MI: melt index) upon melting. .

The adsorbent amount of the present invention is preferably 10 to 300 g / m ² , more preferably 15 to 200 g / m ² , and particularly preferably 20 to 100 g / m ² . When the adsorbent is within this range, sufficient adsorbability can be obtained without impairing adhesion.

  The mixing ratio of the adsorbent and the hot melt resin is preferably 0.3 to 2, and more preferably 0.5 to 1.6, by weight. When the mixing ratio is less than 0.3, the amount of hot melt resin is increased with respect to the adsorbent, and the bonding processability is improved. However, since the hot melt resin coats the adsorbent, the adsorbing performance tends to decrease. . When the mixing ratio of the adsorbent and the hot melt resin exceeds 2, the ratio of the hot melt resin is not so high, the bonding processability is liable to deteriorate, and the laminate is liable to be peeled off.

  The adsorbent used in the present invention has an adsorption function for odorous substances in the air. For example, a porous powder or a powder obtained by immobilizing a chemical adsorbent on a porous powder is preferably used. It is done. Although not particularly limited as the porous powder, for example, activated carbon obtained by calcination of coconut shell, tar, resin, etc., impregnated activated carbon chemically treated such as basic, acidic, neutral, zeolite, silica gel, activated clay, alumina, etc. It is selected from adsorbents such as a porous powder or a granular substance having a function of physical adsorption / chemical adsorption or a mixture thereof.

  Hot melt resins such as polyethylene, polypropylene, polyethylene copolymer, polypropylene copolymer, ethylene-vinyl acetate, polyester, copolymer polyester, polyamide, etc. are usually used for processing of adhesive interlining, etc. Or a granular hot-melt resin.

  The particle size of the hot melt resin powder is preferably 40 to 1000 μm, more preferably 100 to 1000 μm. The MI (melt index) value representing the viscosity at the time of melting is preferably from 0.1 to 30, and more preferably from 1 to 20. If the particle size of the hot melt resin is less than 40 μm, the hot melt resin tends to float in the air, and processing into a hygroscopic agent tends to be difficult. On the other hand, when the particle size exceeds 1000 μm, there is a problem that the secondary workability of the sheet-like material tends to be lowered.

Basis weight of the laminate sheet of the present invention, the intensity of interest, 50 to 400 g / m ² from breathable, preferably 60~350g / m ^2. If the basis weight is less than 50 g / m ² , the rigidity and strength are lowered and sufficient workability cannot be obtained. If the basis weight is more than 400 g / m ² , the rigidity and strength are increased, but the air permeability is lowered.

The air permeability of the laminate sheet of the present invention is preferably 1 to 350 cc / cm ² / sec, more preferably 1 to 200 cc / cm ² / sec, and still more preferably 30 to 150 cc / cm ² / sec. . Within such a ventilation range, the odorous component is sufficiently transferred within the sheet, the odorous component is sufficiently adsorbed in the adsorption layer, and the deodorized component is sufficiently stored and concentrated. Moreover, the decomposition in the decomposition layer is also rapidly performed.

If the air permeability is less than 1 cc / cm ² / sec, the flow of air into the sheet is reduced, the adsorption rate is lowered, and the deodorizing effect is lowered. On the other hand, if the air permeability exceeds 350 cc / cm ² / sec, the air flow is sufficient, but the odorous component passes through and passes through, reducing the chance of contact with the adsorbent and reducing the deodorizing component. Storage concentration in the adsorption layer becomes insufficient, and the deodorizing effect is reduced.

  The bending resistance of the laminate sheet of the present invention is, when used for a filter material, formed into a pleated shape, a cylindrical shape, etc., for the purpose of increasing the surface area, becomes a filter unit, and retains its shape by a flow rate of air, water, etc. Since it is necessary, appropriate rigidity is required. The bending resistance is preferably 50 mm or more, more preferably 70 to 200 mm, and still more preferably 100 to 200 mm as measured by cantilever. If the bending resistance is less than 50 mm, the rigidity tends to be insufficient, and the shape retainability tends to decrease.

