JP4229232B2 - Washable and reusable biodegradable mesh sheet - Google Patents

Description

  The present invention relates to a woven / knitted base fabric composite mesh sheet which is mainly used for a sheet for industrial materials, and whose disposal processing does not depend on incineration, and even if it is landfilled, the environmental load is as small as possible. More specifically, for example, a mesh sheet for building construction having biodegradability that can be landfilled and used in general building construction such as building construction, condominium construction, house construction, and renovation work, or demolition work, The present invention relates to a mesh sheet for construction work that can be repeatedly used by washing in use.

At building construction sites such as building construction, condominium construction, house building, and renovation work, or demolition work, the entire building is covered and seated, and the safety of building work and safety measures around the construction site Is planned. In particular, construction sites require work environments such as daylighting and ventilation, and mesh sheets are often used for these curing sheets. This mesh sheet has the flameproof performance of Article 4 (JIS L1091A method) of the Fire Services Act construction regulations and the performance (tensile strength x elongation, tensile strength, Satisfies the strength of the fastening portion and the penetration resistance test by dropping the steel pipe. Generally, a curing mesh sheet is a fiber reinforced composite obtained by using a synthetic fiber fabric as a base material and coating the synthetic fiber fabric with the synthetic fiber fabric. Usually, a curing mesh sheet is a coarse plain fabric with polyethylene terephthalate (PET) fiber yarns as warp and weft covered with soft polyvinyl chloride resin, 1.8m wide x 3.6m long Or, a sewing product having a size of width 1.8 m × length 5.4 m is frequently used. In particular, the soft polyvinyl chloride resin itself has a high degree of flame retardancy, and since it contains a plasticizer, it has excellent processability and durability, so that it can be used as a cured mesh sheet. It is a material suitable for industrial material sheets.
Cured mesh sheets processed with soft polyvinyl chloride resin are usually used for 1 to 6 months at the construction site, but the entire cured sheet is lightly soiled due to dust stains adhering to the mesh part. Paint spray may scatter and get dirty. However, even if the surface is dirty, the performance of the cured mesh sheet itself is not affected, so the cured mesh sheet that was removed after the building was completed was specially washed with an alkaline detergent by the contractor before the next construction. It is reused (used as lease) for on-site fences. Thus, the cured mesh sheet loses its durability each time it is repeatedly used, and eventually becomes unable to satisfy the temporary industry association certification standard value. By the way, in the industrial waste treatment of polyvinyl chloride resin products, incineration treatment is regulated from the viewpoint of dioxin generation, and in addition to landfill treatment, domestic industrial waste disposal sites have recently become insufficient, and new disposal It is becoming more difficult to create new venues that are very difficult to convince local governments and residents. This is because the environmental impact of plastic products such as these polyvinyl chloride resins that remain permanently in the soil without rot, and concerns about ecosystem pollution caused by chemicals added to plastics. Because it is held. Therefore, recent plastic products have been desired to be those that have as little environmental impact as possible when disposed of and that can be recycled and are easy to use.

  On the other hand, for waste plastics that are molded PVC resin products that are determined to be reusable, compression-molded products of these crushed products are molded into plates or rods. It is used for a few applications as piles and suspicious trees, but the curing mesh sheet contains fiber fabric and is difficult to pulverize, and at the same time it is used outdoors for a long period of time, and the dirt is strong. As for the sheet waste material that has adhered and the resin coating layer has deteriorated, the fact is that such reuse is also avoided. Recently, in the field of industrial material sheets, attempts have been made to replace soft polyvinyl chloride resin with non-vinyl chloride resin in consideration of chemical substances such as hormone-disturbing substances and dioxins, and disposal problems. For example, a curing mesh sheet using a polyethylene resin, a polypropylene resin, a polyurethane resin, or the like has been proposed. Curing mesh sheets made of these non-vinyl chloride resins do not have the risk of generating dioxins or hydrogen halide gas even when incinerated, but they are extremely troublesome because they contain many additives such as flame retardants. As a result, it is disposed of in the landfill in the same manner as a general curing mesh sheet made of soft polyvinyl chloride resin, and no special separation and collection are performed. Especially for polyolefin resins such as polyethylene resins and polypropylene resins that are frequently used as substitutes for soft polyvinyl chloride resin, because of its excellent corrosion resistance and bacteria resistance, when landfill treatment is performed, The contradiction that it stays in the soil for a longer time than the polyvinyl chloride resin product is apparent. Therefore, even if a curing mesh sheet made of non-vinyl chloride resin is used, it is still not the actual situation that the environmental burden can be reduced by the landfill treatment.

Recently, biodegradable plastics have been actively used as a means to alleviate these waste problems, and as a measure to reduce the environmental burden of industrial material sheets as well as the convenience of landfill disposal, curing sheets can be used. For example, Japanese Patent Application Laid-Open No. 9-1703 (Patent Document 1) discloses a biodegradable fiber composite sheet. Since it cannot be obtained, it cannot be used as a curing sheet. Japanese Patent Application Laid-Open No. 2001-303388 (Patent Document 2) shows a mesh sheet for construction work made of a woven fabric made of a fiber made of flame retardant by blending a flame retardant with polylactic acid fiber. Since this mesh sheet is a woven fabric not coated with resin, even if the weaving structure is changed to a plain structure, imitation structure, kneading structure or the like, misalignment occurs in the folded part of the mesh sheet. In the washing process, misalignment occurred on the entire surface of the sheet, which was not suitable for repeated use. Furthermore, since this mesh sheet covers the amount of flame retardant added to the fiber in order to maintain the fiber strength, the flameproof property is essentially insufficient. In JP-A-2001-303391 (Patent Document 3), weaving is performed using core-sheath fibers composed of aliphatic polyesters having different melting points and containing a flame retardant, and this is heat-set to prevent misalignment. A (mesh) sheet for building construction with a woven fabric is disclosed. However, even this (mesh) sheet is unsatisfactory in the effect of preventing misalignment, and does not have the repetitive washability particularly required for lease use. In addition, among the performances required for the mesh sheet for construction work, which are stipulated by the temporary industry association certification standard, it was not possible to satisfy the fitting portion strength and the penetration resistance test by dropping the steel pipe. In the mesh sheet obtained by kneading a flame retardant into these fibers, it is difficult to conveniently maintain a balance between flame resistance and fiber strength.
Japanese Patent Laid-Open No. 2001-303387 (Patent Document 4) discloses a construction sheet and a mesh sheet in which a flame-retardant polylactic acid fiber fabric is provided with a biodegradable polymer compound having flame retardancy. However, the flame retardant to be used for this (mesh) sheet is described in [0007] as follows: "~ If the flame retardant can be removed by washing after use of the sheet, it can be used according to its use. Because the flame retardant is removed during washing as described in "Can be done", these mesh sheet laundry products lack the flameproof performance of Article 4 (JIS L1091A method) of the Fire Service Act. Cannot be reused according to the rules. Even if the sheet has a biodegradability, it may cause a vicious cycle of sprinkling waste and putting a burden on the landfill process when the use of a single wash is limited. It might be. Therefore, the mesh sheet of Patent Document 4 did not have the repetitive washability necessary for lease use. JP 2003-211592 A (Patent Document 5) is provided with a resin coating layer containing a decomposable polymer material containing a flame retardant organic substance on a base fabric made of a fabric containing a degradable polymer material fiber. Although a decomposable composite sheet is disclosed, this decomposable composite sheet does not have sufficient washing resistance.

JP-A-9-1703 (all pages) JP 2001-303388 A (all pages) JP 2001-303391 A (all pages) JP 2001-303387 A (all pages) JP 2003-215992 A (all pages)

  Although the above-mentioned architectural curing mesh sheet having biodegradability described in [Patent Documents 2 to 5] is provided with flameproofing properties, any architectural curing mesh sheet is absolutely free from washing resistance on the premise of repeated use. There is no consideration. Therefore, even if these building-curing mesh sheets having biodegradability are put into practical use, washing after use may cause misalignment of the entire mesh sheet, resulting in problems in strength, and imparting flame retardancy. The used flame retardant component was removed by washing, and as a result, flame resistance was impaired, and none of the mesh sheets could be reused by washing. The problem of the present invention is that it can be used for mesh sheets for construction work, and can be reused without causing a drop in fireproofing and strength due to washing during use, and can be reclaimed in landfill during disposal. The object is to provide a biodegradable mesh sheet that can be used.

  As a result of repeated research and examination to solve the above-mentioned problems, the present invention i). 5 microencapsulated flame retardant imparting agent is added to 100 parts by mass of biodegradable resin on the entire surface of a mesh-like woven / knitted base fabric formed by weaving and knitting multifilament yarns having biodegradability and forming voids. A mesh-like composite formed by impregnating a coating layer of a flame-retardant composition containing ˜75 parts by mass into a capillary gap between filaments of a multifilament yarn at a specific ratio and fixing the filaments to each other; ii). The outermost coating with a flame retardant composition mainly composed of a biodegradable resin containing 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin on the entire surface of the mesh composite. A multi-layer mesh composite with layers, iii). A mesh-shaped woven / knitted base fabric, which is formed by weaving and knitting multifilament yarns having biodegradability and forming mesh spaces, is subjected to a pretreatment containing a microencapsulated flame retardant, and the entire surface of the pretreated base fabric In addition, a coating layer made of a flame retardant composition containing 5 to 75 parts by mass of melamine flame retardant particles is impregnated into a capillary gap between filaments of a multifilament yarn at a specific ratio with respect to 100 parts by mass of a biodegradable resin. The mesh-like composite obtained by fixing the filaments to each other can be reused without washing, resulting in a reduction in flameproofing and strength due to washing. The present invention was completed by finding that it can be reused.

That is, the laundry reusable biodegradable mesh sheet (1) of the present invention is produced from a mesh-like woven or knitted fabric that is manufactured by weaving and knitting multifilament yarn having biodegradability, and having a mesh void. A mesh-like composite having a base fabric, and a covering layer made of a flame retardant composition mainly composed of a biodegradable resin, covering the entire exposed surface of the multifilament yarn constituting the base fabric, The flame-retardant composition forming the coating layer contains 5 to 75 parts by mass of a microencapsulated flame-retardant imparting agent with respect to 100 parts by mass of the biodegradable resin, and the filament of the multifilament yarn impregnating the MakeHoso voids are fixed filaments with each other,
The microencapsulated flame retardant imparting agent is at least one biodegradable resin selected from a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer) resin, and a polyvinyl alcohol (copolymer) resin. One or more nitrogen atom-containing compounds selected from urea derivatives, guanidine derivatives, and melamine salts, or phosphates, metal (organic) phosphates, phosphate ester derivatives, phosphones It consists of 1 or more types of the microcapsule containing the 1 or more types of phosphorus atom containing compound chosen from the acid type compound and the phosphinic acid type compound .
In the reusable biodegradable mesh sheet (1) of the present invention, an outermost coating layer made of a flame retardant composition mainly comprising a biodegradable resin is further formed on the entire surface of the mesh composite. It is preferable that the outermost coating layer contains 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin.
The reusable biodegradable mesh sheet (2) of the present invention comprises a base fabric comprising a mesh woven or knitted fabric in which mesh spaces are formed by weaving and knitting multifilament yarn having biodegradability, A mesh-like composite having a coating layer formed of a flame retardant composition mainly composed of a biodegradable resin on the entire surface of the base fabric, wherein the base fabric contains a microencapsulated flame retardant imparting agent. The flame retardant composition that has been subjected to a pretreatment with a treatment agent and that forms the coating layer contains 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. And, impregnating the capillary gap between the filaments of the multifilament yarn to fix the filaments together,
The microencapsulated flame retardant imparting agent is at least one biodegradable resin selected from a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer) resin, and a polyvinyl alcohol (copolymer) resin. One or more nitrogen atom-containing compounds selected from urea derivatives, guanidine derivatives, and melamine salts, or phosphates, metal (organic) phosphates, phosphate ester derivatives, phosphones It consists of 1 or more types of the microcapsule containing the 1 or more types of phosphorus atom containing compound chosen from the acid type compound and the phosphinic acid type compound .
In the reusable biodegradable mesh sheet (1) or (2) of the present invention, the mesh porosity of the mesh composite is preferably 5 to 50%.
In the reusable biodegradable mesh sheet (1) or (2) of the present invention, the multifilament yarn having biodegradability is composed of a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer). It is preferably a yarn having a fineness of 227 to 2222 dtex composed of one or more selected from a resin and a polyvinyl alcohol (copolymer) resin, or a mixed yarn of these and regenerated cellulose fibers.
In the reusable biodegradable mesh sheet (1) or (2) of the present invention, the biodegradable resin forming the coating layer is made of a polylactic acid (copolymer) resin, an aliphatic polyester (co-polymer). Polymerization) It is preferably made of at least one selected from resins and polyvinyl alcohol (copolymerization) resins.
The reusable biodegradable mesh sheet of the present invention containing melamine flame retardant particles, wherein the melamine flame retardant particles are a composite of melamine cyanurate, melamine sulfate, (poly) phosphate compound and melamine derivative. It is preferable that it is 1 or more types selected from the thing.
In the reusable biodegradable mesh sheet (1) or (2) of the present invention, the ratio of the mass of the base fabric to the mass of the mesh composite is preferably 40 to 80%. .
In the reusable biodegradable mesh sheet (1) or (2) of the present invention, the mesh-shaped knitted fabric is any one of plain weave, imitation fabric, cocoon fabric, Russell fabric, and triaxial fabric. there it is preferable.
In the reusable biodegradable mesh sheet (1) or (2) of the present invention, the multifilament yarn is impregnated and fixed into a capillary space between filaments of the multifilament yarn by the flame retardant composition. It is preferable that the material is impregnated and fixed at a solidity rate of 75 to 100% from the outside with respect to at least the weft radius of the cross section .

