JP4806785B2 - Photocatalytic functional sheet material - Google Patents

Description

比較例１および２に比較して、実施例１は、防汚性および硬化性の点で風合いに変化なく優れた光触媒機能性シート材である。
【００３７】
【発明の効果】
如上の通り、本発明、即ち光触媒を、接着層を介して高分子可塑剤を含有する塩化ビニル樹脂の表面に構成することによって、従来の通常の液状可塑剤を含有する塩化ビニル樹脂が抱えていた可塑剤成分の拡散による初期汚染の発生、および塩化ビニル樹脂層の硬化の問題が改善され、非常に優れた光触媒機能性シ−ト材が得られる。
【図面の簡単な説明】
【図１】本発明の光触媒機能を片面に有するシ−ト材の断面模式図である。
【図２】本発明の光触媒機能を両面に有するシ−ト材の断面模式図である。
【図３】本発明の光触媒機能を片面に有するシ−ト材の断面模式図である。
【符号の説明】
１：繊維補強材
２：高分子可塑剤を含有する塩化ビニル樹脂層
３：接着層
４：光触媒層
５：液状可塑剤を含有する塩化ビニル樹脂層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocatalytic functional sheet material which has a very excellent antifouling effect and does not cause curing of a vinyl chloride resin.
[0002]
[Prior art]
A photocatalyst-carrying tent site campus having a structure in which a photocatalyst layer is provided on a sheet material via an adhesive layer is disclosed in JP-A-10-237769. The patent describes a plasticizer component that diffuses from a sheet material by firmly bonding the photocatalyst layer by providing a photocatalyst layer with an adhesive layer on a vinyl chloride resin containing a normal liquid plasticizer. In addition to preventing a decrease in the photocatalytic activity due to the photocatalytic action, the sheet material has a function of preventing the deterioration of the sheet material due to the photocatalytic action, and the adhesive layer itself is not easily deteriorated by the photocatalytic action.
[0003]
The patent greatly suppresses the diffusion of the plasticizer component from the vinyl chloride resin containing a normal liquid plasticizer into the photocatalyst layer, and suppresses the decrease in photocatalytic activity. However, the diffusion of the normal liquid plasticizer component to the photocatalyst layer cannot be completely suppressed, and the plasticizer component diffuses to the photocatalyst layer at the initial stage of sheet material production, so that the photocatalytic activity is the plasticizer component. It has a drawback that it is used in the way of disassembling, resulting in contamination. However, when the initial plasticizer component is less diffused and the photocatalytic activity begins to break down the soil, there is a tendency for the contamination to disappear.
[0004]
In other words, the patent is very excellent in that the occurrence of contamination of the sheet material is reduced, but the disadvantage that contamination occurs at an early stage during the manufacture of the sheet material and the normal liquid plasticity. There was a defect that caused the vinyl chloride resin to cure due to the diffusion of the agent component.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a photocatalytic functional sheet material that has a very excellent antifouling property and does not cause curing of a vinyl chloride resin.
[0006]
[Means for Solving the Problems]
The above-mentioned object is to provide a photocatalytic functional sheet material, in which a resin layer made of a vinyl chloride resin containing a polymer plasticizer, an adhesive layer, and a photocatalyst layer are sequentially provided on at least one side of a fiber reinforcing material, This is achieved by a photocatalytic functional sheet material in which the fiber reinforcing material is a woven or knitted fabric, and further by a photocatalytic functional sheet material in which the woven or knitted fabric is a glass fiber fabric.
[0007]
Since the outermost layer is provided with a photocatalyst layer, the organic soil adhering to the surface of the photocatalyst is quickly decomposed by the photocatalytic action, and the remaining inorganic soil is free of organic soil that serves as an adhesive. Therefore, there is an advantage that it is quickly washed away when it rains.
[0008]
In addition, since the adhesive layer is provided on the photocatalyst layer and the resin layer, the photocatalyst layer is firmly adhered to the resin layer, and the sheet material is prevented from being deteriorated by the photocatalytic action.
[0009]
Since a vinyl chloride resin containing a polymer plasticizer is used for the resin layer, there is no diffusion of the plasticizer from the resin layer, and the photocatalytic effect such as the advantages described above can be maximized.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0011]
In the photocatalytic functional sheet material of the present invention, if one side of the fiber reinforcing material is a vinyl chloride resin containing a polymer plasticizer, a photocatalytic layer is provided on the resin layer via an adhesive layer. At that time, the resin layer may not be provided on the other surface of the fiber reinforcing material, or a general resin layer or a general resin layer containing a liquid plasticizer may be provided.
