JP2019126921A - Dust resistant film, and sailcloth, mesh sheet, and tarpaulin using these - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dust-proof (effect due to antistatic property) soft vinyl chloride resin film and film without using a surfactant or wax, and to use them for dust-proof property (effect due to antistatic property). ) Providing industrial material sheets. SOLUTION: The plasticizer mainly contains a vinyl chloride resin and a plasticizer, and as the plasticizer, at least isophthalic acid dialkyl ether esters, terephthalic acid dialkyl ether esters, cyclohexanedicarboxylic acid dialkyl ether esters, dicarboxylic acid dialkyl ether esters, etc. A film containing one or more alkyl ether ester compounds selected from trimellitic acid tris (alkyl ether esters) and pyromellitic acid tetrakis (alkyl ether esters), and antifouling conductivity on one or more sides of this film. The layer is formed on the entire surface or in a network with an area occupancy of 20% or more. [Selection diagram] None

Description

  The present invention relates to a dust-proof soft vinyl chloride resin film that does not contain a phthalic acid compound (ortho) as a plasticizer component, and in particular, 1) a dust-proof film using a soft vinyl chloride resin film in a coated state. The present invention relates to a canvas and a mesh sheet for industrial materials having excellent properties and electrical conductivity, and 2) a tarpaulin for industrial materials having excellent dust resistance and electrical conductivity obtained by laminating soft vinyl chloride resin films.

  Phthalate esters are widely used mainly as plasticizers and molding aids for vinyl chloride resins, but in recent years the suspicion that they are endocrine disrupters affecting human and animal hormones are intensified, and they are used mainly in Europe With the progress of regulations, the European Chemical Organization has listed three substances, DBP, DEHP (DOP), and BBP, on the list of candidate substances of very high concern (SVHC) of the REACH regulation, and then added 10 more phthalates to the SVHC list. Added to. Furthermore, the RoHS Directive, which restricts the use of specified hazardous substances in electronic and electrical equipment established by the EU European Union, recently added DEHP (DOP), BBP, DBP, and DIBP as specified hazardous substances. Usage restrictions on equipment are being considered. In Japan and the United States, DEHP (DOP), DBP, BBP, DINP, DIDP, and DNOP are designated as restricted substances for use in childcare products and toys for infants, and the Ministry of Health, Labor and Welfare has designated DEHP (DOP) food equipment and It is prohibited to use in applications such as containers. For this reason, recent soft vinyl chloride resin products have shifted to products that use safer plasticizers as product designs in accordance with the REACH regulations and the RoHS directive, but depending on the type of plasticizer to be replaced, The problem arises that the moldability and physical properties of the

  The trend of product design in accordance with the REACH regulations and the RoHS directive has spread to industries other than toys, food appliances and containers, etc., and a movement to change plasticizers has become noticeable and plasticizers Manufacturers are also beginning to focus on proposals for alternatives, but no alternatives have been proposed for a general-purpose dialkyl ether ester compound (Patent Document 1) known as a conductive plasticizer. Applicant of the present invention is a tarpaulin material used for sheet warehouses, tent houses, pavilions, flexible containers, aquariums, etc., canvas materials used for truck hoods, seat covers, etc. Those who are engaged in the business of manufacturing industrial material sheets made of soft vinyl chloride resin that are used outdoors for a long time, such as mesh sheet materials used for sunshades, etc. However, since it is used in a large area close to daily life, there is a concern that a small amount of product odor may be volatilized and breathed out, and plasticizer components bleed from landfilled products From the viewpoint of fear of contamination of groundwater, etc., an industrial material sheet made of soft vinyl chloride resin that does not use phthalate ester compounds (Patent Documents 2 to 5) was proposed. These soft vinyl chloride resin industrial material sheets retain their free colorability unless they are mixed with surfactants or waxes that may cause bleed contamination, poor printing, or poor bonding between sheets. While it is difficult to impart dustproofness and conductivity, it is therefore possible to use a dustproof and electrically conductive soft vinyl chloride resin film having free coloring according to the REACH regulation and the RoHS directive, and these A dustproof and conductive industrial material sheet conforming to the REACH Regulation and RoHS Directive has been desired.

JP 2000-103017 A JP, 2015-217608, A JP, 2015-223700, A JP, 2016-022708, A JP, 2015-033179, A

  The present invention provides free colorability according to the REACH regulations and the RoHS directive without using surfactants or waxes that may cause adverse effects such as bleed contamination, printing defects, and poor bonding between sheets. Dust-proof and conductive soft vinyl chloride resin films, and dust-proof and conductive industrial material sheets according to REACH regulations and RoHS directives using these films (for sheet warehouses, tent houses, and pavilions) Tarpaulin materials used for flexible containers and tanks, canvas materials used for truck hoods, seat covers, etc., mesh sheet materials used for building curing sheets, breathable sunscreens, etc.) It is.

  As a result of conducting researches and studies in view of the above-mentioned present conditions, the present inventor mainly contains a vinyl chloride resin and a plasticizer, and as a plasticizer, at least an isophthalic acid dialkyl ether ester, a terephthalic acid dialkyl ether ester, One or more alkyl ether ester compounds selected from cyclohexanedicarboxylic acid dialkyl ether esters, dicarboxylic acid dialkyl ether esters, trimellitic acid tris (alkyl ether esters), and pyromellitic acid tetrakis (alkyl ether esters) By containing, a dustproof and conductive soft vinyl chloride resin film having a free coloring property according to the REACH regulation and the RoHS directive can be obtained, and furthermore, according to the REACH regulation and the RoHS directive using these films. Dustproof And electrically conductive industrial materials sheet has completed the present invention have found that the obtained.