Architectural curing mesh sheets (1) and (2) obtained by the present invention are defined in the fire prevention performance Article 4 (JIS L1091A method) of the Fire Service Act, JIS A8952 and the Temporary Industry Association Certification Standard. While satisfying the performance (penetration resistance test by dropping steel pipe, etc.), when disposing it, the mesh sheet decomposes over time due to the landfill process, and eventually the entire mesh sheet disappears from the soil. It is an extremely useful industrial material sheet in modern Japan where industrial waste disposal sites are lacking. Although mesh sheets having biodegradability have been proposed in the past, these mesh sheets cannot withstand the harsh washing for washing dirt, and have flame resistance that was initially possessed after washing. However, in the present invention, it should be noted that these mesh sheets have washing resistance. It is possible to repeatedly use it at the construction site by maintaining the initial flameproofness even after washing, that is, the building curing mesh sheet obtained by the present invention has durability and durability during use that did not exist conventionally. It is an extremely useful industrial material sheet that combines biodegradability after use.

Washing reusable biodegradable mesh sheet of the present invention (1) is, i). 5 microencapsulated flame retardant imparting agent is added to 100 parts by mass of biodegradable resin on the entire surface of a mesh-like woven / knitted base fabric formed by weaving and knitting multifilament yarns having biodegradability and forming voids. A mesh-like composite formed by impregnating a capillary gap between filaments of a multifilament yarn with a coating layer made of a flame retardant composition containing ~ 75 parts by mass, and fixing the filaments together; or ii). Further on the entire surface of the mesh composite, the outermost coating with a flame retardant composition mainly comprising a biodegradable resin containing 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. A biodegradable mesh sheet (2) which is a multi-layer mesh composite having a layer and is reusable in the present invention is iii). A mesh-shaped woven / knitted base fabric, which is formed by weaving and knitting multifilament yarns having biodegradability and forming mesh spaces, is subjected to a pretreatment containing a microencapsulated flame retardant, and the entire surface of the pretreated base fabric In addition, a capillary layer between filaments of a multifilament yarn is impregnated with a coating layer of a flame retardant composition containing 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. It is a mesh-like composite obtained by forming so as to fix each other.

A multifilament yarn having biodegradability is used for the yarn constituting the mesh woven or knitted fabric used in the present invention. The biodegradable yarn has a fineness of 277 to 2222 dtex of at least one selected from polylactic acid (copolymer) resin, aliphatic polyester (copolymer) resin, and polyvinyl alcohol (copolymer) resin. Multifilament yarns are preferable, and these are cultivated by microorganisms under specific environmental conditions, and the microorganisms cleave the bond between the main chain and side chain of the resin constituting these yarns, thereby reducing the molecular weight. At the same time, microorganisms accumulate and metabolize these low-molecular compounds as their own nutrients, so that these high-molecular compounds are eventually decomposed into CO ₂ and H ₂ O.

Examples of the polylactic acid-based (copolymerization) resin include a polylactic acid resin having an average molecular weight of 10,000 or less obtained by dehydration polymerization of lactic acid, and a lactide that is a cyclic dimer of L-lactic acid (obtained by lactic acid fermentation of glucose). High molecular weight polylactic acid resin (-OCHCH ₃ CO-) _n obtained by ring-opening polymerization of (trade name: Lacty / Shimadzu Corporation, trademark: Lacia / Mitsui Chemicals, Inc., trademark: Lactron / Kanebo Co., Ltd., etc. ), Polyglycolic acid (aliphatic polyester resin) having an (O—CH ₂ —CO—) unit, a copolymer resin of lactic acid and glycolic acid, a copolymer resin of lactic acid and butyric acid, lactic acid and valeric acid Polylactic acid-based copolymers such as copolymer resins of lactic acid and malic acid, copolymer resins of lactic acid and caprolactam, and copolymers of glycolic acid and lactones If the resin is preferably used as a multifilament yarn material.

The aliphatic polyester (copolymer) resins, aliphatic polyols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol) and aliphatic dicarboxylic acids (adipic acid, succinic acid, sebacic Aliphatic polyester resins obtained by polycondensation with acids, etc. (Trademark: Bionore / Showa High Polymer Co., Ltd., Trademark: Lunare / Nippon Shokubai Co., Ltd., Trademark: Upec / Mitsubishi Gas Chemical Co., Ltd.), cyclic Aliphatic polyester resin based on ω-hydroxy acid obtained by ring-opening polymerization of esters (lactones such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone) (trademark: Cellgreen PH / Daicel Chemical Industries, Ltd.) )) And aliphatic polyester-based copolymer resins as aliphatic short-chain ester-based polyester resins. (Dihydroxypolyethylene adipate) and aliphatic diisocyanate (hexamethylene diisocyanate) polycondensate, polyester-ether copolymer resins, specifically cyclic ester-ether ring-opening polymer, cyclic ether and cyclic ester- Ring-opening copolymer with ether, ring-opening copolymer of cyclic acid anhydride and excess cyclic ether, ring-opening polymer of cyclic ester with polyether oligomer, condensation polymer between telechelic oligomer, bicyclic lactone And acetal-ester type polyester resins having a tetrahydropyran ring obtained by ring-opening polymerization of ethers, and ether-ester type polyester resins, or polyester resins having a tetrahydrofuran ring obtained by ring-opening polymerization of bicyclic lactones. Further, polyester-carbonate copolymer resins, which are specifically ring-opening polymers such as cyclic trimethylene carbonate and 2,2-dimethyltrimethylene carbonate, and copolymers of these carbonates and lactones, And a copolymer of carbonate and ethylene oxide. Also, polyester-amide copolymer resins, which are specifically cyclic ester-amide ring-opening polymer, ring-opening copolymer of cyclic ester and cyclic amide (lactam), aliphatic polyester and polyamide (nylon) And interpolymer transesterification products, and α-pyrrolidone, ε-caprolactam and ω-laurolactam are used as cyclic amides, and δ-valerolactone, ε-caprolactone and the like are used as lactones. However, a copolymer of ε-caprolactam and ε-caprolactone is particularly preferable from the viewpoints of mechanical properties and biodegradability.

As the aliphatic polyester-based (copolymerization) resin, it is preferable to use a microbial-produced polyester-based compound synthesized by microorganisms (bacteria) in the microbial cells and stored in granular form in the microbial cells. Poly having hydroxyalkanoic acid as a monomer unit such as butyric acid (3HB), 3-hydroxyvaleric acid (3HV), 3-hydroxypropionic acid (3HP), 4-hydroxybutyric acid (4HB) and a carboxylic acid having 3 to 5 carbon atoms (Hydroxyalkanoate: PHA), PHA is stored in the body of microorganisms, decomposes by microorganisms themselves when they encounter starvation, and is metabolized and consumed as an energy source for life activity. Further, a poly (hydroxyalkanoate-based polyester resin (for example, poly-4-hydroxybutyric acid: trademark Biogreen / Mitsubishi Gas Chemical Co., Ltd.) obtained by polymerizing these alone or two or more monomers is polymerized. Poly (hydroxyalkanato) -based polyester resin, etc. In the present invention, in particular, poly (3HB-co-3HV: trademark Biopol / Nihon Monsanto Co., Ltd.), which is a copolymer resin of 3HB and 3HV, Trademark Biofan / Gunze Co., Ltd.) Poly (3HB-co-4HB), which is a copolymer resin of 3HB and 4HB, can be preferably used as the multifilament yarn.

  As a polyvinyl alcohol-based (copolymerization) resin, a polyvinyl alcohol resin obtained by saponifying (saponifying degree 77 to 99 mol%) a polyvinyl acetate resin as a precursor, and a polyvinyl acetate resin copolymer Resins (for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid and esterified products thereof, maleic anhydride and ring-opened products thereof, vinyl compounds such as vinyl pyrrolidone and vinyl pivalate, and carbon number of 4 or more. Examples thereof include polyvinyl alcohol-based copolymer resins obtained by saponifying a precursor of a copolymer of the fatty acid with a vinyl ester of a fatty acid. In particular, a polyvinyl alcohol (based) resin is excellent in mechanical strength and biodegradability, and is preferable as a resin used for a multifilament yarn.

  The polylactic acid (copolymer) resin, aliphatic polyester (copolymer) resin, and polyvinyl alcohol (copolymer) resin are mainly degradable by microorganisms such as bacteria, bacteria, and molds. Furthermore, it is preferable to have hydrolyzability that promotes degradability by these microorganisms in the presence of moisture. Particularly in a polylactic acid-based (copolymerized) resin and an aliphatic polyester-based (copolymerized) resin, the molecular structure that particularly increases the hydrolysis efficiency has an ester bond (—COO—) content of 40 to 80 in the unit structure. Those having an atomic weight%, particularly 45 to 76 atomic weight% are preferred.

  In the present invention, the biodegradable multifilament yarn may be used in combination with regenerated cellulose fiber. The regenerated cellulose fiber is separated from plants such as flax, cotton, grass, kenaf, bamboo, and bark. Cellulose acetate (cellulose) obtained by esterifying the hydroxyl group of purified cellulose, cellulose nitrate (celluloid), cellulose derivatives such as methylcellulose and carboxymethylcellulose obtained by etherifying the hydroxyl group of cellulose, and cellulose treated with carbon disulfide Examples thereof include fibers spun from xanthate and regenerated cellulose obtained by acidifying xanthate, which are mixed with the biodegradable multifilament or the biodegradable multifilament yarn. As an external regenerated cellulose fiber In coated covering yarn can be used in the form of such core spun yarns. This mixed use of the regenerated cellulose fiber is effective for impregnating the capillary space of the multifilament yarn. The mixing ratio of the regenerated cellulose fiber is preferably within 100% by mass, particularly 10 to 50% by mass, based on the biodegradable multifilament yarn. When the mixed ratio of regenerated cellulose fibers exceeds 100% by mass, the resulting mesh sheet has the performance defined by JIS A8952 and the temporary industry association certification standards (tensile strength x elongation, tensile strength, strength at the fitting part) , A penetration resistance test by dropping a steel pipe) may not be satisfied.