By using a prefilter on at least one side of the laminate sheet of the present invention, the state of contamination on the surface becomes clear and the filter life can be further extended. As the prefilter, a non-woven fabric of a needle punch method or a thermal bond method of a polypropylene short fiber, a polyester short fiber having a fiber diameter of 10 to 30 μm and a fiber length of 30 to 70 mm is preferably used. The basis weight of the short fiber nonwoven fabric is preferably 50 to 150 g / m ² , and the average apparent density is preferably 0.01 to 0.15 g / cm ³ .

  In the laminate sheet of the present invention, it is preferable that layers (A layer) containing an adsorption acting substance and layers (B layer) containing a decomposition acting substance (photocatalyst) are alternately arranged in multiple layers. As a whole, the layers are preferably three layers, five layers, seven layers, etc., and the surface layer is preferably a layer containing a decomposition agent. In the three-layer structure, a layer containing an adsorbent substance is disposed in the middle, and has a B1 / A / B2 configuration (1, 2 mean the first and second sheets, respectively). In the five-layer structure, the arrangement of B1 / A1 / B2 / A2 / B3 is preferable, and in the seven-layer structure, the arrangement of B1 / A1 / B2 / A2 / B3 / A3 / B4 is preferable.

  In such an arrangement, the adsorption agent layer and / or the decomposition agent layer are preferably arranged in multiple layers having a concentration gradient for each layer unit. For example, a high concentration region can be set in the central portion of the stacked body, and a high concentration region can be set in the surface layer portion of the stacked body.

The concentration or weight setting of each layer is appropriately designed according to the required characteristics in the application field.
As a specific configuration, for example, if the configuration is B1 (30 g / m ² ) / A (80 g / m ² ) / B2 (30 g / m ² ), a laminate of 140 g / m ² is obtained. In the case of B1 (20 g) / A1 (40 g) / B2 (15 g) / A2 (80 g) / B3 (20 g), a total of 175 g / m ² is obtained. In seven layers, a laminate of 190 g / m ² as a whole in B1 (20 g) / A1 (30 g) / B2 (10 g) / A2 (40 g) / B3 (10) / A3 (60 g) / B4 (20 g) Become.

  In the present invention, a breathable sheet containing a photocatalyst having a function of decomposing odorous substances, the sheet generates active oxygen by irradiation with light such as ultraviolet rays, and oxidatively decomposes many odorous substances, It is obtained by applying a processing agent having antibacterial and bactericidal action.

  As specific processing agents, for example, sulfides such as copper sulfide and zinc sulfide, oxides such as titanium oxide, zinc oxide and oxide tank stainless steel, metal chalcogenite and the like are used singly or in combination. As a photocatalyst agent, it can be used in sol or gel form, and may be used in powder form. Examples of photocatalyst processing methods include a method of forming a water-insoluble precipitate from an aqueous solution containing metal ions such as titanium halide and titanium sulfide, a method of preparing from metal alkoxytitanium, and a gas phase method of oxidizing at high temperature. . In particular, for the purpose of suppressing the decomposition of fibers and the like, it is supported on an inorganic substance such as silica, alumina-silica, zirconia or apatite, a porous substance, or is treated or coated with an organic polymer substrate or a binder resin, In order to prevent the deterioration of the fiber, it is used without being in direct contact.

  Next, in supporting the photocatalyst on the breathable sheet, in order to improve durability such as washing with water, a binder resin such as an acrylic resin, a urethane resin, a silicone resin, a melamine resin, or a fluorine resin is used. Preferably used. As a specific processing method, in order to give affinity to the fiber surface of the nonwoven fabric which is a breathable sheet, after applying the binder resin treatment, the photocatalyst is applied or a mixed solution of the binder resin and the photocatalyst is used. It can also be processed in the same bath. The coating method is performed by immersion in a processing agent, dehydration between two rolls, drying treatment, impregnation processing method, gravure roll method, kiss roll method, spray method, or the like.

The coating amount of the photocatalyst is preferably 0.1 to 10 g / m ² , more preferably 0.2 to 5 g / m ² , and particularly preferably 0.3 to 3 g / m ² . When the coating amount is less than 0.1 g / m ^{2, the} coating amount is small, the degradability is low, and the deodorization and antibacterial properties may be lowered.