[0012]
Further, if both sides of the fiber reinforcing material are resin layers made of a vinyl chloride resin containing a polymer plasticizer, a photocatalyst layer may be provided on both sides via an adhesive layer, or only on one side via an adhesive layer. A photocatalytic layer may be provided. What is necessary is just to select suitably according to the use purpose for which a photocatalytic function is required.
[0013]
Examples of the fiber reinforcing material used in the present invention include polyamide fibers, polyaramid fibers, polyester fibers, polyvinyl alcohol fibers, and glass fibers. Examples of the fiber form include woven fabrics, knitted fabrics, and non-woven fabrics, and woven fabrics and knitted fabrics are particularly preferable from the viewpoint of strength.
The type and form of the fiber can be appropriately selected and used depending on the application. For example, if it is used for a tent, a polyester fiber woven fabric and a glass fiber woven fabric are preferable. A textile fabric is preferred.
[0014]
As the vinyl chloride resin used in the present invention, a vinyl chloride homopolymer or a copolymer of vinyl chloride and another monomer is used. Other monomers copolymerized with vinyl chloride include α-olefins such as ethylene and propylene; vinyl compounds such as vinyl acetate, acrylic acid esters, alkyl vinyl ethers, vinyl bromide, vinyl fluoride, vinylidene chloride, styrene, and acrylonitrile. Or a vinylidene compound etc. can be illustrated. When the vinyl chloride resin is a copolymer, it may be a random copolymer or a graft copolymer. As an example of the graft copolymer, for example, an ethylene / vinyl acetate copolymer or a thermoplastic urethane polymer may be used as a backbone polymer, and vinyl chloride may be graft polymerized thereon.
[0015]
As the polymer plasticizer used in the present invention, known polymer plasticizers can be used. For example, ethylene / vinyl acetate / carbon monoxide copolymer, ethylene / (meth) acrylate / monoxide Preferred examples include ethylene copolymer polymer plasticizers such as carbon copolymers and ethylene / vinyl acetate copolymers having a high vinyl acetate content.
[0016]
As a compounding quantity of the polymeric plasticizer mix | blended with a vinyl chloride resin used for this invention, 20-200 weight part of polymeric plasticizers per 100 weight part of vinyl chloride resins are preferable.
[0017]
In the present invention, if one side of the fiber reinforcing material is a vinyl chloride resin layer containing a polymer plasticizer, a resin layer may not be provided on the other side, and a general resin layer or a normal liquid plastic layer may be provided. A general resin layer containing an agent may be provided. Typical resin layers include vinyl chloride, polyurethane, ethylene-vinyl acetate copolymer, polypropylene, polyethylene, polyacrylonitrile, polyester, polyamide, fluororesin, silicone resin, styrene-butadiene rubber, and chlorosulfonate. Polyethylene rubber, polyurethane rubber, butyl rubber, isoprene rubber, silicone rubber, fluorine rubber, and other known materials may be used. A normal liquid plasticizer may be appropriately selected and used depending on the application. For example, when used in a tent, vinyl chloride containing a normal liquid plasticizer can be used on one side.
[0018]
In the present invention, as a bonding method for providing a resin layer made of vinyl chloride resin on one side or both sides of the fiber reinforcing material, or a general resin layer on one side of the fiber reinforcing material, a known method may be used. A method of bonding the resin layer to the fiber reinforcing material through an adhesive such as urethane, epoxy, or silicon-modified is mentioned.
[0019]
As the adhesive layer used in the present invention, an acrylic resin, an acrylic-silicon resin, an epoxy-silicon resin, a silicon-modified resin, a urethane resin, an epoxy resin in which silicon, polysiloxane, or colloidal silica is introduced by a commonly practiced method, Examples thereof include polyester resins and alkyd resins. Silicon-modified resins including acrylic-silicon resins and epoxy-silicon resins are excellent in terms of durability, and are particularly preferable.
[0020]
When the resin of the adhesive layer is a silicon-modified resin such as an acrylic-silicon resin or an epoxy-silicon resin, as a method for introducing silicon into the resin, a transesterification reaction, a graft reaction using a silicon macromer or a reactive silicon monomer , Hydrosilylation reaction, block copolymerization method and the like.