  The biodegradable multifilament yarn is obtained by heating the above-described biodegradable resin to a temperature equal to or higher than the melting temperature (melting point) to form a fluid, viscous melt and liquefying it from a spinneret having pores having a specific diameter. It can be produced using a known melt spinning method and equipment which are extruded and rapidly cooled and solidified to obtain a continuous fiber spinning base yarn. A biodegradable resin suitable for this production method is preferably a polylactic acid-based copolymer resin having a melting point of 120 ° C. or higher and a fiber strength from the viewpoint of spinnability. A polylactic acid multifilament yarn obtained by copolymerizing 1 to 10% by mass of 20000 polyethylene glycol is preferred. In addition, multifilament yarns (50 to 300 filaments) that are drawn by heating or cold drawing and then twisted can be preferably used. Moreover, the multifilament yarn may have a core-sheath layer structure made of the above-described biodegradable resins having two different cross-sections, ie, a core-sheath. The fineness of these biodegradable multifilament yarns is preferably in the range of 277 to 2222 dtex, particularly in the range of 277 to 1111 dtex, and two or three yarns of 277 to 2222 dtex can be used. It can also be used as a twisted product.

For the production of polyvinyl alcohol (copolymerized) resin yarn (multifilament yarn), an organic solvent-based wet cooling gel spinning method is preferred. This method uses polyvinyl alcohol (copolymerized) resin as dimethyl sulfoxide, N - methyl-2-pyrrolidone, N, N ^'- as a spinning stock solution obtained by dissolving in a polar organic solvent such as dimethylacetamide, which was dissolved in methanol, wet spinning into a poor solvent bath, such as ethanol or by dry-wet spinning, In this method, solvent removal and coagulation is performed, and the obtained spinning yarn is subjected to wet drawing, followed by drying and heat treatment. Polyvinyl alcohol yarn used in the present invention has a melting point of 150 to 200 ° C. and a saponification degree of 77 to 99 mol%, particularly 92 to 98 mol% with respect to 100 mol% of vinyl acetate. It is preferable in terms of practical strength and biodegradability.

  The base fabric used in the present invention, that is, a mesh-like woven or knitted fabric woven and knitted with a multi-filament yarn having biodegradability as warp and weft, and the mesh void ratio (missing area ratio) of the mesh-like woven or knitted fabric is Coarse fabrics in the range of 5-50%, preferably 10-35% can be used. As the multifilament yarn constituting the mesh woven or knitted fabric used in the present invention, a yarn having a fineness of 277 to 2222 dtex can be used. These yarns may be used alone, or two to three are twisted to form one yarn, and two are arranged in parallel to make one apparent yarn (Basket weaving) It can be used in a configuration in which three yarns are arranged in parallel to make up one apparent yarn (pattern weaving). In the case of an architectural curing mesh sheet (Category 2), for example, a mesh-like woven or knitted fabric in which 24 to 26 warp yarns and 25 to 28 weft yarns per inch are laid with 277 dtex multifilament yarns, 1 556 dtex multifilament yarn is 1 A mesh woven or knitted fabric in which 18 to 20 warp yarns and 18 to 20 weft yarns are driven is preferable. In the case of an architectural curing mesh sheet (Category 1 type), for example, a yarn composed of 3 multifilament yarns of 833 dtex is 1 10 to 12 warp yarns per inch, mesh woven or knitted fabric driven with 10 to 12 weft yarns, mesh consisting of 6 to 8 warp yarns and 6 to 8 weft yarns per inch, made of 1111 dtex multifilament yarns Woven and knitted fabric, 2222 dtex multifilament yarns from 12 to 12 warps per inch Mesh, woven or knitted fabric with 4 to 12 weft yarns, mesh woven or knitted fabric with 15 to 17 warp yarns per inch and 15 to 17 weft yarns per inch, 2222 dtex multifilament yarn 2 A mesh woven or knitted fabric in which 4 to 5 warp yarns and 4 to 5 weft yarns are printed per inch is preferable in a penetration resistance test by dropping a steel pipe as defined in JIS A8952.

  Either a woven fabric or a knitted fabric can be used for the mesh-like woven or knitted fabric used in the present invention, and examples of the woven fabric include plain woven fabric, twill woven fabric, satin woven fabric, imitation woven fabric, and cocoon woven fabric. Russell knitted fabric can be preferably used as the knitted fabric. These mesh woven fabrics can be woven using a known loom such as a shuttle loom, a shuttleless loom (rapier method, gripper method, water jet method, air jet method). As the mesh woven or knitted fabric used in the present invention, plain weave, imitation woven fabric, cocoon woven fabric, and Russell knitted fabric are the most versatile, and excellent in balance of longitudinal physical properties and tear strength are preferable. A triaxial woven fabric can also be used for the mesh woven or knitted fabric used in the present invention. The triaxial woven fabric is a woven fabric which is composed of three-direction yarns and is woven so that triangular or hexagonal mesh voids are formed by entanglement of the yarns. In particular, a triaxial woven fabric includes warp, and a woven fabric formed by entwining a bi-directional bias (slanted) yarn is preferable because of excellent dimensional stability in the processing direction. The structure of this triaxial woven fabric can also be a basket weave (hexagonal mesh) by applying two twills. In particular, by using a triaxial woven fabric in the present invention, the mesh sheet obtained by the present invention can be provided with a stable resistance against external forces from multiple directions. A high mesh sheet can be obtained. There is no particular limitation on the number of warp yarns or weft yarns and bias yarns driven in the mesh woven or knitted fabric by these triaxial woven fabrics, but multifilament yarns of 277 to 2222 dtex in each direction are 4 to 30 yarns per inch, preferably 7 A mesh-like woven or knitted fabric obtained by implanting -24 pieces can be used.

The mesh porosity (knitting area ratio) of these mesh woven or knitted fabrics used in the present invention is preferably 5 to 50%, particularly preferably 10 to 35%. The mesh porosity is a part where the fiber yarns are entangled, and the mesh porosity is a value relative to the unit area of the mesh woven or knitted fabric. If the mesh porosity is less than 5%, the resulting mesh sheet is inferior in transparency and air permeability. If the mesh porosity exceeds 50%, the strength and dimensional stability of the mesh sheet obtained are insufficient. Therefore, the performance (tensile strength × elongation, tensile strength, strength at the fitting portion, penetration resistance test by dropping the steel pipe) defined in JIS A8952 and the temporary industry association certification standard may not be satisfied. Also, it may become misaligned by washing and cannot be reused. The mesh porosity can be obtained as a value obtained by subtracting 100 from the unit area of the mesh woven or knitted fabric, which is obtained by calculating the area occupied by the fiber yarn as a percentage. (For example, the unit void ratio can be 100 cm ² by 10 cm in the warp direction × 10 cm in the weft direction.) As a particularly simple method, the warp direction is obtained by printing a mesh woven or knitted fabric using a commercially available copying machine. Cut out a square (2.54 cm x 2.54 cm in the weft direction) and cut out the printed portion (square) of the mesh woven or knitted fabric from the paper or film that was enlarged and printed at an arbitrary magnification using a copying machine. Further, a method in which the void portion is further cut out to determine the total mass (S ₁ ) of the void portion, and the value of S ₁ × 100 / S is regarded as the mesh porosity is suitable. Basis weight of the mesh-like woven or knitted fabric used in the present invention, building curing mesh sheet (Category 2 class) those 75~150g / ^{m 2,} the ones 200~350g / ^{m 2} in the building curing mesh sheet (Category 1 class) Is suitable.

  In the mesh sheet of the present invention, a coating layer made of a flame retardant composition mainly composed of a biodegradable resin is formed on the entire surface of the mesh woven or knitted fabric, that is, the entire exposed surface of the multifilament yarn constituting the mesh woven or knitted fabric. The flame retardant composition forming the coating layer contains 5 to 75 parts by mass of a microencapsulated flame retardant imparting agent with respect to 100 parts by mass of the biodegradable resin, and the multifilament yarn It is impregnated at a specific ratio into the capillary gap between the filaments to fix the filaments together, and the biodegradable resin forming the coating layer is an emulsion or an aqueous dispersion of an aqueous dispersion or an aqueous solution. The emulsion of the biodegradable resin and the aqueous dispersion are preferably used in the production of the mesh sheet of the invention. Surface, i.e., may be provided a coating layer by the biodegradable resin to the entire surface of the exposed surface of the multifilament yarn that constitutes it. This coating layer is preferably provided so that the ratio of the mass of the mesh-like woven or knitted fabric (base fabric) to the mass of the mesh sheet is 40 to 80% by mass, particularly 45 to 65% by mass. That is, the coating layer is provided so that the ratio of the mass of the coating layer (including the resin-impregnated portion to the multifilament yarn) in the mass of the mesh sheet is 20 to 60% by mass, particularly 35 to 55% by mass. It is preferable. If the proportion of the mass of the mesh woven or knitted fabric (base fabric) is less than 40% by mass, the resulting mesh sheet may be insufficient in strength and cannot be used for a building curing sheet, and exceeds 80% by mass. Insufficient flameproofness may not be obtained, and at the same time washing resistance may be insufficient. The mesh porosity (mesh area ratio) of the obtained mesh sheet (mesh composite) is preferably 5 to 50%.

  The biodegradable resin is one or more emulsions selected from polylactic acid (copolymer) resins, aliphatic polyester (copolymer) resins, or aqueous dispersions of aqueous dispersions, or polyvinyl alcohol (copolymerization). Resin aqueous solutions can be used, which mainly have degradability by microorganisms such as bacteria, bacteria, and molds, and in the presence of moisture, hydrolyzate that promotes degradability by these microorganisms. It is what has. In particular, in a polylactic acid-based (copolymerized) resin and an aliphatic polyester-based (copolymerized) resin, the molecular structure that particularly increases the hydrolysis efficiency has an ester bond (—COO—) content of 40 to 40% in the unit structure. Those having 80 atomic weight%, particularly 45 to 76 atomic weight% are preferred. The polylactic acid-based (copolymerization) resin and the aliphatic polyester-based (copolymerization) resin can be blended with a plasticizer as necessary to impart arbitrary flexibility to the coating layer. Examples of the plasticizer include non-phthalic plasticizers such as dioctyl adipate, tributyl acetylcitrate, dibutyl sebacate, dioctyl sebacate, and aliphatic polyester plasticizers such as adipic acid polyester and sebacic acid polyester. Can be mentioned.

Polylactic acid-based (copolymerization) resins are obtained by ring-opening polymerization of polylactic acid resin obtained by dehydration polymerization of lactic acid and lactide, which is a cyclic dimer of L-lactic acid (obtained by lactic acid fermentation of glucose). High molecular weight polylactic acid resin (—OCHCH ₃ CO—) _n , polyglycolic acid (aliphatic polyester resin) having (O—CH ₂ —CO—) unit, copolymer resin of lactic acid and glycolic acid, lactic acid Copolymer resin of lactic acid and butyric acid, Copolymer resin of lactic acid and valeric acid, Copolymer resin of lactic acid and malic acid, Copolymer resin of lactic acid and caprolactam, and others, glycolic acid and lactones A polylactic acid copolymer resin such as a copolymer can be used.