That is, the dustproof film of the present invention mainly comprises a vinyl chloride resin and a plasticizer, and as the plasticizer, at least an isophthalic acid dialkyl ether ester (group of [Chemical formula 1], terephthalic acid dialkyl ether ester ([Chemical formula 2] ], Cyclohexanedicarboxylic acid dialkyl ether ester ([Chemical group 3]), dicarboxylic acid dialkyl ether ester ([Chemical group 4]), trimellitic acid tris (alkyl ether ester) ([Chemical group 5] group) ) And one or more alkyl ether ester compounds selected from pyromellitic acid tetrakis (alkyl ether ester) (the group of [Chemical Formula 6]), and an antifouling conductive layer is formed on at least one side of the film. , 1) overall formation, or 2) a reticulated continuum having an area occupancy of at least 20% It is preferable to have been made.
(Wherein R ₁ and R _{2 each} represent a linear or branched alkyl group having 3 to 15 carbon atoms, and A ₁ and A _{2 each} have 2 to 4 carbon atoms) .m showing an alkylene group, n is an integer of 1 to 7, _{a 1} and _a 2, _{R 1} and _{R 2,} and m and n each is a good .A ₁ be different even in the same The total carbon number of R ₁ and A ₂ and R ₂ is 5 to 17. [Chemical formula 3] is 1,2-cyclohexanedicarboxylic acid dialkyl ether ester, 1,3-cyclohexanedicarboxylic acid dialkyl ether ester, 1,4-dicarboxylic acid Any of cycloalkyldicarboxylic acid dialkyl ether esters may be used.)
([Chemical Formula 4]: wherein R ₁ and R ₂ represent a linear or branched alkyl group having 3 to 15 carbon atoms, A ₁ and A ₂ represent an alkylene group having 2 to 4 carbon atoms, A ₃ represents an alkylene group having 4 to 12 carbon atoms, m and n are integers of 1 to 7, and A ₁ and A ₂ , R ₁ and R _2, and m and n are the same or different. The total carbon number of A ₁ and R ₁ and A ₂ and R ₂ is 5 to 17.)
(Wherein R ₁ , R ₂ and R _{3 each} represent a linear or branched alkyl group having _{3 to} 15 carbon atoms, and A ₁ , A ₂ and A _{3 each} have 2 to 2 carbon atoms) And m, n and o each represents an integer of 1 to 7, and A ₁ and A ₂ and A ₃ , R ₁ and R ₂ and R _3, and m and n and o are respectively the same. The total carbon number of A ₁ and R _1, A ₂ and R _2, and A ₃ and R ₃ is 5 to 17.)
(Wherein R ₁ , R ₂ , R ₃ and R _{4 each} represent a linear or branched alkyl group having ₃ to 15 carbon atoms, and A ₁ , A ₂ , A ₃ and A 4 ₄ represents an alkylene group having 2 to ₄ carbon atoms, m, n, o and p each represents an integer of 1 to 7, and A ₁ , A ₂ , A ₃ and A ₄ , R ₁ , R ₂ , R ₃ and R ₄ and m, n, o and p may be the same or different from each other: A ₁ and R _1, A ₂ and R _2, A ₃ and R _3, and A ₄ and R ₄ The number is 5 to 17.)

In the dustproof film of the present invention, the plasticizer may further comprise a dialkyl ester of isophthalic acid (group of [Chemical Formula 7]), a dialkyl ester of terephthalic acid (Group of Chemical Formula 8), or a dialkyl ester of cyclohexanedicarboxylic acid (Chemical Formula 9). Group), dicarboxylic acid dialkyl ester ([Chemical group 10]), trimellitic acid tris (alkyl ester) ([Chemical group 11]), and pyromellitic acid tetrakis (alkyl ester) ([Chemical group 12] group) It is preferable to use in combination one or more alkyl ester compounds selected from
(Wherein R ₅ and R _{6 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ and R ₆ are each identical to each other) [Chem. 9] may be any of 1,2-cyclohexanedicarboxylic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, 1,4-cyclohexanedicarboxylic acid dialkyl ester .)
([Chemical Formula 10]: wherein R ₅ and R ₆ represent a linear or branched alkyl group having 3 to 17 carbon atoms, and A ₄ represents an alkylene group having 4 to 12 carbon atoms. R ₅ , R ₆ may be identical to or different from each other.)
(Wherein R ₅ , R ₆ and R _{7 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ , R ₆ and R ₇ are each identical to each other) Or may be different.)
(Wherein R ₅ , R ₆ , R ₇ and R _{8 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ , R ₆ and R ₇ , R ₇ Each ₈ may be the same or different.)

  In the dustproof film of the present invention, the antifouling conductive layer preferably contains one or more selected from carbon nanotubes, fullerenes, and π-electron conjugated conductive polymers.

  In the dustproof film of the present invention, the antifouling conductive layer is made of at least one nanoparticle selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound It is preferable that 1-10 mass% nanoparticle network is comprised with respect to the said coating-film layer.

  The canvas and mesh sheet of the present invention are provided with the dust-proof film described in any one of paragraphs [0007] to [0010] in a coated state on the entire surface of the fabric, using the fabric as a base material. It is preferable.

  In the tarpaulin of the present invention, it is preferable that the dustproof film described in any one of the paragraphs [0007] to [0010] be laminated on the entire surface of the fabric using the fabric as a base material.

  According to the present invention, free coloring in accordance with the REACH regulations and the RoHS directive is possible without using surfactants or waxes that may cause adverse effects such as bleed contamination, printing defects, and poor bonding between sheets. And dust-proof and conductive soft vinyl chloride resin films and dust-proof and conductive industrial material sheets conforming to the REACH regulation and RoHS directive using these films are obtained. It can be widely used for warehouses, tent houses, pavilions, flexible containers, water tanks, truck tops, seat covers, construction curing sheets, ventilation, etc.