[0021]
When the resin of the adhesive layer contains polysiloxane, it is preferable that the polysiloxane is a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product formed from the hydrolyzate. When the number of carbon atoms of the alkoxy group of the silicon alkoxide exceeds 6, it is expensive and the hydrolysis rate is very slow, so that it is difficult to cure in the resin.
[0022]
As a method for introducing polysiloxane into acrylic-silicon resin and epoxy-silicon resin, a method in which a silicon alkoxide monomer is mixed into a resin solution and hydrolyzed with moisture in the air when forming an adhesive layer, silicon alkoxide in advance is partially Examples include a method of mixing the hydrolyzed product with a resin and further hydrolyzing with moisture in the air when forming the adhesive layer. Any known method may be used as long as it can be uniformly mixed with the resin.
[0023]
In the present invention, as a method of providing an adhesive layer on the surface of a vinyl chloride resin containing a polymer plasticizer, an adhesive layer resin solution is applied by a roll coater, a gravure coater, dipping, spray spraying or the like. And a method of drying. The thickness of the adhesive layer is preferably 0.5 μm or more.
[0024]
Examples of the photocatalyst in the photocatalyst layer used in the present invention include TiO ₂ , ZnO, SrTiO ₃ , CdS, GaP, InP, GaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO ₂ , and the like, and these photocatalysts include Pt, Rh, RuO ₂ , Nb, Cu, Examples thereof include metals such as Sn, Ni, and Fe, and those added with these metal oxides.
[0025]
In the present invention, as a method for forming the photocatalyst layer on the adhesive layer, for example, a suspension in which the photocatalyst is dispersed in a metal oxide gel or metal hydroxide gel solution is used in the same manner as that for providing the adhesive layer. By applying, the photocatalyst layer can be formed on the adhesive layer. Also, the photocatalyst is dispersed in the state of a metal oxide gel or metal hydroxide gel precursor solution, and when coated onto the adhesive layer, it is hydrolyzed or neutralized to form a sol or gel to form a photocatalyst layer You may let them.
[0026]
As the thickness of the photocatalyst layer used in the present invention, a thickness of 0.1 μm to 5 μm is preferable because it exhibits high photocatalytic activity and exhibits translucency, and the catalyst layer becomes inconspicuous. The photocatalytic activity is higher when the photocatalyst layer is thicker, but hardly changes when the thickness exceeds 5 μm. When the thickness is less than 0.1 μm, the translucency is improved, but the ultraviolet light used by the photocatalyst is also transmitted, so that a high photocatalytic activity cannot be expected.
[0027]
【Example】
[0028]
Hereinafter, the present invention will be specifically described with reference to the accompanying drawings, examples, and comparative examples. In addition, this invention is not limited only to these Examples.
[0029]
Example 1
The sheet material having a photocatalytic function according to this embodiment is as shown in FIG. 1, and includes a fiber reinforcing material 1, a vinyl chloride resin layer 2 containing a polymer plasticizer, an adhesive layer 3, and a photocatalyst layer 4. And the resin layer 5.
[0030]
The fiber reinforcement 1 is a glass fiber fabric (manufactured by Kanebo Corporation, KS2478, mass 325 g / m ² ). This glass fiber fabric 1 is made of ECDE75 1/2 glass yarn with a plain weave with a warp density of 29/25 mm and a weft density of 29/25 mm. A vinyl chloride resin layer containing a polymer plasticizer containing 100 parts by weight of a polymer plasticizer (made by Mitsui DuPont Polychemical, trade name: Elvalloy) on one side of the glass fiber fabric 1 with respect to 100 parts by weight of the vinyl chloride resin. The vinyl chloride resin layer 5 containing a liquid plasticizer containing 70 parts by weight of 2 and DOP which is a normal liquid plasticizer with respect to 100 parts by weight of the vinyl chloride resin was bonded via a urethane-based adhesive (not shown). . A polysiloxane (manufactured by Corcote Co., Ltd., trade name) was added to an isopropanol-ethyl acetate (50/50) solution containing 10% by weight of an acrylic-silicone resin having a silicon content of 3% by weight on one side of the sheet material. A solution obtained by adding 20% by weight of methyl silicate 51) to the acrylic-silicone resin together with a surfactant was applied with a roll coater and dried to obtain an adhesive layer 3. Thereafter, a solution in which a nitric acid acidic titania sol having a titanium oxide content of 5% by weight is dispersed in a nitric acid acidic silica sol having a silicon oxide content of 5% by weight with a surfactant is applied with a roll coater and dried to be a photocatalyst. Layer 4 was obtained.