  Furthermore, by covering the fiber surface of the nonwoven fabric, which is a breathable sheet, with a binder resin film, the fiber surface becomes compatible, and the photocatalytic agent supportability can be improved. The amount of the binder resin is 0.1 wt% to 20 wt%, preferably 0.5 to 15 wt%, based on the fiber weight. When the amount of the binder resin is less than 0.1 wt%, the affinity is insufficient. On the other hand, when it exceeds 20 wt%, the fibers are fixed to each other, and problems such as deterioration of physical properties are likely to occur.

  In particular, when a mixed solution of a photocatalyst and a binder resin is applied, the weight ratio of the binder resin to the photocatalyst is preferably 0.01 to 3.0, more preferably 0.05 to 2.5 in order to sufficiently exhibit the characteristics of the photocatalyst. It is. If the amount of the binder resin exceeds 3 times that of the photocatalyst, the photocatalyst is likely to be covered with the resin film, and the photocatalytic function tends to be extremely lowered.

An example of the manufacturing method of the laminated sheet of this invention is demonstrated.
The mixed powder of adsorbent and hot melt resin mixed using a powder mixer such as a homomixer or a rotary mixer on the thermoplastic synthetic fiber nonwoven fabric that has been coated with the photocatalyst, and a rotating brush and vibration The amount of powder is adjusted to 10 to 1000 g / m ² with a powder shaker and the like. The thermoplastic synthetic fiber non-woven fabric is laminated thereon, and then bonded by heating and pressing with a roll-like or belt-like heating device.

  Specifically, using a belt-shaped heating device such as a metal roll, metal, rubber, woven fabric, or non-woven fabric, conditions for softening or melting the hot melt resin are set, for example, a temperature of 100 to 220 ° C., a pressure The adsorbent and the breathable sheet are integrated into a laminate in 1 to 100 N / cm for a time of 1 to 60 seconds.

The deodorant / antibacterial action of the laminate sheet of the present invention will be described. FIG. 1 is a graph showing the deodorizing effect of ammonia with respect to the standing time based on an example described later under a relatively high concentration ammonia condition of 200 ppm of initial ammonia. In the case of using only the adsorbent (A), the ammonia residual rate becomes 45% after 30 minutes, but the ammonia adsorption thereafter becomes saturated, and the subsequent ammonia deodorizing effect is not seen. In the case of using only the photocatalyst layer (B), although the ammonia concentration is lowered by the deodorizing effect by the photocatalyst, there is about 10% ammonia remaining even after 120 minutes, which is not a sufficient deodorizing effect. When the decomposition layer (photocatalyst layer) and the adsorption layer, which are embodiments of the present invention, coexist (C), the ammonia deodorizing effect is remarkable, and the ammonia residual rate is about 10% after 30 minutes and 30 minutes have elapsed. Later it becomes below the detection limit.
As described above, the present invention has an excellent ammonia deodorizing effect, and adsorption and decomposition proceed in parallel, so that a synergistic effect of adsorption and decomposition is exhibited, and an excellent deodorizing effect can be obtained.