The dustproof film of the present invention mainly comprises a vinyl chloride resin and a plasticizer, and contains at least one or more alkyl ether ester compounds (having one or more ether bonds in the alkyl chain) as a plasticizer, It is preferable that the mass ratio of the alkyl ether ester compound and the alkyl ester compound is 3: 1 to 1: 3, particularly preferably 2: 1 to 1: 1, further containing one or more alkyl ester compounds as necessary. . The alkyl ether ester compounds are isophthalic acid dialkyl ether esters (group of [Chemical formula 1], terephthalic acid dialkyl ether esters (group of [chemical formula 2], cyclohexanedicarboxylic acid dialkyl ether esters (group of [chemical formula 3]), dicarboxylic acids Acid dialkyl ether ester (group of [Chemical formula 4], trimellitic acid tris (alkyl ether ester) (group of [chemical formula 5], and pyromellitic acid tetrakis (alkyl ether ester) (group of [chemical formula 6]) One or more selected species can be mentioned.
(Wherein R ₁ and R _{2 each} represent a linear or branched alkyl group having 3 to 15 carbon atoms, and A ₁ and A _{2 each} have 2 to 4 carbon atoms) .m showing an alkylene group, n is an integer of 1 to 7, _{a 1} and _a 2, _{R 1} and _{R 2,} and m and n each is a good .A ₁ be different even in the same The total carbon number of R ₁ and A ₂ and R ₂ is 5 to 17. [Chemical formula 3] is 1,2-cyclohexanedicarboxylic acid dialkyl ether ester, 1,3-cyclohexanedicarboxylic acid dialkyl ether ester, 1,4-dicarboxylic acid Any of cycloalkyldicarboxylic acid dialkyl ether esters may be used.)
([Chemical Formula 4]: wherein R ₁ and R ₂ represent a linear or branched alkyl group having 3 to 15 carbon atoms, A ₁ and A ₂ represent an alkylene group having 2 to 4 carbon atoms, A ₃ represents an alkylene group having 4 to 12 carbon atoms, m and n are integers of 1 to 7, and A ₁ and A ₂ , R ₁ and R _2, and m and n are the same or different. The total carbon number of A ₁ and R ₁ and A ₂ and R ₂ is 5 to 17.)
(Wherein R ₁ , R ₂ and R _{3 each} represent a linear or branched alkyl group having _{3 to} 15 carbon atoms, and A ₁ , A ₂ and A _{3 each} have 2 to 2 carbon atoms) And m, n and o each represents an integer of 1 to 7, and A ₁ and A ₂ and A ₃ , R ₁ and R ₂ and R _3, and m and n and o are respectively the same. The total carbon number of A ₁ and R _1, A ₂ and R _2, and A ₃ and R ₃ is 5 to 17.)
(Wherein R ₁ , R ₂ , R ₃ and R _{4 each} represent a linear or branched alkyl group having ₃ to 15 carbon atoms, and A ₁ , A ₂ , A ₃ and A 4 ₄ represents an alkylene group having 2 to ₄ carbon atoms, m, n, o and p each represents an integer of 1 to 7, and A ₁ , A ₂ , A ₃ and A ₄ , R ₁ , R ₂ , R ₃ and R ₄ and m, n, o and p may be the same or different from each other: A ₁ and R _1, A ₂ and R _2, A ₃ and R _3, and A ₄ and R ₄ The number is 5 to 17.)

The alkyl ester compound used in combination with the above alkyl ether ester compound according to need is isophthalic acid dialkyl ester (group of [Chemical formula 7], terephthalic acid dialkyl ester (group of [chemical formula 8]), cyclohexanedicarboxylic acid dialkyl ester ([ 9], dicarboxylic acid dialkyl ester (group of [compound 10], trimellitic acid tris (alkyl ester) (group of [compound 11]), and pyromellitic acid tetrakis (alkyl ester) ((compound 12) And one or more selected from the group consisting of
(Wherein R ₅ and R _{6 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ and R ₆ are each identical to each other) [Chem. 9] may be any of 1,2-cyclohexanedicarboxylic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, 1,4-cyclohexanedicarboxylic acid dialkyl ester .)
([Chemical Formula 10]: wherein R ₅ and R ₆ represent a linear or branched alkyl group having 3 to 17 carbon atoms, and A ₄ represents an alkylene group having 4 to 12 carbon atoms. R ₅ , R ₆ may be identical to or different from each other.)
(Wherein R ₅ , R ₆ and R _{7 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ , R ₆ and R ₇ are each identical to each other) Or may be different.)
(Wherein R ₅ , R ₆ , R ₇ and R _{8 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ , R ₆ and R ₇ , R ₇ Each ₈ may be the same or different.)

  The amount of the plasticizer contained in the dustproof film of the present invention is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the plasticizer has an alkyl ether ester compound (one or more ether bonds in the alkyl chain). In the case of having an alkyl ester compound in combination with 10 to 150 parts by mass, preferably 30 to 80 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, the mixing ratio of the alkyl ether ester compound and the alkyl ester compound Is 3: 1 to 1: 3, preferably 2: 1 to 1: 1. For example, when the compounding amount of the alkyl ether ester compound is 50 parts by mass, the compounding amount of the alkyl ester compound is 25 parts by mass (mass ratio 2: 1), and when the compounding amount of the alkyl ether ester compound is 35 parts by mass, As for the compounding quantity of an ester compound, 35 mass parts (mass ratio 1: 1) is especially preferable. The dustproof film of the present invention further comprises a chlorinated paraffin compound and an aromatic phosphate such as tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, etc., as necessary for imparting flame resistance. The compound may be used together as a flameproofing agent and a plasticizer, about 5 to 15% by mass with respect to the amount of the plasticizer. In addition, when imparting heat resistance to the dustproof film of the present invention, a reactive acrylic compound having two or more (meth) acryloyl groups at the molecular end or side chain, and an allyl phthalate compound having two or more allyl groups Etc. can be used together with about 5 to 15% by mass with respect to the above-mentioned plasticizer.