[0031]
Comparative Example 1
Instead of the vinyl chloride resin layer containing the polymer plasticizer of Example 1, a vinyl chloride resin containing a liquid plasticizer containing 70 parts by weight of DOP which is a normal liquid plasticizer with respect to 100 parts by weight of the vinyl chloride resin. A sheet material was obtained in the same manner as in Example 1 except that the layer was used.
[0032]
Comparative Example 2
A vinyl chloride resin layer containing DOP which is a normal liquid plasticizer on both sides of Kanebo Co., Ltd. B-type membrane sheet, glass fiber fabric (Kanebo Co., Ltd., KS2478, mass 325 g / m ² ). Are bonded to each other through an adhesive and an acrylic antifouling treatment is applied to one side thereof as Comparative Example 2.
[0033]
<Evaluation of antifouling properties>
The sheet materials of Example 1 and Comparative Examples 1 and 2 were cut to a width of 30 cm and a length of 80 cm, set on an outdoor exposure table at a south surface and an angle of 45 °, and the state of surface contamination after one month was stored in a cool and dark place. This was compared with a comparative sample that was not exposed outdoors.
(○: not dirty, △, slightly dirty × quite dirty)
[0034]
<Evaluation of curing degree of sheet material>
The sheets of Example 1 and Comparative Examples 1 and 2 were cut to a width of 30 cm and a length of 80 cm, set on an outdoor exposure table at a south surface and an angle of 45 °, and after one month, the texture of the sheets was cooled in a dark place. Compared with each comparison sample that had been stored outdoors and not exposed outdoors.
(○: no change in texture compared to the comparative sample, △: the texture is somewhat harder than the comparative sample, × the texture is considerably harder than the comparative sample (= hardened))
[0035]
The above Example 1 and Comparative Examples 1 and 2 are summarized in Table 1.
[0036]
[Table 1]

Compared with Comparative Examples 1 and 2, Example 1 is an excellent photocatalytic functional sheet material with no change in texture in terms of antifouling properties and curability.
[0037]
【The invention's effect】
As described above, the present invention, that is, the photocatalyst is formed on the surface of a vinyl chloride resin containing a polymer plasticizer through an adhesive layer, thereby holding a conventional vinyl chloride resin containing a normal liquid plasticizer. The occurrence of initial contamination due to the diffusion of the plasticizer component and the problem of curing the vinyl chloride resin layer are improved, and a very excellent photocatalytic functional sheet material is obtained.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view of a sheet material having a photocatalytic function of the present invention on one side.
FIG. 2 is a schematic sectional view of a sheet material having the photocatalytic function of the present invention on both sides.
FIG. 3 is a schematic sectional view of a sheet material having the photocatalytic function of the present invention on one side.
[Explanation of symbols]
1: Fiber reinforcing material 2: Vinyl chloride resin layer containing polymer plasticizer 3: Adhesive layer 4: Photocatalyst layer 5: Vinyl chloride resin layer containing liquid plasticizer

Claims (1)

A resin layer made of a vinyl chloride resin containing a polymer plasticizer, an adhesive layer, and a photocatalyst layer are sequentially provided on one side of a fiber reinforcement made of glass fiber fabric,
A resin layer is provided on the other side of the fiber reinforcement,
A resin layer made of a vinyl chloride resin containing the polymer plasticizer is bonded to the fiber reinforcing material via an adhesive of urethane type, epoxy type, or silicon modified type,
The polymer plasticizer is an ethylene / vinyl acetate / carbon monoxide copolymer, an ethylene / (meth) acrylic ester / carbon monoxide copolymer, or an ethylene / vinyl acetate copolymer. And
The polymer plasticizer is blended in an amount of 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
The adhesive layer, acrylic introduced silicon or polysiloxane or colloidal silica - silicon resin, or epoxy to introduce silicon or polysiloxane or colloidal silica - Ri Do a silicon resin,
The resin layer provided on the other surface of the fiber reinforcing material is made of a vinyl chloride resin containing a liquid plasticizer, and the fibers are bonded via any one of urethane-based, epoxy-based, and silicon-modified adhesives. A photocatalytic functional sheet material characterized by being bonded to a reinforcing material .

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