The present invention will be described based on examples.
The measurement method is as follows.
(1) Weight per unit area (g / m ² ): A sample of 20 cm in length × 25 cm in width is cut out at three places, the weight is measured, and the average value is calculated by converting to mass per unit. (JIS-L-1096)
(2) Average fiber diameter (μm): Take a 500 times magnified photograph with a microscope, and obtain the average value of 10 fibers.
(3) Breathability: Conforms to the JIS-L-1096 Frajoule method.
(4) Bending softness: compliant with JIS-L-1096 cantilever method (5) Peelability: Determine whether to peel after processing by sensory inspection.
○: Level at which peeling by hand is difficult ×: Easy peeling by hand
(6) Deodorant: ND in the table represents the detection limit (below the minimum scale of the detection tube).
<Ammonia> ND is 10 ppm or less.
After putting a sample of 5cm x 10cm square into a tetra-bag bag with an internal volume of 1L, inject ammonia gas to 200ppm and keep this bag at 25 ° C in the incubator.
The deodorizing performance was measured by irradiating an ultraviolet lamp for a predetermined time at 40 cm and measuring the ammonia concentration.
However, as for the ultraviolet lamp, four FL10SBLBs manufactured by Toshiba Lighting & Technology were installed in the above incubator.
The measurement results were expressed as the ratio (%) of the residual ammonia gas concentration to the initial ammonia gas concentration.
(The residual concentration after 1 hour of the ammonia concentration in the bag without the sample was 190 ppm, and the residual ammonia concentration after 160 hours was 160 ppm.)
<Acetaldehyde> ND is 1 ppm or less.
After putting a sample of 5cm x 10cm square into a tetra-bag bag with a 1L capacity, injecting acetaldehyde gas to 20ppm and injecting ultraviolet rays at an interval of 40cm in an incubator kept at 25 ° C. Deodorizing performance was measured by irradiating the lamp and measuring the acetaldehyde concentration.
The measurement results were expressed as the ratio of the residual ammonia gas concentration to the initial acetaldehyde gas concentration.
(The residual concentration after 1 hour of the concentration of acetaldehyde in the bag without the sample was 18 ppm.)
(7) Antibacterial: A sample 5cm x 5cm square is used and conforms to the JIS-L-1902 quantitative test (bacterial solution absorption method).
Test strain: Method for measuring the number of viable Staphylococcus aureus: Pour plate culture method
Culturing time: 18 hours (during UV irradiation with UV intensity of 0.1 mV / cm ² during cultivation)
The results were expressed as bacteriostatic activity values. A bacteriostatic activity value of 2.2 or higher is judged to have an antibacterial effect.
(8) Deodorization and antibacterial properties after cleaning As a cleaning condition, an immersion method was adopted. 100cc of distilled water was put into a 5cm x 10cm, 200cc container, the sample was immersed and dried, and this operation was repeated 5 times, and then the deodorization and antibacterial properties after washing were measured.

[Example 1]
As a breathable sheet, a polyethylene terephthalate (PET, melting point 263 ° C.) is melt-spun by a spunbond method using a spinneret, and a PET web having an average fine diameter of 15 μm is accumulated on a collection net. After forming a fiber web of m ^2, a thermoplastic synthetic fiber nonwoven fabric was obtained by thermocompression bonding with an embossing roll having an crimping area ratio of 11% (the nonwoven fabric has an air permeability of 260 cc / cm ² / sec).
The obtained non-woven fabric was subjected to a process for applying a titanium oxide photocatalyst agent. As a photocatalyst agent, Lion's product name Lionite PC-541S 15% aqueous solution was prepared and subjected to immersion, dehydration, and drying steps to obtain photocatalyst carrying sheets B1 and B2 layers (respectively, photocatalyst agent) The coating amount is 1.0 g / m ² ).

Next, an adsorbent of coconut shell activated carbon powder fractionated to a particle size of 75 μm to 200 μm and a polyethylene hot melt agent having a particle size of 75 μm to 200 μm (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name Sunfain PAK melting point 80 to 35 ° C., MI value 2) .5) is mixed with a rotary powder mixer so that the adsorbent amount is 30 g / m ² and the hot melt adhesive amount is 50 g / m ² (adsorbent amount / adhesive amount = 0.6). The powder was adjusted to a coating amount of 80 g / m ² by using a powder supply device to obtain an intermediate layer A1.

Next, in the laminating process, using a heat-resistant belt-like heating and pressurizing device, the mixed powder is applied on the supporting sheet B1, and then the supporting sheet B2 is overlaid, and the atmosphere at a temperature of 170 ° C. The laminate sheet having a basis weight of 140 g / m ² was obtained by passing through the inside and bonding and integration.

  Table 1 shows the deodorant and antibacterial results of the obtained laminate sheet. From the results of Table 1, the laminate sheet of the present invention is soft with a thickness of 0.55 mm, has sufficient air permeability, excellent deodorant properties and antibacterial properties, and does not cause peeling between the nonwoven fabric and the nonwoven fabric. It was found that sufficient lamination and integration were achieved.