  Examples of the dicarboxylic acid used in the production of the alkyl ether ester compounds represented by the formulas [Chemical Formula 1] to [Chemical Formula 6] (having one or more ether bonds in the alkyl chain) include adipic acid, azelaic acid, sebacic acid, and succinic acid. Acids, dicarboxylic acids such as isophthalic acid and terephthalic acid, trivalent or higher polyvalent carboxylic acids, divalent carboxylic acids having an epoxycyclohexane ring, aromatic polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, and the like An acid anhydride of carboxylic acid can be used. Specific examples of such alkyl ether ester compounds include diethyl cellosolve isophthalic acid, dibutyl cellosolve terephthalate, 1,2-cyclohexane dibutyl cellosolve, 1,3-cyclohexane dibutyl cellosolve, 1,4-cyclohexane dibutyl cellosolve, diethyl cellosolve adipate. Reaction of carboxylic acid with mono- and poly-alkylene glycol monoalkyl ether by dibutyl cellosolve adipate, diethyl cellosolve sebacate, dibutyl cellosolve sebacate, trisdibutyl cellosolve trimellitate, tetrakis dibutyl cellosolve pyromellitic acid, etc. Things are listed. Mono- and poly-alkylene glycol monoalkyl ethers are adducts of alcohol and ethylene oxide, such as propanol, butanol, hexanol, heptanol, octanol, and nonanol, addition compounds of alcohol and propylene oxide, and adducts of alcohol and butylene oxide. Or an adduct of alcohol and two or more alkylene oxides selected from alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, which are specifically ethylene glycol monooctyl ether, diethylene glycol monomethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol monoheptyl ether, triethylene glycol monomethyl ether, triethylene glycol (Mono-poly) alkylene glycol monoalkyl ethers such as tylene glycol monopropyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monooctyl ether, dipropylene glycol monobutyl ether, butylene glycol monoethyl ether, In addition, diethylene glycol di-2-ethyl hexonate, tetraethylene glycol di-2-ethyl hexonate, hexaethylene glycol di-2-ethyl hexonate, triethylene glycol diethyl butyrate, polyethylene glycol diethyl butyrate, polypropylene Glycol diethyl hexonate, triethylene glycol dibenzoate, tetraethylene glycol dibenzo Zoeto, polyethylene glycol dibenzoate, polypropylene glycol dibenzoate or polyethylene glycol-2-ethylhexonate benzoate, and the like.

  Regarding the alkyl ester compounds of the above [Chemical Formula 7] to [Chemical Formula 9], the plasticizer of isophthalic acid dialkyl ester (the group of [Chemical Formula 7]) is synthesized, for example, by an esterification reaction of isophthalic acid and 2-ethylhexanol. Particularly preferable is di (2-ethylhexyl) isophthalate, and dibutyl isophthalate, diisobutyl isophthalate, dihexyl isophthalate, diheptyl isophthalate, dinonyl isophthalate, diisononyl isophthalate, diisodecyl isophthalate, didecyl isophthalate and butyl benzyl isophthalate. Etc. are exemplified. The plasticizer of the terephthalic acid dialkyl ester ([Chemical Group 8]) is particularly preferably, for example, di-2-ethylhexyl terephthalate (dioctyl terephthalate) synthesized by esterification reaction of terephthalic acid and 2-ethylhexanol. Other examples include dibutyl terephthalate, diisobutyl terephthalate, dihexyl terephthalate, diheptyl terephthalate, dinonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, didecyl terephthalate, butyl benzyl terephthalate and the like. The plasticizer of the dialkyl ester of cyclohexanedicarboxylic acid (group of [Chemical 9]) is, for example, di-2-ethylhexyl cyclohexanedicarboxylate (also known as dioctylcyclohexanedicarboxylate) obtained by hydrogenating the benzene ring of DOP (dioctyl phthalate). Particularly preferred, other dibutyl cyclohexanedicarboxylate, diisobutylcyclohexanedicarboxylate, dihexylcyclohexanedicarboxylate, diheptylcyclohexanedicarboxylate, dinonylcyclohexanedicarboxylate, diisononylcyclohexanedicarboxylate, diisodecylcyclohexanedicarboxylate, didecylcyclohexanedicarboxylate, butylbenzylcyclohexanedicarboxylate, etc. Is exemplified. The cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical 9]) includes variations of the dialkyl ester in the above specific examples in the 1,2-position, 1,3-position, and 1,4-position of the cyclohexane ring. To do.

  Regarding the alkyl ester compounds represented by the above [Chemical Formula 10] to [Chemical Formula 12], the dicarboxylic acid dialkyl ester (the group of [Chemical Formula 10]) is synthesized by, for example, an esterification reaction between adipic acid and 2-ethylhexanol. Di (2-ethylhexyl) adipate is particularly preferred, and other dibutyl adipate, diisobutyl adipate, dihexyl adipate, diheptyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, didecyl adipate, butylbenzyl adipate In particular, di (2-ethylhexyl) sebacate synthesized by an esterification reaction of sebacic acid and 2-ethylhexanol is particularly preferable, and other dibutyl sebacate, diisobutyl sebacate, dihexyl sebacate, diheba sebacate Chill, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, didecyl sebacate, sebacic acid butyl benzyl are exemplified. The plasticizer of trimellitic acid tris (alkyl ester) ([Chemical Group 11]) is, for example, trimellitic acid tris synthesized by esterification of trimellitic acid or trimellitic anhydride and 2-ethylhexanol. (2-ethylhexyl) is particularly preferable, and other tritrimellitic acid tributyl, trimellitic acid tris (isobutyl), trimellitic acid trihexyl, trimellitic acid triheptyl, trimellitic acid trinonyl, trimellitic acid tris (isononyl), trimellitic acid triisodecyl And trimellitic acid tridecyl, trimellitic acid tris (butylbenzyl) and the like. The plasticizer of pyromellitic acid tetrakis (alkyl ester) ([Chemical group 12]) is, for example, pyromellitic acid tetrakis synthesized by esterification reaction of pyromellitic acid or pyromellitic acid anhydride with 2-ethylhexanol. (2-ethylhexyl) is particularly preferable, and to tetrabutyl pyromellitic acid, tetrakis (isobutyl) pyromellitic acid, tetrahexyl pyromellitic acid, tetraheptyl pyromellitic acid, tetranonyl pyromellitic acid, tetrakis (isononyl) pyromellitic acid, pyromellitic acid Examples include tetraisodecyl acid, tetradecyl pyromellitic acid, and tetrakis (butyl benzyl) pyromellitic acid.