Aliphatic polyester-based (copolymerization) resins include aliphatic polyols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.) and aliphatic dicarboxylic acids (adipic acid, succinic acid, sebacin) Units are aliphatic polyester resins obtained by polycondensation with acid, etc., and ω-hydroxy acids obtained by ring-opening polymerization of cyclic esters (lactones such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone). As aliphatic polyester resins and aliphatic polyester copolymer resins, polycondensates of aliphatic short-chain ester polyols (dihydroxypolyethylene adipate) and aliphatic diisocyanates (hexamethylene diisocyanate), polyester-ether copolymers Resins, these are Ring-opening polymer of cyclic ester-ether, ring-opening copolymer of cyclic ether and cyclic ester-ether, ring-opening copolymer of cyclic acid anhydride and excess cyclic ether, cyclic by polyether oligomer Ring-opening polymer of ester, condensation polymer between telechelic oligomer, acetal-ester type polyester resin having tetrahydropyran ring obtained by ring-opening polymerization of bicyclic lactones, and ether-ester type polyester resin, or bicyclic ring An emulsion or aqueous dispersion such as a polyester resin having a tetrahydrofuran ring obtained by ring-opening polymerization of lactones. Further, polyester-carbonate copolymer resins, which are specifically ring-opening polymers such as cyclic trimethylene carbonate and 2,2-dimethyltrimethylene carbonate, and copolymers of these carbonates and lactones, Copolymers of carbonates and ethylene oxides, and polyester-amide copolymer resins, which are specifically cyclic ester-amide ring-opening polymers, cyclic esters and cyclic amides (lactams). Ring copolymer, an interpolymer transesterification product of aliphatic polyester and polyamide (nylon), etc., as cyclic amide, α-pyrrolidone, ε-caprolactam, ω-laurolactam, and lactone as Emulsion or aqueous disk purge of δ-valerolactone, ε-caprolactone, etc. Can be used.

  As the aliphatic polyester-based resin, it is preferable to use an emulsion or aqueous dispersion of a microbial-produced polyester compound synthesized by microorganisms (bacteria) in the cells and stored in a granular form in the cells. Poly (3- (hydroxybutanoic acid) (3HB), 3-hydroxyvaleric acid (3HV), 3-hydroxypropionic acid (3HP), 4-hydroxybutyric acid (4HB) having 3 to 5 carbon alkanoic acid as a monomer unit Hydroxyalkanoates). Moreover, it is a homopolymer obtained by polymerizing these alone, or a poly (hydroxyalkanoate) -based polyester resin obtained by polymerizing two or more monomers. In the present invention, poly (3HB-co-3HV), which is a copolymer resin of 3HB and 3HV, and poly (3HB-co-4HB), which is a copolymer resin of 3HB and 4HB, can be preferably used. . These hydroxyalkanoates can be blended with a plasticizer as necessary to impart arbitrary flexibility to the coating layer, and at the same time, these plasticizers can be used as a bait for microorganisms.

  As a polyvinyl alcohol-based (copolymerization) resin, a polyvinyl alcohol resin obtained by saponifying (saponifying degree 77 to 99 mol%) a polyvinyl acetate resin as a precursor, and a polyvinyl acetate resin copolymer Resins (for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid and esterified products thereof, maleic anhydride and ring-opened products thereof, vinyl compounds such as vinyl pyrrolidone and vinyl pivalate, and carbon number of 4 or more. A copolymer of a fatty acid with a vinyl ester) is used as a precursor, and a polyvinyl alcohol copolymer resin obtained by saponification thereof is used, and these are used in a state dissolved in water.

  In addition, a binder resin can be used in combination with the biodegradable resin for the purpose of enhancing the washing resistance in the resin coating layer. Examples of these binder resins include polyvinyl acetate and vinyl acetate-acrylate ester. Polymeric resins, vinyl acetate-dibutyl maleate copolymer resins, vinyl acetate-veova copolymer resins, vinyl acetate-ethylene copolymer resins (VAE), ethylene-vinyl acetate copolymer resins (EVA), and other vinyl acetate copolymer resins , Acrylic ester-methyl methacrylate copolymer resin, acrylic ester-styrene copolymer resin and other acrylic ester copolymer resins, polyester polyurethane resins, polyether polyurethane resins, polycarbonate polyurethane resins, polycaprolactone polyurethanes Resin, acrylic polyurethane Polyurethane resins such as fats, polyester resins, polyamide resins, polyethylene oxide resins, ionomer resins, and other thermoplastic resins, and hydroxyl groups, carboxylic acid groups, quaternary ammonium bases, etc. are introduced into these resin structures. It is an emulsion such as a functional group-containing modified resin made water-based, or an aqueous dispersion such as a dispersion. Others, butadiene polymer, styrene-butadiene copolymer, carboxyl-modified styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene copolymer, 2-vinylpyridine-styrene-butadiene copolymer, etc. A thermoplastic rubber emulsion or latex can also be used. These binder resins can be used in the range of 1 to 25 parts by mass with respect to 100 parts by mass of the biodegradable resin. However, when the addition amount exceeds 25 parts by mass, the biodegradation rate may be slow. Further, for the purpose of further enhancing the washing resistance, a curing agent or a crosslinking agent may be added to the biodegradable resin and the combination of the biodegradable resin and the binder resin. An epoxy curing agent, a melamine curing agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, and the like are added in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the biodegradable resin. Can be used in a range. If the amount added exceeds 5 parts by mass, the biodegradation rate may be slow.

The microencapsulated flame retardant imparting agent contained in the flame retardant composition forming the coating layer contains at least one nitrogen atom-containing compound such as a urea derivative, a guanidine derivative, or a melamine salt. It is a microcapsule. These are specifically i). Urea derivatives such as urea, thiourea, dimethylolurea, diacetylurea, ethyleneurea, trimethylurea, N-benzoylurea, and guanylurea phosphate, ii). Guanidine derivatives such as guanidine, dicyandiamide, dicyandiamidicin, guanidine sulfamate, guanidine phosphate, guanidine sulfate, and guanidine phosphate, iii). Examples include melamine salts such as melamine phosphate, melamine borate, and melamine silicate. In the present invention, urea derivatives and guanidine derivatives that generate ammonia gas during thermal decomposition are preferable from the viewpoint of imparting flameproofing properties. The microencapsulated flame retardant imparting agent contains at least one or more phosphorus atom-containing compounds such as phosphates, metal (organic) phosphates, phosphate ester derivatives, phosphonic acid compounds, phosphinic acid compounds, One or more microcapsules. These are specifically iv). Phosphoric acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, ammonium phosphate, and metal salts thereof (specifically, calcium dihydrogen phosphate, calcium hypophosphite, monopotassium phosphate, potassium hypophosphite) Etc.), v). Metal salt of phosphoric acid monoalkyl ester represented by PO (OR) (OH) ₂ , metal salt of phosphoric acid dialkyl ester represented by PO (OR) ₂ OH, and P (OR) (OH) ₂ Metal organophosphates such as the metal salts of phosphorous acid monoalkyl esters shown, and the metal salts of dialkyl phosphites shown with P (OR) ₂ OH (the metals that form salts with these are Na, K, Li, Ca, Ba, Mg, Al, Zn, etc., wherein R represents an alkyl group), vi). Phosphate esters such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, and aromatic condensed phosphate esters, vii). Phosphonic acids such as methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid and butylphosphonic acid, viii). Examples include phosphinic acids such as dimethylphosphinic acid, methylethylphosphinic acid, diethylphosphinic acid, and phenylphosphinic acid. In the present invention, phosphoric acid ester derivatives, phosphonic acid compounds, and the like are preferable from the viewpoint of imparting flameproofness. In addition, the wash resistance of the mesh sheet obtained by simply using the non-microcapsule compounds of i) to viii) as a flame retardant composition is insufficient, and it is difficult to ensure the flame resistance after washing. It becomes.

The microencapsulated flame retardant is obtained by coating a nitrogen-containing or phosphorus-containing compound (solid or liquid) selected from the above nitrogen atom-containing compound and phosphorus atom-containing compound with a biodegradable film-forming substance. In the present invention, the microencapsulated flame retardant can be used in combination with a plurality of types of microcapsules. Film-forming material is laid preferred are the nitrogen-containing compounds and hard water resistance microcapsules membrane wall a phosphorus atom-containing compound is eluted by washing enclosing, these polylactic acid described above (copolymerization) resins, aliphatic polyester is (copolymerization) membrane wall containing resins, polyvinyl alcohol (the copolymer) of one or more biodegradable resins selected from resins. In the production of a microencapsulated flame retardant, the microcapsule membrane wall of a condensation polymer such as polylactic acid (copolymer) resin or aliphatic polyester (copolymer) resin is emulsified in an organic solvent or water. It is formed by polycondensation at the interface of fine particles of the encapsulated inclusion substance (solid or liquid). Microcapsules made of water-soluble polymers such as polyvinyl alcohol (copolymerization) resin finely disperse the encapsulated substance (solid or liquid) in an aqueous solution of the water-soluble polymer, and add a non-solvent or inorganic electrolyte to the polymer. formed by the core Solvay Activation methods to phase separate from the aqueous system by, also in the contrary, the polylactic acid (copolymerization) resins, aliphatic polyester (copolymer) dissolved polymer such as a resin in an organic solvent Then, the core substance that is phase-separated from the polymer-soluble organic solvent system is obtained by finely dispersing the inclusion substance (solid or liquid) in the polymer solution and adding a non-solvent for the polymer or a liquid polymer for inducing phase separation to the polymer. It is formed by a solution method. In particular, microcapsules obtained by phase separation from an aqueous solution of a water-soluble polymer preferably have a microcapsule membrane wall insoluble in water using calcium chloride, zirconium nitrate, borax or the like as a curing agent.

  The average particle size of the microencapsulated flame retardant imparting agent used in the present invention is 0.5 to 20 μm, preferably 1 to 10 μm. When the average particle size is less than 0.5 μm, the ratio of the microcapsule membrane wall is too high to provide sufficient flame resistance to the resulting mesh sheet, and when it exceeds 20 μm, the strength of the microcapsules is unstable. The microcapsules may be destroyed by friction such as washing. The microencapsulated flame retardant imparting agent is preferably contained in an amount of 5 to 75 parts by mass, particularly 10 to 50 parts by mass with respect to 100 parts by mass of the biodegradable resin. When the content of the microencapsulated flame retardant imparting agent is less than 5 masses, the resulting mesh sheet has insufficient flame resistance, and when the content exceeds 75 mass parts, the abrasion resistance of the mesh sheet obtained May be insufficient. A coating layer, a dip-nip method, a transfer method, etc. are formed on the mesh woven or knitted fabric (base fabric) with a flame retardant composition containing the above microencapsulated flame retardant imparting agent in this biodegradable resin. The process is performed once or twice, and dried through a hot air oven to remove moisture. The formed coating layer (including the resin-impregnated portion of the multifilament yarn) is preferably provided so as to be 20 to 60% by mass, particularly 35 to 55% by mass with respect to the mass of the mesh sheet. At this time, it is preferable that the capillary space between the filaments of the multifilament yarn is impregnated with a flame retardant composition at a specific ratio to fix the filaments to each other.