[Example 2]
As a breathable sheet, polyethylene terephthalate (PET, melting point 263 ° C.) was melt-spun by a spunbond method using a spinneret, and a PET web having an average fine diameter of 12 μm was accumulated on a collection net. As a whole, a laminated fiber web having a weight per unit area of 19 g / m ² was obtained by thermocompression bonding with an embossing roll having a compression area ratio of 23% to obtain a thermoplastic synthetic fiber nonwoven fabric. (The air permeability of the nonwoven fabric is 280cc / cm ² / sec)
Photocatalytic titanium oxide was processed into the obtained nonwoven fabric. As the photocatalyst agent-imparting process, an aqueous solution of Lion Corp., trade name Lionite PC-541S 30% was prepared and subjected to immersion, dehydration, and drying steps to obtain photocatalyst carrying sheets B1 and B3. (Photocatalyst coating amount 1.3g / m ² )
Subsequently, the composite nonwoven fabric B2 was used in the middle part. Composite nonwoven fabric B2 is spunbonded using a two-component spinneret, melt-spun low-density polyethylene (LDPE, melting point 115 ° C.) as a sheath component and polyethylene terephthalate (PET, melting point 263 ° C.) as a core component, After obtaining a sheath-core type composite fiber web having an average fine diameter of 16 μm, it was integrated by thermocompression bonding with an embossing roll having a crimping area ratio of 12% to obtain a thermoplastic synthetic fiber nonwoven fabric. (Weight per unit 20g / m ² , breathability 310cc / cm ² / sec)
Next, an adsorbent of coconut shell activated carbon powder fractionated to a particle size of 75 μm to 200 μm and a polyethylene hot melt agent having a particle size of 75 μm to 200 μm (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name Sunfain PAK melting point 80 to 35 ° C., MI value 2 .5) is a mixed powder mixed with a rotary powder mixer so that the adsorbent amount is 10 g / m ² and the adhesive amount is 30 g / m ² (adsorbent amount / adhesive amount = 0.3). Was adjusted so as to have a coating amount of 40 g / m ² using a powder supply device, thereby forming an intermediate layer A1. Further, the intermediate layer A2 was a mixed powder having an adsorbent amount of 60 g / m ² and an adhesive amount of 50 g / m ² (adsorbent amount / adhesive amount = 1.2), and the coating amount was 110 g / m ² .

Next, the laminating process was performed in the same manner as in Example 1. However, as a first step, the two non-woven fabrics B1 and B2 and the mixed powder A1 were bonded together as the first step. Then, as a second step, the mixed powder A2 was applied to the non-woven fabric of B3, overlapped so that B2 became an intermediate portion, and heated and pressurized to be bonded and integrated. A multilayer sheet (210 g / m ² ) having a multilayer structure in which the adsorption layer (A1A2) and the decomposition layer (B1B2) were alternately arranged was obtained. Table 1 shows the deodorant and antibacterial results of the obtained multilayer structure laminate sheet of the present invention.

From the results shown in Table 1, the laminate sheet of the present invention is excellent in deodorizing properties and antibacterial properties, the nonwoven fabric and the nonwoven fabric are not separated from each other, and the composite nonwoven fabric is sufficiently integrated. It was found that was obtained.
Compared with Example 1, the lifetime of the deodorizing effect could be extended by multilayering.

[Example 3]
In the basis of the breathable sheet, the B1 layer is processed to a binder weight of 22 g / m ² to 23.5 g / m ² and further photocatalyzed to give a total weight of 25 g / m ² (nonwoven fabric 22 g / m ² , photocatalyst 1.5 g / m ²⁾ . m ² , binder 1.5 g / m ² ), B2 layer is binder processed to 44 g / m ² to 47 g / m ^2, and further photocatalyst processed to 50 g / m ² overall weight (nonwoven fabric 44 g / m ² , A thermoplastic synthetic fiber nonwoven fabric was used in the same manner as in Example 1 except that the photocatalyst was 3 g / m ² and the binder was 3 g / m ² ).
Next, for the purpose of improving the supportability and durability of the photocatalyst agent, the resulting nonwoven fabric was subjected to binder processing, and then the photocatalyst agent was applied. Non-woven fabric binder processing was performed by immersing the non-woven fabric in water-soluble resin, dehydration, and drying treatment. ).