  The vinyl chloride resin contained in the dustproof film of the present invention is a homopolymer of vinyl chloride monomer (a homopolymer having a degree of polymerization of 1000 to 4000), an emulsion polymer (wheat flour) and a suspension polymer (granulated sugar). Can be used. The vinyl chloride resin of the emulsion polymer forms a paste-like composition together with a plasticizer and an additive, is used for coating and dipping coating, and is heated and gelled to form the dustproof film (thickness 0.01 mm) of the present invention. 1 mm) can be obtained in the form of a coated film. A fabric made by impregnating and forming a coating film of this paste-like composition on a fabric is a canvas for industrial materials, and a mesh sheet for industrial materials impregnated in a coarse fabric and formed on a coarse fabric. The suspension polymer vinyl chloride resin forms a compound-like composition together with a plasticizer and an additive, is subjected to calendar molding, and is heated and kneaded and heated and rolled to form a dustproof film (thickness 0.1 mm to 1 mm) can be obtained. A tarpaulin for industrial materials is obtained by laminating a dustproof film made of this vinyl chloride resin on both sides of a fabric. In the present invention, the vinyl chloride resin includes a vinyl chloride resin copolymer and a graft copolymer having a vinyl chloride resin as a main chain, and the copolymer component includes α-olefins having 2 to 30 carbon atoms, acrylic acid, and the like. Examples thereof include vinyl compounds such as esters, methacrylic acid and esters thereof, maleic acid and esters thereof, vinyl acetate, vinyl propionate and alkyl vinyl ether. The dustproof film includes polyol compounds, chlorinated polyethylene, butyl rubber, acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer, styrene-butadiene copolymer, etc. About 5-25 mass% can be used together with respect to a vinyl chloride-type resin for the purpose of improvement, heat resistant characteristic improvement, impact relaxation etc. In addition, reactive compounds such as polyisocyanate compounds, carbodiimide compounds, and oxazoline compounds are added to form a crosslinked structure in a dust-proof film (including a coating film) to improve heat resistance, or to fabrics, knitted fabrics, etc. The adhesion to a fabric or the like can also be improved.

  In addition, the dustproof film can contain various arbitrary amounts of known additives for synthetic resins as components other than plasticizers. As stabilizers for vinyl chloride resins, calcium zinc composites, barium zinc composites, Inhibitors of organic tin laurate, organic tin mercaptite, epoxy, etc. are used alone or in combination, and by using about 1 to 10 parts by mass with respect to 100 parts by mass of vinyl chloride resin, thermal discoloration at the time of molding is suppressed, Improve weather resistance. Furthermore, light stabilizers (such as hindered amine compounds), UV absorbers (such as benzotriazole compounds, benzophenone compounds), and antioxidants (such as phenol compounds and vitamin E compounds) are added to 100 parts by mass of the vinyl chloride resin. By using about 0.1-5 mass parts, the thermal discoloration at the time of shaping | molding is suppressed synergistically, and a weather resistance is improved synergistically. In the dustproof film of the present invention, flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, bromine-substituted organic compounds and the like, fillers such as calcium carbonate, barium sulfate, silica etc. Can be blended in an amount compatible with the above. Further, the dustproof film of the present invention may be a transparent film containing no flame retardant or filler, or a light translucent film containing a flame retardant or filler, and may be an inorganic pigment (titanium oxide, brassica). , Carbon black, etc.), transparent pigments arbitrarily colored with organic pigments (azo, quinacridone, phthalocyanine, nitro, perylene, etc.), colored light translucent, colored shading, Either may be sufficient.

A composite of a fabric (woven fabric, knitted fabric, coarse woven fabric) and the dustproof film (in the form of a coated film) of the present invention is a canvas for industrial material, which is impregnated in coarse woven fabric and formed on coarse woven fabric Mesh sheet. Further, a composite of a fabric (woven fabric, knitted fabric, coarse woven fabric) and the dustproof film of the present invention with a fabric is a tarpaulin for industrial materials. Fabric, synthetic fibers, natural fibers, semisynthetic fibers, inorganic fibers or mass 50 to 500 g / ^{m 2} from the mix fibers are woven consisting of two or more thereof, preferably the mass 65~280g / ^{m 2} basis weight fabric, Knitted and coarse woven fabrics. Synthetic fibers include nylon fiber, vinylon fiber, polypropylene fiber, polyester fiber, wholly aromatic polyester fiber, ultrahigh molecular weight polyethylene fiber, wholly aromatic polyamide (aramid) fiber, and heterocyclic polymer fiber (polybenzoxazole fiber, poly Benzimidazole fiber) and the like. Examples of natural fibers include cotton, hemp and kenaf, and examples of semisynthetic fibers include rayon and acetate. Examples of inorganic fibers include glass fibers, silica fibers, alumina fibers, silica alumina fibers, carbon fibers and the like. In the present invention, in particular, known fabrics such as multifilament yarns by synthetic fibers, spun yarns, plain fabrics by covering yarns, twill weaves, satin weaves, imitation wovens, imitation wovens, basket weaves, triaxial weaves, tetraaxial weaves and the like can be used. These fabrics may be subjected to water repellent treatment, water absorption prevention treatment, adhesion treatment, flame retardant treatment, and the like as necessary. The fabric used in the present invention is preferably a plain fabric made of polyester fiber, aramid fiber, carbon fiber, glass fiber, or the like.