Further, in the mesh sheet of the present invention, an outermost coating layer made of a flame retardant composition mainly composed of a biodegradable resin may be further formed on the entire surface of the mesh composite. The coating is preferably a flame retardant composition containing 5 to 75 parts by mass, particularly 10 to 50 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. If the content of the melamine-based flame retardant particles is less than 5 mass, the resulting mesh sheet has insufficient flame resistance, and if the content exceeds 75 mass parts, the resulting mesh sheet has insufficient wear resistance. It may become. The melamine flame retardant particles are at least one selected from melamine cyanurate, melamine sulfate, and a composite of a (poly) phosphate compound and a melamine derivative, and the particle size thereof is 0.1 to 20 μm, Preferably it is 1-10 micrometers. In addition, the composite of the (poly) phosphate compound and the melamine derivative is specifically composed of ammonium polyphosphate particles having a polymerization degree n of 100 to 1200 represented by (NH ₄ PO ₃ ) _n , a melamine resin, Coated ammonium polyphosphate surface coated with melamine derivatives such as urea resin, triazine resin, (poly) ammonium phosphate and melamine, dimer of melamine, trimer of melamine, urea, triazine, (iso) cyanurate derivative, (Poly) ammonium phosphate derivative which is a condensate with one or more nitrogen-containing compounds such as (iso) cyanuric acid derivative, (poly) phosphoric acid and melamine, melamine dimer, melamine trimer, urea , Triazine, (iso) cyanurate derivatives, (iso) cyanuric acid derivatives and other condensates with one or more nitrogen-containing compounds ( Li) phosphate derivatives and the like. Examples of the cyanurate derivative include trimethyl cyanurate and triethyl cyanurate, and examples of the isocyanurate derivative include trimethyl isocyanurate and triethyl isocyanurate. The cyanuric acid derivatives are cyanuric acid amide, guanamine, benzoguanamine, trimethylol melamine, cyanuric acid trimethyl ester, cyanuric acid diamide, and 1,3,5-triazine, 2,4,6-trioxy-1,3,5-triazine. The isocyanuric acid derivatives include isocyanuric acid monoimide, isocyanuric acid diimide, isocyanuric acid triimide, calcium cyanamide (lime nitrogen), trimethyldicyanamide, tricarbimide, and dicyanamide trimer (melon). The outermost coating layer is formed on the mesh composite with the flame retardant composition containing melamine flame retardant particles in the biodegradable resin by the coating method, dip-nip method, transfer method, etc. This is done by drying to remove moisture. The outermost coating layer is preferably provided so that the total coating amount with the base coating layer is 20 to 60% by mass, particularly 35 to 55% by mass with respect to the mass of the mesh composite. At this time, it is preferable that the capillary space between the filaments of the multifilament yarn is impregnated with the flame retardant composition of the base coating layer to fix the filaments to each other.

Further, the mesh sheet of the present invention is obtained by applying a biodegradable resin to the mesh woven or knitted fabric (base fabric) subjected to a pretreatment with a pretreatment agent containing the above-described microencapsulated flame retardant. The flame retardant composition may be a mesh-like composite having a coating layer formed of a flame retardant composition containing 5 to 75 of the melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. parts by weight containing, and securing the filaments each other by impregnating the flame-retardant composition in capillary voids between the filaments of this time multifilament yarn. In the pretreatment with the pretreatment agent containing the microencapsulated flame retardant, a solution containing the microencapsulated flame retardant dispersed in water or alcohol as a solvent is used as a pretreatment agent solution. The whole mesh woven or knitted fabric is dipped in, and simultaneously pulled up and squeezed with a mangle roll to remove excess pretreatment solution, and then dried through a hot air oven or the like. The amount of the above-mentioned microencapsulated flame retardant imparting agent contained in this pretreatment solution is preferably 5 to 30 parts by mass, particularly 10 to 20 parts by mass with respect to 100 parts by mass of the solvent. When the amount of the microencapsulated flame retardant imparting agent is less than 5 parts by mass, the flame resistance of the resulting mesh sheet becomes insufficient, and when the content exceeds 30 parts by mass, the liquid viscosity increases and the mesh sheet Processing may be difficult. Further, in this pretreatment, in order to firmly fix the above-described microencapsulated flame retardant imparting agent on the above-mentioned mesh woven or knitted fabric (base fabric), an appropriate amount of the above-described aqueous biodegradable resin dispersion is used as a binder. be able to. The binder amount (solid content) is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass, with respect to 100 parts by mass of the microencapsulated flame retardant. The coating layer formed on the entire surface of the pretreated mesh woven or knitted fabric is formed of a flame retardant composition containing 5 to 75 parts by mass of the melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. . This coating layer is preferably provided so that the ratio of the mass of the mesh-like woven or knitted fabric (base fabric) to the mass of the mesh sheet is 40 to 80% by mass, particularly 45 to 65% by mass. That is, the coating layer is provided so that the ratio of the mass of the coating layer (including the resin-impregnated portion to the multifilament yarn) in the mass of the mesh sheet is 20 to 60% by mass, particularly 35 to 55% by mass. It is preferable. If the proportion of the mass of the mesh woven or knitted fabric (base fabric) is less than 40% by mass, the resulting mesh sheet may be insufficient in strength and cannot be used for a building curing sheet, and exceeds 80% by mass. And washing resistance may be insufficient.

  The mesh sheet of the present invention may be colored by adding an appropriate amount of a known color pigment or dye to the coating layer and the flame retardant composition forming the outermost coating layer. Conventionally known pigments such as pigments and inorganic pigments can be used, and combinations thereof are not limited. From the viewpoint of landfill disposal of mesh sheets, coloring pigments and dyes that do not contain halogen in the molecular structure It is preferable to select and color. In addition, UV absorbers (benzophenone compounds, benzotriazole compounds, salicylic acid compounds and anilide compounds), antioxidants (hindered phenol compounds, amine compounds, and phosphite compounds) as weather resistance imparting agents It is preferable to use about 0.1 to 3 parts by mass of a light stabilizer (hindered amine compound) or the like with respect to 100 parts by mass of the biodegradable resin.

The method of forming the (outermost) coating layer in the mesh sheet of the present invention is to add a microencapsulated flame retardant or a melamine-based difficulty to an emulsion of a biodegradable resin, an aqueous dispersion of an aqueous dispersion, or an aqueous solution. Using a flame retardant composition containing flame retardant particles, the coating process such as a coating method, a dip-nip method, and a transfer method is performed once or twice, followed by drying through a hot air oven to remove moisture. . The formed coating layer (including the resin-impregnated portion of the multifilament yarn) is provided so as to be 20 to 60% by mass, particularly 35 to 55% by mass with respect to the mass of the mesh sheet. The composite porosity is preferably 5 to 50%, particularly preferably 10 to 35%. The mesh porosity is a stitched portion formed by entanglement of the biodegradable resin-coated fiber yarn, and the mesh porosity is a value relative to the unit area of the mesh sheet. If the mesh porosity is less than 5%, the resulting mesh sheet is inferior in transparency and air permeability. If the mesh porosity exceeds 50%, the strength and dimensional stability of the mesh sheet obtained are insufficient. Therefore, the performance (tensile strength × elongation, tensile strength, strength at the fitting portion, penetration resistance test by dropping the steel pipe) defined in JIS A8952 and the temporary industry association certification standard may not be satisfied. Also, it may become misaligned by washing and cannot be reused. The mesh porosity can be obtained as a value obtained by subtracting from 100 the area occupied by the biodegradable resin-coated fiber yarn as a percentage with respect to the unit area of the mesh sheet. (For example, the unit porosity can be 100 cm ² by 10 cm in the warp direction × 10 cm in the weft direction.) As a particularly simple method, a mesh sheet is printed using a commercially available copying machine, and 2. Cut out a square of 54 cm x 2.54 cm in the weft direction, and cut out the printed portion (square) of the mesh sheet from the paper or film that has been enlarged and printed with a copier at an arbitrary magnification. A method is suitable in which the portion is cut out to obtain the total mass (S ₂ ) of the void portion, and the value of S ₂ × 100 / S is regarded as the mesh porosity. Further, it is preferable that the capillary gap between the filaments of the multifilament yarn is impregnated with the flame retardant composition and the filaments are fixed to each other, and the impregnation and fixation with the flame retardant composition is at least the background of the cross section of the multifilament yarn. It is preferable to be impregnated and fixed at a solidity rate of 75 to 100%, particularly 85 to 100% from the outside with respect to the radius. When the filling rate of the flame retardant composition with respect to the weft radius of the multifilament yarn cross section is less than 75%, the resulting mesh sheet may have insufficient washing resistance. The solidification rate of the flame retardant composition with respect to the weft radius of the cross section of the multifilament yarn can be calculated from an enlarged copy of a photograph taken with an electron microscope. That is, the radius (Rf) and (Rw) from the enlarged copy of the electron micrograph are set with the warp radius (Rf) of the cross section of the multifilament yarn being the thickness direction of the mesh sheet and the weft radius (Rw) being the width direction of the mesh sheet. Next, measure the depth of the impregnated and fixed portion with the flame retardant composition with respect to the radius, and calculate this as (Rfd) and (Rwd) as Rfd × 100 / Rf and Rwd × 100 / Rw, respectively. Can do.

  For printing on the mesh sheet of the present invention, for example, gravure printing, screen printing, inkjet printing, and the like are possible. Inkjet printing can be easily performed using a commercially available inkjet printer, and any of water-based ink, solvent-based ink, and oil-based ink can be used as the ink. Also, in printing methods such as gravure printing and screen printing, commercially available dedicated inks adapted to the respective printing methods can be used, but biodegradable resins can be used as the resin binder for these printing inks. preferable. Further, in a mesh sheet premised on repeated use for leasing, these printing inks are preferably inks that can be removed by washing.

Example
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to the range of these examples. Test methods relating to flameproof evaluation, penetration resistance test, washing test and biodegradation performance evaluation of mesh sheets in the following examples and comparative examples are as follows.

(1). Tested according to JIS L-1091 for flame resistance, and evaluated according to the following criteria. (A mass of 450 g / m ² or less applied category 3 of the A-1 method, and those exceeding a mass of 450 g / m ² applied category 3 of the A-2 method.)
○: Carbonization area 40 cm ² or less, after flame time 5 seconds or less, residual dust time 20 seconds or less,
The carbonization distance is 20 cm or less. (Meets the standard)
X: One or more items of carbonization area, after flame time, residual dust time, carbonization distance
The standard value is exceeded. (Does not meet the standard)
(2). Penetration resistance test [Certified Industrial Association Certification Criteria]
Targeting the center part of the mesh sheet fixed to the 30 ° tilt test frame specified in JIS A8952, a steel pipe drop (product conforming to JIS A8952 standard) with a mass of 3 to 5 kg is allowed to fall freely, and the mesh sheet is resistant to penetration. And the state of breakage (breakage) were observed.
○: No penetration of the steel pipe drop. (Meets the standard)
Δ: There is no penetration of the steel pipe drop, but the mesh sheet is severely cracked. (Does not meet the standard)
X: The steel pipe falling body breaks the mesh sheet and penetrates completely. (Does not meet the standard)

(3). Washing resistance of an unused mesh sheet sewing product (1.8m width x 3.6m length: lengthwise 8 folds x widthwise 4 folds) using an industrial rotary washing machine with a washability capacity of 450L Evaluated. The washing liquid is a weakly alkaline industrial detergent (Trademark: Genbunais: [Sodium alkyl benzene sulfonate as surfactant, sulfate as process agent, silicate and carbonate as alkali agent, aluminosilicate as water conversion agent , And fluorescent brightening agent: Genbu Co., Ltd.)] and 500 g of sodium metasilicate 9 hydrate (Sanpo Chemical Industry Co., Ltd.) as an alkaline agent dissolved in 300 L of warm water of 40 ° C., The appearance immediately after washing for 30 minutes was observed.
○: (outermost) No appearance abnormality such as falling off or swelling of the coating layer. (Reusable)
Δ: (Outermost) Swelling of the coating layer is observed. (There is a problem with reuse)
X: (Outermost) The coating layer swells and falls off partially. (Cannot be reused)
(4). Flameproofing property after washing The same flameproofing test as in the above test (1) was carried out by rinsing the mesh sheet of the above test (3) with industrial water for 5 minutes and drying it at room temperature for 24 hours. Went. (Judgment criteria are the same)