Titanium oxide was processed as a photocatalyst for the nonwoven fabric. As the photocatalyst agent-imparting process, an aqueous solution of Lion Corp., trade name Lionite PC-541S 30% was prepared and subjected to immersion, dehydration, and drying steps to obtain photocatalyst carrying sheets B1 and B3.
Next, an adsorbent of coconut shell activated carbon powder fractionated to a particle size of 75 μm to 200 μm and a polyethylene hot melt agent having a particle size of 75 μm to 200 μm (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name Sunfain PAK melting point 80 to 35 ° C., MI value 2) .5) is a mixed powder mixed with a rotary powder mixer so that the adsorbent amount is 30 g / m ² and the adhesive amount is 50 g / m ² (adsorbent amount / adhesive amount = 0.6). Was adjusted to an application amount of 80 g / m ² using a powder supply device to obtain an intermediate layer A1.
Next, the laminating process uses a heat-resistant belt-like heating and pressurizing device to apply the mixed powder on the support sheet B1, and then superimpose the support sheet B2 in an atmosphere at a temperature of 170 ° C. And laminated by bonding to obtain a laminate of the present invention. Table 1 shows the deodorant and antibacterial results of the obtained laminate sheet of the present invention.

From the results of Table 1, the laminate of the present invention is excellent in deodorizing properties and antibacterial properties, and the nonwoven fabric and the nonwoven fabric are not peeled off, and the composite nonwoven fabric is sufficiently integrated. It was found that was obtained.
Furthermore, even if it was repeatedly immersed and dried in water 5 times, it was a laminate sheet with little deterioration in deodorant antibacterial performance and excellent cleaning durability.

[Example 4]
A thermoplastic synthetic fiber nonwoven fabric of B1, B2, and B3 was used as the breathable sheet, and a photocatalyst carrying sheet was obtained by performing immersion, dehydration, and drying treatments using a mixed solution of a photocatalyst agent and a binder. As photocatalyst, Taihei Kagaku Sangyo Co., Ltd. photocatalytic apatite, 30% concentration of trade name PHOTOHAP PCAP-L20, as binder, water-soluble acrylic resin made by Dainippon Ink Industries, trade name Boncoat R-3380A 5% concentration The mixed solution was used as a processing agent.
In the above breathable sheet, the B1 layer and the B2 layer are processed into a non-woven fabric basis weight of 23 g / m ² to obtain a photocatalyst of 1.5 g / m ² , a binder of 0.5 g / m ² and an overall basis weight of 25 g / m ^2. The layer was processed into a nonwoven fabric basis weight of 46 g / m ² to give a photocatalyst of 3 g / m ² , a binder of 1 g / m ² and an overall basis weight of 50 g / m ² .

Next, the A1 layer and the A2 layer were formed using a powder obtained by mixing an adsorbent (coconut shell activated carbon) and an adhesive (polyethylene hot melt resin). The A1 layer has an adsorbent of 10 g / m ² , an adhesive amount of 30 g / m ² and a coating amount of 40 g / m ² , and the A2 layer has an adsorbent of 50 g / m ² and an adhesive of 50 g / m ² .

Next, the laminating process was performed twice in the same manner as in Example 2 to obtain a laminate sheet having a multilayer structure.
As a first step, after bonding the two nonwoven fabrics B1 and B2 and the mixed powder A1, the mixed powder A2 is applied to the nonwoven fabric of B2 so that the B2 nonwoven fabric is in the middle Then, the laminate sheet of the multilayer structure of the present invention was obtained by laminating by heating and pressing (however, the laminating apparatus and temperature were the same as in Example 1). Table 1 shows the deodorant and antibacterial results of the obtained laminate sheet.

From the results shown in Table 1, the laminate sheet of the present invention is excellent in deodorizing properties and antibacterial properties, the nonwoven fabric and the nonwoven fabric are not peeled off, and the composite nonwoven fabric is sufficiently integrated. It was found that was obtained.
Further, even when immersed in water, the deodorizing and antibacterial performance was hardly lowered, and the washing durability and life extension were excellent.