  Among the fabrics used in the present invention, fabrics suitable for canvas are spun yarns (short fiber spun yarn) in the range of 10th (591 dtex) to 60th (97 ddtex), especially 10th (591 dtex), 14th (422 dtex), 16 This is a plain woven fabric having a void porosity of less than 5% using spun yarns having a count (370 dtex), a 20th count (295 dtex), a 24th count (246 dtex), and a 30th count (197 dtex). Specifically, a spun plain woven fabric having a weaving density of 50 to 70 warps and 40 to 60 wefts per inch using 20th single yarn or 20th twin yarn is suitable. Examples of these spun yarns include a core-sheath type, which includes an aramid fiber multifilament yarn as a core component, and a sheath component formed by tying polyester fiber short fibers around the outer periphery. This can drastically improve the ability to prevent hole opening. The fabric suitable for the mesh sheet is a plain woven fabric or imitation woven fabric using a multifilament yarn of 277 to 2222 dtex, preferably 555 to 1666 dtex, and having a void ratio of 20 to 60%, preferably 25 to 40%. , Triaxial fabric and so on. Suitable fabrics for tarpaulins are plain woven fabrics, twill woven fabrics, and satin woven fabrics using multifilament yarns of 277 to 2222 dtex, preferably 555 to 1666 dtex, and voids of 5 to 30%, preferably 10 to 25%. Examples include woven fabric, basket woven fabric, triaxial woven fabric, and tetraaxial woven fabric. These mesh and tarpaulin fabrics include ripstop base fabrics. For example, a portion of warp and / or weft yarns of polyester multifilament yarns are regularly or randomly replaced with aramid fiber multifilament yarns. And arranged. With such specifications, the tear strength and the ability to prevent breakage due to protrusions can be dramatically improved.

  The method of forming a dust-proof film (coating state) on the fabric is selected from, for example, an emulsion polymerization type vinyl chloride resin (100 parts by mass) (from [Chemical group 1] to (Chemical group 6)). The plasticizer (40 to 80 parts by mass) and, if necessary, a plasticizer selected from (group of [Chemical 7]) to (group of [Chemical 12]) is used in combination. 80 parts by weight) of the paste sol composition, known coating methods such as dipping (double-sided processing on fabric), coating (single-sided or double-sided processing on fabric, knife coating, gravure coating, clearance coating, etc. The coated film is formed on the front and back of the fabric by In the case of an industrial material canvas, a gap between the fabric (a gap between a fiber yarn and a fiber yarn and a filament constituting a fiber yarn) by dipping or coating, or a combination means of dipping and coating on the fabric The gap) is impregnated with the paste-like composition, and both surfaces of the canvas fabric are coated with the paste-like composition, and the coating film is formed by heat-treating the gel to form a coating film having a thickness of 0.5 mm. Obtain a canvas of about 1.5 mm. In the case of a mesh sheet, the paste-like composition is impregnated in the interstices of the filaments constituting the fiber yarn by dipping or coating the coarse fabric, and the entire surface of the fine-grained fabric is a paste-like composition. The coating film is formed by heat treatment and gelation to obtain a mesh sheet having a thickness of about 0.5 mm to 2 mm. Further, in the case of tarpaulin, a dustproof film having a thickness of 0.1 mm to 0.3 mm, preferably molded by means of calendar rolling or T-die extrusion on both sides of the fabric with a certain degree of opening, is thermocompression bonded by a laminator, The dust-proof films on the front and back are partially bridge-fused at the openings of the fabric, whereby the dust-proof films are laminated on the front and back to obtain a tarpaulin having a thickness of about 0.5 mm to 1.5 mm.

  1) An antifouling conductive layer is entirely formed on one side or more of a film mainly containing a vinyl chloride resin and a specific plasticizer (one or more selected from the group of [Chemical Formula 1] to [Chemical Formula 6]), or 2) Use of these antifouling conductive layer-forming films, the fabric described in paragraphs [0022] and [0023] as a base material, and the entire surface of the fabric. The canvas, mesh sheet, and tarpaulin produced by providing the above-mentioned antifouling conductive layer-forming film, 3) or a canvas substrate, mesh sheet substrate, and tarpaulin substrate after producing one or more surfaces of these substrates Further, there can be exemplified an embodiment in which the antifouling conductive layer is a canvas, a mesh sheet, and a tarpaulin in which the antifouling conductive layer is formed on the entire surface or is formed in a net shape with an area occupation ratio of 20% or more. The antifouling conductive layer comprises a). It contains at least one selected from carbon nanotubes, fullerenes and π-electron conjugated conductive polymers, and particularly preferably contains a binder resin from the viewpoint of imparting antifouling properties and wear durability. The content of carbon nanotubes and / or fullerene is 0.1 to 6% by mass, preferably 0.3 to 3% by mass with respect to the coating layer, and the π-electron conjugated conductive polymer is singly or acrylic. Resin, urethane resin, fluorocopolymer resin (fluoroolefin copolymer resin obtained by copolymerizing fluororesin monomer with vinyl monomer), etc., can be used at any concentration, and these single resins or combined resins Can be used in combination with carbon nanotubes and / or fullerenes as binder resins. The binder resin contained in the antifouling conductive layer is 94 to 99.9% by mass with respect to the coating layer, and the binder may be any of an organic compound, an inorganic compound, and a mixture of an organic compound and an inorganic compound, Organic compounds include (meth) acrylic resin, (meth) acrylic copolymer resin, (meth) acrylate radical polymer (ultraviolet curable resin), urethane resin, acrylic modified urethane resin, silicon modified urethane resin, polyester based Examples thereof include resins, vinyl acetate resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, and fluorine-containing copolymer resins. Examples of inorganic compounds include sol-gel thin films mainly composed of metal oxide gels and / or metal hydroxide gels such as silica sol, alumina sol, zirconia sol and niobium oxide sol, and silicon compounds such as polysiloxane, colloidal silica and silica. . b). Furthermore, in the antifouling conductive layer of a), at least one nanoparticle selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound (methyltrimethoxy) Silane, methyltriethoxysilane, etc.) in a mixing ratio of nanoparticles and silane compound or hydrolysis product thereof in a mass% ratio of 20: 1 to 3: 1, and 1 to 10 with respect to the coating layer. By configuring a mass% nanoparticle network, the antistatic effect can be further enhanced.

In particular, each of the antifouling conductive layers formed on the net is a film or a continuous body having an area occupancy of 20% or more, preferably 35 to 70% per one surface of a canvas, a mesh sheet, and a tarpaulin. , 0.05 to 20 g / ^{m 2,} preferably it is to incidental conductive network of 0.5 to 10 g / ^{m 2,} and freely canvas, mesh sheet, and the coloring of such tarpaulins. Such an antifouling conductive layer (conductive network) is a regular continuum such as a square lattice, a triangular lattice, a honeycomb, a round hole punching, or a mesh, or an irregular continuum, or even a single stroke. Writing letters or patterns, letters of lottery, etc. are exemplified. Such an antifouling conductive layer (conductive network) is formed by means such as gravure printing or screen printing.