(5). Penetration resistance test after washing The mesh sheet of the above test (3) was rinsed with industrial water for 5 minutes and dried at room temperature for 24 hours, and the same penetration resistance test as in the above test (2) was performed. Went. (Judgment criteria are the same)
(6) Evaluation of biodegradability (A)
A piece of mesh sheet (15 cm wide × 20 cm long) was placed horizontally on a horticultural humus as an embedment specimen, the specimen was covered with a thickness of 15 centimeters of horticultural humus, and the specimen was buried in the horticultural humus. . The container in which the specimen was buried was kept at 50 ° C. and 95% humidity at all times, and the specimen was taken out after 3 months and 6 months. (Reference to JIS K6953-1999) A 3 cm wide × 12 cm long sample collected from this specimen was dried at 30 ° C. for 24 hours, and subjected to a stagnation wear test according to the JIS L1096 test method (Scott type method) to evaluate the degree of deterioration. (Toyo Seiki Seisakusho Co., Ltd., Scott Scratch Resistance Tester: Stagnation load 1.0 kgf)
<Evaluation of biodegradability A>
(Double-circle): The test piece fractured | ruptured by the number of times of stagnation 1-5 times, or collapsed at the time of mounting | wearing. (Degradability is good)
○: The test piece broke after 6-20 times of stagnation. (Decomposition is progressing considerably)
(Triangle | delta): Only the surface of the test piece was worn out and deteriorated by 21-50 times of stagnation. (Progress of decomposition is slow)
X: There is no abnormality in a test piece by 50-100 times of stagnation. (Slow decomposition or not decomposed)

(7) Evaluation of biodegradability (B)
Samples 3 cm wide x 20 cm long were taken from the test specimens 3 months and 6 months after taken in test (6), dried at 30 ° C for 24 hours, and the tensile strength was measured by the JIS L1096 test method (strip method). The retention rate relative to the initial value was determined. (Toyo Seiki Seisakusho Co., Ltd. Universal Tensile Tester Strograph V10: Marking interval 100 mm: Tensile speed 200 mm / min)
<Evaluation of biodegradability B>
A: Strength retention 10% or less (good degradability)
○: Strength retention rate of 11 to 25% (decomposition proceeds)
Δ: Strength retention 26 to 50% (slow progress of decomposition)
X: Strength retention rate of 51% or more (decomposition has not progressed much)
[Example 1]

Three multifilament yarns having a melting point of 168 ° C. and a fineness of 1111 dtex, obtained by melt spinning from a polylactic acid resin obtained by copolymerizing 96% by mass of L-lactic acid and 4% by mass of polyethylene glycol having a number average molecular weight of 6000, apparent one to warp and knitted woven mesh shape with woven from weft (warp implantation density seven /2.54cm× weft implantation density seven /2.54cm of Mosha fabrics: weight 185 g / ^{m 2:} porosity 28% ) Was used as the base fabric of the mesh sheet. This base fabric (weaving width 205 cm, length 100 m) is dipped (immersed) in a liquid bath of the flame retardant composition (1) having the following composition, and the flame retardant composition (1) is adhered thereto. The knitted fabric is pulled up and simultaneously niped with a mangle roll (squeezing pressure 5 kgf / cm ² ) to attach the flame retardant composition (1) to the entire surface of the mesh woven fabric and at the same time flame retardant inside the multifilament yarn. The composition (1) was impregnated. This was heat-treated in a hot air drying furnace at 140 ° C. for 2 minutes to obtain a mesh composite intermediate having a thickness of 0.66 mm and a mass of 300 g / m ² . This intermediate is again dipped (immersed) in a liquid bath of the flame retardant composition (1) to further adhere the flame retardant composition (1) to the entire surface of the intermediate, and this is niped (squeezed pressure) with a mangle roll. 2 kgf / cm ² ), heat-treated in a hot air drying oven at 140 ° C. for 2 minutes, and a flame-retardant composition mainly composed of a biodegradable resin on the entire surface of the biodegradable mesh woven / knitted fabric. The coating layer according to (1) is formed at 52.0%, and the flame retardant composition (1) is impregnated into the capillary space between the filaments of the multifilament yarn to fix the filaments to each other. A mesh sheet having 74 mm, a mass of 385 g / m ² , and a mesh porosity of 26% was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
<Coating liquid for forming coating layer: Flame retardant composition mainly composed of biodegradable resin (1)>
Biodegradable resin: (Product number) Randy CP-05A: Poly L-lactic acid resin emulsion
: Solid content concentration 40% by mass: Miyoshi Oil & Fat Co., Ltd. 250 parts by mass Microencapsulated flame retardant (1): Polylactic acid-coated dicyandiamide particles (average particle size 8 μm: dicyandiamide content 35% by mass) 40 parts by mass oxidation Titanium pigment: (Part No.) Ryudai W69 White: Dainippon Ink & Chemicals, Inc .:
Aqueous pigment (white) (solid content 50% by mass) 4 parts by mass Carbon black pigment: (Part No.) Ryudai W Black BK: Dainippon Ink & Chemicals, Inc .: Aqueous pigment (black) (solid content 50% by mass) 1 mass Part weather resistance stabilizer: (Part No.) ULS-383MG:
Benzophenone polymer emulsion (solid content 30% by mass) 4 parts by mass [Example 2]

The mesh woven or knitted fabric of Example 1 was changed to a triaxial flat woven fabric (basket woven fabric). A triaxial plain fabric is a multifilament having a melting point of 168 ° C. and a fineness of 1111 dtex obtained by melt spinning from a polylactic acid resin obtained by copolymerizing 96% by mass of L-lactic acid and 4% by mass of polyethylene glycol having a number average molecular weight of 6000. Mesh-like woven or knitted fabric woven from warp yarns and bias yarns with two yarns aligned (13 warp density / 2.54 cm × 13 weft density / 2.54 cm: mass 225 g / m ² : porosity 22 %) Was used as the base fabric of the mesh sheet. 40 parts by weight of the microencapsulated flame retardant imparting agent (1) of the flame retardant composition (1) in the coating liquid for forming the coating layer of Example 1 is applied to this base fabric (weaving width 205 cm, length 100 m). Microencapsulated flame retardant imparting agent (2) “aliphatic polyester resin-coated urea particles (average particle size 8 μm: urea content 35 mass%)” Flame retardant composition changed to 40 parts by mass (2) coating liquid In the same manner as in Example 1, the process of “dip (immersion) -nip-drying” was performed twice in the same manner as in Example 1, and the entire surface of the biodegradable mesh knitted / knitted fabric was mainly composed of the biodegradable resin. The coating layer made of the flame retardant composition (2) is formed at 44.0%, and the flame retardant composition (2) is impregnated in the capillary gap between the filaments of the multifilament yarn to fix the filaments to each other. It has a thickness of 0.72 mm, mass 402 g / ^{m 2,} eyes There was obtained a void rate of 20% of the mesh sheet. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
[Example 3]

実施例１〜３のメッシュシートの積層構造を図１に示す。
［実施例４］ A melting point of 168 ° C. obtained by melt spinning the mesh woven or knitted fabric of Example 1 from a polylactic acid resin obtained by copolymerizing 96% by mass of L-lactic acid and 4% by mass of polyethylene glycol having a number average molecular weight of 6000, Mesh woven or knitted fabric woven from warps and wefts with three apparent multifilament yarns with a fineness of 833dtex (11 warp density / 2.54 cm x 11 weft density / 2.54 cm imitation fabric) : Mass 225 g / m ² : Porosity 14%). 40 parts by weight of the microencapsulated flame retardant imparting agent (1) of the flame retardant composition (1) in the coating liquid for forming the coating layer of Example 1 is applied to this base fabric (weaving width 205 cm, length 100 m). Microencapsulated flame retardant imparting agent (3) “Polyvinyl alcohol resin-coated phosphonic acid particles (average particle size 8 μm: phosphonic acid content 35% by mass)” Flame retardant composition (3) coating changed to 40 parts by mass Using the liquid, the process of “dip (immersion) -nip-drying” was performed twice in the same manner as in Example 1, and the biodegradable resin was mainly formed on the entire surface of the mesh-like woven / knitted fabric base having biodegradability. The coating layer made of the flame retardant composition (3) is formed at 45.4%, and the flame retardant composition (3) is impregnated into the capillary space between the filaments of the multifilament yarn to fix the filaments to each other. Thickness 0.72mm, mass 41 g / ^{m 2,} to obtain an eye fit porosity of 12% of the mesh sheet. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
The phosphonic acid is, for example, a compound represented by the chemical formula shown in the chemical formulas (1) and (2). In Example 3, a mixture of the compounds of the chemical formulas (1) and (2) ((product number) K- 19A, Meisei Chemical Co., Ltd.).

The laminated structure of the mesh sheets of Examples 1 to 3 is shown in FIG.
[Example 4]

Example 1 and same Mosha woven mesh-like woven or knitted fabric according to (warp implantation density seven /2.54cm× weft implantation density seven per 2.54 cm: Mass 185 g / ^{m 2:} porosity 28%) as a base fabric Using. A mesh woven or knitted fabric in which this base fabric was dipped (immersed) in a liquid bath of the same flame retardant composition (1) as in Example 1 and the flame retardant composition (1) was adhered thereto. At the same time as pulling up, it is niped with a mangle roll (squeezing pressure 5 kgf / cm ² ) to attach the flame retardant composition (1) to the entire surface of the mesh woven or knitted fabric and at the same time, the flame retardant composition ( 1) was impregnated. This was heat-treated in a hot air drying oven at 140 ° C. for 2 minutes to obtain an intermediate of a mesh composite having a thickness of 0.68 mm and a mass of 300 g / m ² . This intermediate was dipped (immersed) in a liquid bath of the following flame retardant composition (4) to adhere the flame retardant composition (4) onto the entire surface of the coating layer. Is niped with a mangle roll (squeezing pressure 2 kgf / cm ² ), heat-treated for 2 minutes in a hot air drying oven at 140 ° C., and a biodegradable resin is applied to the entire surface of the biodegradable mesh woven / knitted fabric. The total coating layer of the coating layer of the main flame retardant composition (1) and the outermost coating layer of the flame retardant composition (4) is formed at 52.0%, and the capillaries between the filaments of the multifilament yarn A mesh sheet having a thickness of 0.75 mm, a mass of 385 g / m ² , and a mesh porosity of 26%, in which the flame retardant composition (1) was impregnated in the voids to fix the filaments to each other, was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
<Coating liquid for forming coating layer: flame retardant composition mainly composed of biodegradable resin (4)>
Biodegradable resin: (Product number) Randy CP-05A: Poly L-lactic acid resin emulsion
: Solid content concentration 40% by mass: Miyoshi Oil & Fats Co., Ltd. 250 parts by mass Melamine flame retardant particles (1): Product number: MC640: Melamine cyanurate
: Nissan Chemical Co., Ltd. 25 parts by mass Titanium oxide pigment: (Part No.) Ryudai W69 White: Dainippon Ink & Chemicals, Inc .:
Aqueous pigment (white) (solid content 50% by mass) 4 parts by mass Carbon black pigment: (Product No.) Ryudai W Black BK:
Dainippon Ink & Chemicals, Inc .: Water-based pigment (black) (solid content 50% by mass) 1 part by weight Weathering stabilizer: (Part No.) ULS-383MG:
Benzophenone polymer emulsion (solid content 30% by mass) 4 parts by mass [Example 5]

Example 2 identical triaxial plain weave and (basket woven) by a mesh-like woven or knitted fabric (warp implantation density thirteen /2.54cm× weft implantation density 13 present per 2.54 cm: Mass 225 g / ^{m 2:} porosity 22% ) Was used as the base fabric. A mesh woven or knitted fabric in which this base fabric was dipped (immersed) in a liquid bath of the same flame retardant composition (2) as in Example 2 and the flame retardant composition (2) was adhered thereto. At the same time as pulling up, it is niped with a mangle roll (squeezing pressure 5 kgf / cm ² ) to attach the flame retardant composition (2) to the entire surface of the mesh woven or knitted fabric and at the same time, the flame retardant composition ( 2) was impregnated. This was heat-treated in a hot air drying furnace at 140 ° C. for 2 minutes to obtain an intermediate of a mesh composite having a thickness of 0.66 mm and a mass of 355 g / m ² . This intermediate was dipped (immersed) in the liquid bath of the flame retardant composition (4) of Example 4 to deposit the flame retardant composition (2) on the entire surface of the coating layer. This was niped with a mangle roll (squeezing pressure 2 kgf / cm ² ) and heat-treated for 2 minutes in a hot air drying oven at 140 ° C. to biodegrade the entire surface of the biodegradable mesh woven / knitted fabric. The total coating layer of the coating layer made of the flame retardant composition (2) mainly composed of the heat-resistant resin and the outermost coating layer made of the flame retardant composition (4) is formed at 46.7%, and the filament of the multifilament yarn A mesh sheet having a thickness of 0.73 mm, a mass of 422 g / m ² , and a mesh porosity of 20%, in which the flame retardant composition (2) was impregnated in the interstitial capillaries to fix the filaments to each other, was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
[Example 6]