[Comparative Example 1]
A composite sheet was obtained in the same manner except that the photocatalytic processing was not performed on the thermoplastic synthetic fiber nonwoven fabric of Example 1. The properties of the composite sheet are listed in Table 1.
From the results of Table 1, in Comparative Example 1, the composite sheet has a low ammonia deodorization property, about 40% of ammonia remains after 120 minutes, and the deodorization and decomposition of ammonia is insufficient. It became low.
[Comparative Example 2]
Using the photocatalyst-processed thermoplastic synthetic fiber nonwoven fabric prepared in Example 1, a composite sheet was prepared by laminating in the same manner without using activated carbon as an adsorbent. The properties of the composite sheet are listed in Table 1.
From the results shown in Table 1, the obtained sheet was antibacterial, but it had a low deodorizing property because there was no adsorbent.

[Example 5]
A filter unit for an air purifier was made using the antibacterial / deodorant sheet of Example 3 of the present invention.
Using thick paper with a thickness of 1.6 mm, it was attached to the cardboard frame after pleating with a height of 25 mm, a pitch of 5 mm, and a number of crests of 70, with an outer frame size of 25 cm long × 35 cm wide. The outer frame was folded 10 mm, and both ends and upper and lower attachments used an adhesive to create a filter unit 3 cm wide, 25 cm long, and 35 cm wide.
This filter unit was excellent in shape retention even when the pressure loss was measured at a wind speed of 0.1 to 2 m / sec. As shown in Table 2, the pressure loss did not cause a problem that the pleat shape was maintained even when the wind speed was increased, and the pressure loss was abnormally increased due to contact with the pleat tip. Moreover, it was a durable filter material with excellent characteristics even when washed with water.

  The laminate sheet of the present invention is excellent in deodorizing performance due to the adsorption / decomposition function, the surface layer has antibacterial and bactericidal properties, and further has a low performance deterioration in cleaning and has excellent cleaning durability. Therefore, it is suitable for uses such as daily life materials, interior interiors, building materials, various filter materials such as air purifiers and dehumidifiers.

The figure which shows the deodorizing effect of the laminated body sheet of this invention.

Claims (13)

A laminate sheet comprising a layer containing an odorous substance adsorbing substance and a breathable sheet layer containing a photocatalyst for decomposing the odorous substance. ^2. The laminate sheet according to claim 1, wherein the laminate has an air permeability of 1 to 350 cc / cm ² / sec. The laminate sheet according to claim 1, wherein a weight ratio of the adsorption agent to the photocatalyst is in a range of 5 to 300. The layered sheet according to any one of claims 1 to 3, wherein the layer containing the adsorptive agent is made of an adsorbent and a hot melt resin. The laminate sheet according to any one of claims 1 to 4, wherein the breathable sheet is a thermoplastic synthetic fiber nonwoven fabric layer. The laminate sheet according to claim 4, wherein the breathable sheet layer containing the photocatalyst is a non-woven sheet in which the photocatalyst is supported by a binder. The laminate sheet according to any one of claims 1 to 5, wherein the layer containing the adsorption agent and the breathable sheet layer containing the photocatalyst are alternately arranged in multiple layers. The laminate sheet according to claim 7, wherein the adsorption agent and / or photocatalyst has a concentration gradient for each layer unit and is arranged in multiple layers. Laminate sheet according to claim 1, wherein the photocatalyst to the breathable sheet is applied in the range of 0.1 to 10 g / m ^2. The laminate sheet according to claim 4, wherein a mixing ratio of the adsorbent and the hot melt resin is 0.3 to 2. The laminate sheet according to claim 5, wherein the thermoplastic synthetic fiber nonwoven fabric is a long fiber nonwoven fabric or a needle punch processed long fiber nonwoven fabric. The laminate sheet according to claim 5 or 11, wherein at least one of the thermoplastic synthetic fiber nonwoven fabrics is composed of a composite fiber having a core-sheath structure. A deodorized antibacterial molded article obtained by molding the laminate sheet according to any one of claims 1 to 12.

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