A mesh-like woven or knitted fabric made of the same imitation woven fabric as in Example 3 (warp driving density 11 pieces / 2.54 cm × weft driving density 11 pieces / 2.54 cm: mass 225 g / m ² : porosity 14%) Using. A mesh woven or knitted fabric in which this base fabric was dipped (immersed) in a liquid bath of the same flame retardant composition (3) as in Example 3 and the flame retardant composition (3) was adhered thereto. At the same time as pulling up, it is niped with a mangle roll (squeezing pressure 5 kgf / cm ² ) to adhere the flame retardant composition (3) to the entire surface of the mesh woven or knitted fabric, and at the same time, the flame retardant composition ( 3) was impregnated. This was heat-treated in a hot air drying furnace at 140 ° C. for 2 minutes to obtain an intermediate of a mesh composite having a thickness of 0.66 mm and a mass of 355 g / m ² . This intermediate was dipped (immersed) in a liquid bath of the following flame retardant composition (5) for forming the outermost layer coating, and the flame retardant composition (3) on the entire surface of the coating layer (5 ) is deposited and which was nip (tourniquet 2 kgf / cm ²⁾ with a mangle roll, which was heat-treated for 2 minutes in a hot air drying oven at 140 ° C., the entire surface of the mesh-like woven or knitted base fabric having biodegradability A multifilament yarn comprising 47.7% of a total coating layer of a coating layer composed of a flame retardant composition (3) mainly composed of a biodegradable resin and an outermost coating layer composed of a flame retardant composition (5) A mesh sheet having a thickness of 0.73 mm, a mass of 430 g / m ² , and a mesh porosity of 12%, in which the flame retardant composition (3) is impregnated in the capillary gap between the filaments of the stripes and the filaments are fixed to each other Obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The flame retardant composition (5) was prepared by adding 25 parts by mass of the melamine flame retardant particles (1) to the melamine flame retardant particles (2) “melamine polyphosphate” : (Part No.) PMP-100: Nissan Chemical Industries, Ltd.] What was changed to 25 parts by mass was used. The performance of the obtained mesh sheet is shown in Table 1.
The laminated structure of the mesh sheets of Examples 4 to 6 is shown in FIG.
[Example 7]

A mesh woven or knitted fabric made of the same imitation woven fabric as in Example 1 (warp driving density 7 pieces / 2.54 cm × weft driving density 7 pieces / 2.54 cm: mass 185 g / m ² : porosity 28%) This base fabric was dipped (immersed) in a pretreatment agent bath having the following pretreatment composition (1), and the base fabric to which the microencapsulated flame retarding agent (1) of Example 1 was adhered was drawn. At the same time, it was niped with a mangle roll (squeezing pressure 2 kgf / cm ² ), and the microencapsulated flame retardant (1) was impregnated inside the multifilament yarn of the mesh woven or knitted fabric. This was heat-treated in a hot air drying oven at 140 ° C. for 2 minutes to obtain a pretreated base fabric having a mass of 192 g / m ² . Next, the same flame-retardant composition (4) as in Example 4 was dipped (immersed) in the liquid bath to pull up the mesh woven or knitted fabric to which the flame-retardant composition (4) was adhered, and at the same time, mangle roll in nip (tourniquet 5 kgf / cm ^2), was impregnated flame retardant composition (4) simultaneously multifilament yarn inside the flame retardant composition when adhered to the entire surface of the mesh-like woven or knitted fabric (4) . This was heat-treated in a hot air drying furnace at 140 ° C. for 2 minutes to obtain an intermediate of a mesh composite having a thickness of 0.68 mm and a mass of 305 g / m ² . This intermediate is again dipped (immersed) in the liquid bath of the flame retardant composition (4) to further adhere the flame retardant composition (4) to the entire surface of the intermediate, and this is niped (squeezed pressure) with a mangle roll. 2 kgf / cm ² ), heat-treated in a hot air drying oven at 140 ° C. for 2 minutes, and a flame-retardant composition mainly composed of a biodegradable resin on the entire surface of the biodegradable mesh woven / knitted fabric. The coating layer according to (4) is formed at 52.6%, and the flame retardant composition (4) is impregnated into the capillary space between the filaments of the multifilament yarn to fix the filaments to each other. A mesh sheet having a size of 74 mm, a mass of 390 g / m ² , and a mesh porosity of 26% was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
<Pretreatment composition (1)>
Microencapsulated flame retardant (1): Polylactic acid-coated dicyandiamide particles (average particle size 8 μm: dicyandiamide content 35% by mass) 20 parts by mass Trademark: Serogen WS: Carboxymethylcellulose: Daiichi Kogyo Seiyaku Co., Ltd. 10 masses Part diluted water (distilled water) 100 parts by mass [Example 8]

Mesh-like woven or knitted fabric using the same triaxial flat woven fabric (basket woven fabric) as in Example 2 (warp driving density 13 / 2.54 cm × weft driving density 13 / 2.54 cm: mass 225 g / m ² : porosity 22% ) As a base fabric, and this base fabric was dipped (immersed) in a pretreatment agent bath comprising the following pretreatment composition (2) to adhere the microencapsulated flame retardant imparting agent (3) of Example 3 The base fabric was pulled up and simultaneously niped with a mangle roll (squeezing pressure 2 kgf / cm ² ), and the microencapsulated flame retardant (3) was impregnated inside the multifilament yarn of the mesh woven or knitted fabric. This was heat-treated in a hot air drying oven at 140 ° C. for 2 minutes to obtain a pretreated base fabric having a mass of 234 g / m ² . Next, the same flame-retardant composition (5) as in Example 6 was dipped (immersed) in the liquid bath, and the mesh-shaped woven or knitted fabric to which the flame-retardant composition (5) was adhered was pulled up simultaneously with mangle rolls. in nip (tourniquet 5 kgf / cm ^2), was impregnated flame retardant composition (5) at the same time multifilament yarn inside the flame retardant composition when adhered to the entire surface of the mesh-like woven or knitted fabric (5) . This was heat-treated in a hot air drying oven at 140 ° C. for 2 minutes to obtain an intermediate of a mesh composite having a thickness of 0.68 mm and a mass of 312 g / m ² . This intermediate is again dipped (immersed) in a liquid bath of the flame retardant composition (5) to further adhere the flame retardant composition (5) to the entire surface of the intermediate, and this is niped (squeezed pressure) with a mangle roll. 2 kgf / cm ² ), heat-treated in a hot air drying oven at 140 ° C. for 2 minutes, and a flame-retardant composition mainly composed of a biodegradable resin on the entire surface of the biodegradable mesh woven / knitted fabric. The coating layer according to (5) is formed at 44.8%, and the flame retardant composition (5) is impregnated into the capillary space between the filaments of the multifilament yarn to fix the filaments to each other. A mesh sheet having 74 mm, a mass of 408 g / m ² , and a mesh porosity of 20% was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 1.
<Pretreatment composition (2)>
Microencapsulated flame retardant (3): Polyvinyl alcohol resin-coated phosphonic acid particles (average particle size 8 μm: phosphonic acid content 35% by mass) ”20 parts by mass Trademark: Serogen WS: Carboxymethylcellulose: Daiichi Kogyo Seiyaku ( Co., Ltd. 10 parts by weight diluted water (distilled water) 100 parts by weight The laminated structure of the mesh sheets of Examples 7 and 8 is shown in FIG.

［比較例１］

[Comparative Example 1]

In Example 1, the microencapsulated flame retardant imparting agent (1) of the flame retardant composition (1): 40 parts by mass of polylactic acid-coated dicyandiamide particles (dicyandiamide content 35% by mass) was converted to dicyandiamide (a flame retardant imparting agent ( 1)) It changed to 14 mass parts, and it was set as the flame retardant composition (change 1). (In this change, the effective dicyandiamide amount is the same as in Example 1.) Also, the coating layer was formed into a mesh-like woven or knitted fabric (Example 1) with a flame-retardant composition (Change 1) whose viscosity was adjusted. Changed to double-sided coating (rotary screen method), heat treated for 2 minutes in a hot air drying oven at 140 ° C, difficult to have biodegradable resin as the main component on the entire surface of the biodegradable mesh knitted fabric base fabric A mesh sheet having a thickness of 0.74 mm, a mass of 350 g / m ² , and a mesh porosity of 24%, in which the coating layer of the flammable composition (change 1) was formed at 47.1%, was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 50%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 1 was unsuitable for reuse because of its flameproof specifications because the flameproofness was lost by washing.
[Comparative Example 2]

In Example 2, the microencapsulated flame retardant imparting agent (2) of the flame retardant composition (2): 40 parts by mass of aliphatic polyester resin-coated urea particles (urea content 35 mass%) urea (providing flame retardancy) Agent (2)) Changed to 14 parts by mass to obtain a flame retardant composition (Change 2). (In this change, the effective urea amount is the same as in Example 2.) In addition, the coating layer is formed by the same method as in Example 2 with the step of “dip (immersion) -nip-drying” twice. Thus, a coating layer of 46.2% was formed on the entire surface of the biodegradable mesh knitted or knitted fabric (Example 2) with a flame retardant composition mainly composed of a biodegradable resin (Modification 2). A mesh sheet having a thickness of 0.74 mm, a mass of 418 g / m ² and a mesh porosity of 20% was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 100%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 2 was unsuitable for re-use according to the flame-proof standard because the flame-proof property was lost by washing.
[Comparative Example 3]

In Example 3, the microencapsulated flame retardant imparting agent (3) of the flame retardant composition (3): 40 parts by mass of polyvinyl alcohol resin-coated phosphonic acid particles (phosphonic acid content 35% by mass) was converted to phosphonic acid (flame retardant). The property-imparting agent (3) was changed to 14 parts by mass to obtain a flame retardant composition (change 3). (* In this change, the amount of effective phosphonic acid is the same as in Example 3.) Also, the formation of the coating layer is to a mesh-like woven or knitted fabric (Example 3) using a flame-retardant composition with a viscosity adjusted (Change 3). It is changed to double-sided coating (rotary screen method) and heat-treated in a hot air drying oven at 140 ° C. for 2 minutes, and the entire surface of the biodegradable mesh knitted / knitted fabric is mainly composed of biodegradable resin. A mesh sheet having a thickness of 0.74 mm, a mass of 382 g / m ² , and a mesh porosity of 10.5%, in which the coating layer of the flame retardant composition (change 3) was formed at 41.1%, was obtained. The cross section filling rate of the yarn of the obtained mesh sheet was 60%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 3 was unsuitable for re-use according to the flame-proof standard because the flame-proof property was lost by washing.
[Comparative Example 4]

In Example 4, the microencapsulated flame retardant imparting agent (1) of the flame retardant composition (1): 40 parts by mass of polylactic acid-coated dicyandiamide particles (dicyandiamide content 35% by mass) was converted to dicyandiamide (a flame retardant imparting agent ( 1)) It changed to 14 mass parts, and it was set as the flame retardant composition (change 1). (* In this modified composition, the effective dicyandiamide amount is the same as in Example 4.) Also, the coating layer was formed in a mesh-like woven or knitted fabric (Modified Example 1) using a flame-retardant composition (Modified Example 1) whose viscosity was adjusted. ) To a double-sided coating (rotary screen method) to obtain an intermediate of a mesh composite having a thickness of 0.70 mm and a mass of 345 g / m ² . This intermediate was dipped (immersed) in a liquid bath of the flame retardant composition (4) to adhere the flame retardant composition (change 1) onto the entire surface of the coating layer. Is niped with a mangle roll (squeezing pressure 2 kgf / cm ² ), heat-treated for 2 minutes in a hot air drying oven at 140 ° C., and a biodegradable resin is applied to the entire surface of the biodegradable mesh woven / knitted fabric. 0.76 mm in thickness and mass, in which the total coating layer of the coating layer of the main flame retardant composition (change 1) and the outermost coating layer of the flame retardant composition (4) was formed at 55.4% A mesh sheet having 415 g / m ² and a mesh porosity of 24% was obtained. The cross section filling factor of the yarn of the obtained mesh sheet was 50%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 4 was unsuitable for re-use according to the flame-proof standard because the flame-proof property was lost by washing.
[Comparative Example 5]

In Example 5, microencapsulated flame retardant imparting agent (2) of flame retardant composition (2): Aliphatic polyester resin-coated urea particles (urea content 35 mass%) 40 parts by mass of urea (improving flame retardancy) Agent (2)) Changed to 14 parts by mass to obtain a flame retardant composition (Change 2). (* In this change, the effective urea amount is equivalent to that in Example 5.) In addition, the coating layer was formed by the same method as in Example 2 using the flame retardant composition (Change 2). nip - a step of drying ", thickness 0.66 mm, mass 360 g / m to give a ^second intermediate meshed complex, then the flame retardant composition of the intermediate (4) using" dip ( By the process of “immersion) -nip-drying”, the coating layer and the flame retardancy are formed on the entire surface of the biodegradable mesh woven / knitted fabric with the flame retardant composition mainly composed of the biodegradable resin (change 2). A mesh sheet having a thickness of 0.74 mm, a mass of 427 g / m ² and a mesh porosity of 20%, in which the total coating layer of the outermost coating layer of the composition (4) was 47.3%, was obtained. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 5 was not suitable for re-use according to the flame-proof standard because the flame-proof property was lost by washing.
[Comparative Example 6]

In Example 6, a microencapsulated flame retardant imparting agent (3) of the flame retardant composition (3): 40 parts by mass of polyvinyl alcohol resin-coated phosphonic acid particles (phosphonic acid content 35% by mass) The property-imparting agent (3) was changed to 14 parts by mass to obtain a flame retardant composition (change 3). (In this change, the effective phosphonic acid amount is the same as in Example 6.) Also, the formation of the coating layer is to a mesh-like woven or knitted fabric (Example 3) with a viscosity-adjusted flame retardant composition (Change 3). To a double-sided coating (rotary screen method) to obtain an intermediate of a mesh composite having a thickness of 0.70 mm and a mass of 365 g / m ² . This intermediate was dipped (immersed) in a liquid bath of the flame retardant composition (5) to adhere the flame retardant composition (5) onto the entire surface of the coating layer. Is niped with a mangle roll (squeezing pressure 2 kgf / cm ² ), heat-treated for 2 minutes in a hot air drying oven at 140 ° C., and a biodegradable resin is applied to the entire surface of the biodegradable mesh woven / knitted fabric. The total coating layer of the coating layer made of the main flame retardant composition (change 3) and the outermost coating layer made of the flame retardant composition (5) was formed at 48.0%, thickness 0.77 mm, mass A mesh sheet with 433 g / m ² and a mesh porosity of 10.5% was obtained. The cross section filling rate of the yarn of the obtained mesh sheet was 55%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 6 was unsuitable for re-use according to the flameproof standard because the flameproofness was lost by washing.
[Comparative Example 7]

The pretreatment for the mesh woven or knitted fabric (pattern fabric) of Example 7 was changed to the following composition. (* In this modified composition, the effective dicyandiamide amount is the same as in Example 7.) Also, the coating layer was formed on both sides of the mesh woven or knitted fabric with the flame-retardant composition (4) whose viscosity was adjusted ( This is a rotary screen method, and this is heat-treated in a hot air drying oven at 140 ° C. for 2 minutes. The flame-retardant composition mainly composed of biodegradable resin is formed on the entire surface of the biodegradable mesh woven / knitted fabric. A mesh sheet having a thickness of 0.74 mm, a mass of 355 g / m ² , and a mesh porosity of 24%, in which the coating layer of the product (4) was formed at 47.9%, was obtained. The cross section filling rate of the yarn of the obtained mesh sheet was 45%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 7 was unsuitable for reuse in terms of flameproof specifications because the flameproofness was lost by washing.
<Pretreatment composition (change 1)>
Flame retardant imparting agent (1): Dicyandiamide 7 parts by mass Trademark: Serogen WS: Carboxymethylcellulose: Daiichi Kogyo Seiyaku Co., Ltd. 10 parts by mass Diluted water (distilled water) 100 parts by mass [Comparative Example 8]

From the following composition of Example 8, 20 parts by mass of microencapsulated flame retardant (3): polyvinyl alcohol resin-coated phosphonic acid particles (average particle size 8 μm: phosphonic acid content 35 mass%) was omitted. (Pretreatment composition (change 2)) Also, the formation of the coating layer was changed to double-sided coating (rotary screen method) on the mesh woven or knitted fabric with the flame-retardant composition (5) whose viscosity was adjusted. Heat-treated for 2 minutes in a hot air drying oven, and the coating layer of the flame-retardant composition (5) mainly composed of biodegradable resin is 43.7% on the entire surface of the biodegradable mesh woven or knitted fabric. A mesh sheet having a formed thickness of 0.74 mm, a mass of 400 g / m ² , and a mesh porosity of 18.5% was obtained. The cross section filling rate of the yarn of the obtained mesh sheet was 40%. The performance of the obtained mesh sheet is shown in Table 2. The mesh sheet obtained in Comparative Example 8 was unsuitable for re-use according to the flame-proof standard because the flame-proof property was lost by washing.
<Pretreatment composition (change 2)>
Trademark: Serogen WS: Carboxymethylcellulose: Daiichi Kogyo Seiyaku Co., Ltd. 10 parts by weight Diluted water (distilled water) 100 parts by weight

  The architectural curing mesh sheet obtained by the present invention has the flameproof performance of Article 4 (JIS L1091A method) of the Fire Service Act, and the performance specified by JIS A8952 and the temporary industry association certification standard (penetration resistance due to steel pipe dropping) When the material is disposed of at the same time, the mesh sheet is microbially decomposed over time by the landfill process, and eventually the entire mesh sheet has a characteristic that can disappear from the soil. It is an industrial material sheet that is extremely useful in modern Japan where industrial waste disposal sites are scarce. Although mesh sheets having biodegradability have been proposed in the past, these mesh sheets cannot withstand the harsh washing for washing dirt, and have flame resistance that was initially possessed after washing. However, in the present invention, it should be noted that these mesh sheets have washing resistance. It is possible to repeatedly use it at the construction site by maintaining the initial flameproofness even after washing, that is, the building curing mesh sheet obtained by the present invention has durability and durability during use that did not exist conventionally. It is an extremely useful industrial material sheet that combines biodegradability after use. The architectural curing mesh sheet of the present invention is preferably subjected to a landfill process at a disposal site equipped with appropriate equipment by a specialized supplier.

Explanatory drawing which shows the laminated structure of this invention mesh sheet | seat manufactured in Examples 1-3. Explanatory drawing which shows lamination | stacking manufacture of the mesh sheet | seat of this invention manufactured in Examples 4-6. Explanatory drawing which shows the laminated structure of the mesh sheet | seat of this invention manufactured in Example 7 and 8. FIG.

Claims (10)

Fabricated by weaving and knitting multifilament yarn having biodegradability and covering the entire exposed surface of the multifilament yarn constituting the base fabric, which is made of mesh-like woven or knitted fabric in which mesh gaps are formed And a mesh composite having a coating layer composed of a flame retardant composition mainly composed of a biodegradable resin, wherein the flame retardant composition forming the coating layer is 100 masses of the biodegradable resin. to part, it contains microencapsulated flame retardant 5-75 parts by weight, and are fixed filaments with each other by impregnating the filament between the capillary gap of the multi-filament yarn,
The microencapsulated flame retardant imparting agent is at least one biodegradable resin selected from a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer) resin, and a polyvinyl alcohol (copolymer) resin. One or more nitrogen atom-containing compounds selected from urea derivatives, guanidine derivatives, and melamine salts, or phosphates, metal (organic) phosphates, phosphate ester derivatives, phosphones A reusable biodegradable mesh sheet comprising one or more microcapsules containing at least one phosphorus atom-containing compound selected from an acid compound and a phosphinic acid compound . A multilayer mesh composite in which an outermost coating layer of a flame retardant composition mainly composed of a biodegradable resin is formed on the entire surface of the mesh composite, wherein the outermost coating layer is The reusable biodegradable mesh sheet according to claim 1, comprising 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin. Manufactured by Ojen multifilament yarn having biodegradability, eyes fit gap and base fabric comprising a mesh woven or knitted fabric that is formed on the entire surface of the base fabric, flame mainly containing biodegradable resin A mesh composite having a coating layer formed of a flammable composition, wherein the base fabric has been subjected to a pretreatment with a pretreatment agent containing a microencapsulated flame retardant, and The flame retardant composition forming the coating layer contains 5 to 75 parts by mass of melamine flame retardant particles with respect to 100 parts by mass of the biodegradable resin, and capillary gaps between the filaments of the multifilament yarn Impregnated with each other to fix the filaments together,
The microencapsulated flame retardant imparting agent is at least one biodegradable resin selected from a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer) resin, and a polyvinyl alcohol (copolymer) resin. One or more nitrogen atom-containing compounds selected from urea derivatives, guanidine derivatives, and melamine salts, or phosphates, metal (organic) phosphates, phosphate ester derivatives, phosphones A reusable biodegradable mesh sheet comprising one or more microcapsules containing at least one phosphorus atom-containing compound selected from an acid compound and a phosphinic acid compound .   The reusable biodegradable mesh sheet according to any one of claims 1 to 3, wherein the mesh composite has a mesh void ratio (open area ratio) of 5 to 50%.   The multifilament yarn having biodegradability is a fineness 227 comprising at least one selected from a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer) resin, and a polyvinyl alcohol (copolymer) resin. The laundry-reusable biodegradable mesh sheet according to any one of claims 1 to 4, which is a yarn of ~ 2222 dtex, or a mixed yarn of these and regenerated cellulose fibers.   The biodegradable resin forming the coating layer is composed of one or more selected from a polylactic acid (copolymer) resin, an aliphatic polyester (copolymer) resin, and a polyvinyl alcohol (copolymer) resin. The laundry reusable biodegradable mesh sheet according to any one of claims 1 to 3. The laundry reuse according to claim 2 or 3, wherein the melamine flame retardant particles are at least one selected from melamine cyanurate, melamine sulfate, and a composite of a (poly) phosphate compound and a melamine derivative. Possible biodegradable mesh sheet. The reusable biodegradable mesh sheet according to any one of claims 1 to 7, wherein a ratio of a mass of the base fabric to a mass of the mesh composite is 40 to 80% . The reusable biodegradable laundry according to any one of claims 1 to 8, wherein the mesh-shaped knitted fabric is any one of plain weave, imitation fabric, cocoon fabric, Russell fabric, and triaxial fabric. Mesh sheet. Impregnation and fixation of the multifilament yarn in the capillary gap between the filaments of the multifilament yarn at a depth of 75 to 100% from the outside with respect to at least the weft radius of the cross section of the multifilament yarn. The reusable biodegradable mesh sheet according to any one of claims 1 to 9, which is impregnated and fixed .

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