  The carbon nanotubes have an average fiber diameter of 0.5 to 100 nm and an aspect ratio of 50 to 5000, and may be any of aligned and randomly arranged. Types: Single-walled carbon nanotubes with a diameter of 0.4 nm to 5 nm, double-walled carbon nanotubes with a diameter of 1.5 nm to 5 nm, multi-walled carbon nanotubes with a diameter of 3 nm to 50 nm, cup-stacked carbon nanotubes, oxidized carbon nanotubes, functionalization One or more types selected from carbon nanotubes (terminal modification and / or sidewall modification) and metal (vapor deposition or sputtering) carbon nanotubes, and the arrangement of hexagons (chiral index) constituting the carbon nanotubes is (n, n) Any of an armchair type, a (n, 0) zigzag type, and a (n, m) helical type may be used. These carbon nanotubes can be further improved in conductivity when used in combination with oxides of transition metals such as Ru, Ir, W, Mo, Mn, Ni, and Co. In particular, a π-electron conjugated conductive polymer (described in paragraph [0029]) can also be used as a binder. In particular, metal (vapor deposited or sputtered) carbon nanotubes are carbon nanotubes whose surface is metallized by vapor deposition or sputtering with Au, Ag, Cu, Al, Zn, Ti etc. Au / Ti, Ag / Ti, and Cu / Ti to improve conductivity are effectively improved.

As the fullerene, C ₆₀ fullerene, C ₇₀ fullerene, organically modified fullerene, inorganic modified fullerene, nonmetallic atom-encapsulated fullerene, metal atom-encapsulated fullerene, and the like can be used. And C ₆₀ fullerene 6-membered ring 20 surface, at 5-membered ring 12 surface 32 surface at configured a soccer ball-shaped cage body, organically modified fullerene, C ₆₀ or one or more on the surface of the C _{70 fullerene,} A polymer having a substituent and / or one or more functional groups, or a polymer in which a functional group-substituted fullerene is grafted to a polymer side chain. Endohedral metallofullerenes are atoms of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, lanthanoids, actinoids, or any of the above fullerenes Metal ions are taken in. Nonmetal atom-encapsulating fullerene is any one of the above-mentioned fullerenes such as hydrogenated fullerene containing H, carbonized fullerene containing C, nitrogenated fullerene containing N, oxygenated fullerene containing O, and sulfurized fullerene containing S. is there.

  Specific examples of π-electron conjugated conductive polymers include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers and derivative polymers thereof. The chain is composed of a π-conjugated system, and there are no particular limitations on the side chain, the presence or absence of a substituent, the side chain, and the type of substituent, but polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene) Polypyrrole and polythiophene are particularly preferred, such as poly (3-methoxythiophene), poly (3,4-ethylenedioxythiophene), etc., particularly poly (N-methylpyrrole), poly (3-methylthiophene) and the like. Alkyl-substituted compounds are preferred because of their excellent solubility in organic solvents. In addition, the π electron conjugated conductive polymer is doped with a polymeric carboxylate (polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.), or a polymeric sulfonic acid (polyvinylsulfonic acid, polystyrene sulfonic acid, polyisoprene sulfone) Acid, polyethyl acrylate sulfonate, butyl sulfonate polyacrylate, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or the like, or polymer carboxylate and polymer sulfone The conductivity can be further enhanced by co-doping with an acid in a mass ratio of 2: 1 to 1: 5 The ratio of the π-electron conjugated conductive polymer to the polymeric carboxylate is 10: 1. 1: 1, the ratio of π electron conjugated conductive polymer to polymeric carboxylate and polymeric sulfonic acid is 5: 1 1: 1 is preferable, and the polymeric carboxylate, or the polymeric carboxylate and the polymeric sulfonic acid coexist with the monomer of the π-electron conjugated conductive polymer during the synthesis of the π-electron conjugated conductive polymer. What is doped in the π electron conjugated conductive polymer at the time of oxidative polymerization of the π electron conjugated conductive polymer synthesis is preferable.

In order to process the dustproof film of the present invention, and the canvas, mesh sheet, and tarpaulin provided with the dustproof film into sheet shutters, partitions, floor sheets, equipment covers, flexible containers, etc., these same base materials Bonding, and these different types of base materials (end superposition bonding in the same direction in the same plane) can be bonded by high frequency vibration using a high frequency welder. Specifically, the film material is placed between two electrodes (one electrode is a weld bar), and while applying pressure with the weld bar, the substrate is dustproof by applying a potential difference oscillating at a high frequency (1 to 200 MHz) By bringing the film into a melt-softened state by molecular friction heat, the films are fused at the interface between the substrates, and cooled and solidified in that state to obtain a bonded body. In addition, an ultrasonic fusion method in which the amplitude of ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator is amplified and fusion is performed using frictional heat generated on the boundary surface of the base material, or the electric power of the heater A hot air fusion method in which hot air set steplessly at 100 to 700 ° C. is blown between the substrates through the nozzle to melt and soften the surface of the substrate and press-bond the substrate immediately after passing through the nozzle to fuse. Bonding can be performed by a hot plate fusion method or the like in which an adherend is pressure-bonded and fused using a mold (tort) heated at a temperature higher than the melting temperature of the dustproof film. In the above bonding method, when the area occupation ratio of the antifouling conductive layer is 90 to 100%, the compatibility between the binder resin of the antifouling conductive layer and the dustproof film is poor, or the temperature difference between the softening temperatures is large. Since the larger the larger, the bonding adhesive force between the obtained substrates becomes insufficient, the area occupation ratio of the antifouling conductive layer is 20% or more, preferably a continuous body having an area occupation ratio of 35 to 70%, 0.05 to 20 g / ^{m 2,} preferably as a conductive network of 0.5 to 10 g / ^{m 2,} a region other than the antifouling conductive layer, namely a dust-proof film of the base to be surface-exposed, the other substrate It is desirable to provide a state in which the dust-proof film substrate surfaces on the back surface of each of them are at least thermally melted and can be firmly bonded.

Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the range of these examples. In the following examples and comparative examples, the dustproof effect was evaluated by the surface resistivity.
1) Surface resistivity measurement (JIS K 7194 compliant)
The film material piece was allowed to stand for 24 hours at 23 ° C. and a relative humidity of 50% RH, and then the surface resistivity was measured three times using the following resistivity meter (based on JIS K7194), and the average value was defined as the surface resistivity. As a high resistance and resistivity meter, “Hiresta UP MCP-HT800 (range 10 ³ to 10 ¹⁴ Ω) manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used.
2) Dust-proof Commercially available thin wheat flour (Nisshin Flour Milling Co., Ltd.) is uniformly sprinkled on the surface of a static test specimen, and then the specimen is inverted downward to fix the specimen in tension. With the low strength wheat flour allowed to fall freely, it was strongly hit 5 times with the index finger from the back side to evaluate the shedding properties of the low strength wheat flour.
1: Remaining amount less than 10% by mass: good dust resistance
2: Residual amount 10 mass% to less than 25 mass%: slightly inferior in dustproof property
3: Remaining amount exceeding 25% by mass: Poor in dust resistance

Example 1
The following soft vinyl chloride resin paste sol composition (1) is cast on a polyester (PET) sheet (mirror surface) having a thickness of 50 μm by a clearance coating method, and the whole PET sheet is heated in an electric heating furnace at 180 ° C. for 1 minute. Gelation treatment was performed to obtain a film (1) having a film thickness of 0.2 mm.
<Soft vinyl chloride resin paste sol composition (1)>
Emulsion polymerization vinyl chloride resin (polymerization degree 1700) 100 parts by mass alkyl ether ester compound (1) 40 parts by mass ※ Isophthalic acid diether ester by reaction of isophthalic acid with alcohol in which ethylene oxide is added to n-octanol: (ether bond Equivalent to 2) [Compound 1] Equivalent to diisononyl isophthalic acid (alkyl ester compound 1) [Compound 7] 20 parts by mass Tricresyl phosphate (flame retardant plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer / plasticizer) ) 5 parts by mass barium / zinc complex stabilizer 2 parts by mass antimony trioxide (flame retardant) 10 parts by mass rutile type titanium oxide (white pigment) 5 parts by mass benzotriazole skeleton compound (ultraviolet ray absorber) 0.3 parts by mass Coating liquid (solid content concentration) for the following antifouling conductive layer (1) on the surface side of the film (1) Antifouling of lattice continua (grating width 5 mm, square void 10 mm × 10 mm) having an area occupancy of 55.5% by applying 120 mesh square lattice pattern gravure roll coating using 7.3% by mass) Conductive conductive layer (1) to obtain a dustproof film having a mass of 235 g / m ² .
<Solution for antifouling conductive layer (1)>
Fluoroolefin resin (fluorinated resin: solid content 15% by mass) 100 parts by mass Triisocyanate compound 2 parts by mass * Isocyanurate-modified triisocyanate which is a trimer of xylylene diisocyanate (XDI): 100% active ingredient
Single-walled carbon nanotube (diameter 1.5 to 2.5 nm) 0.2 mass part * Content ratio of carbon nanotube to antifouling conductive layer 1.15 mass%
Benzotriazole skeleton compound (UV absorber) 0.1 parts by mass

Example 2
The following soft vinyl chloride resin compound (1) was calendered (a mirror roll at 190 ° C.) to obtain a film (2) having a thickness of 0.2 mm.
<Soft vinyl chloride resin compound (1)>
Suspension polymerization vinyl chloride resin (polymerization degree 1300) 100 parts by mass alkyl ether ester compound (2) 35 parts by mass ※ Terephthalic acid diether ester by reaction of terephthalic acid with alcohol obtained by adding ethylene oxide to n-octanol: (ether bond Equivalent to having 2) [formula 2] equivalent to diisononyl terephthalate (alkyl ester compound 2) [formula 8] 20 parts by mass Tricresyl phosphate (flame retardant plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plastic) Agent) 5 parts by mass barium / zinc complex stabilizer 2 parts by mass antimony trioxide (flame retardant) 10 parts by mass rutile type titanium oxide (white pigment) 5 parts by mass benzotriazole skeleton compound (ultraviolet ray absorber) 0.3 parts by mass Coating liquid (solid content concentration) for the following antifouling conductive layer (2) on the surface side of the film (2) Using 7.5 mass%) and anti-soiling of a lattice-like continuum (grating width 5 mm, square hole 10 mm × 10 mm) having an area occupancy of 55.5% by coating a square lattice pattern gravure roll with 120 mesh Conductive conductive layer (2) to obtain a dustproof film having a mass of 244 g / m ² .
<Solution for antifouling conductive layer (2)>
Fluoroolefin resin (fluorine-based resin) 80 parts by mass Poly (N-methylpyrrole) (π-electron conjugated conductive polymer) 20 parts by mass Triisocyanate compound 5 parts by mass Isocyanate which is a trimer of xylylene diisocyanate (XDI) Nurate denatured tow rysocyanate: 100% active ingredient
Single-walled carbon nanotube (diameter: 1.5 to 2.5 nm) 0.8 mass part ※ 0.75% by mass of carbon nanotube content to antifouling conductive layer
Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Cyclopentanone (diluent solvent) 200 parts by mass Toluene (diluent solvent) 150 parts by mass Methyl ethyl ketone (diluent solvent) 150 parts by mass

[Example 3]
A film (3 mm) having a film thickness of 0.2 mm in the same manner as in Example 1 except that the soft vinyl chloride resin paste sol composition (1) in Example 1 was changed to the soft vinyl chloride resin paste sol composition (2). Got).
<Soft vinyl chloride resin paste sol composition (2)>
Emulsion polymerization vinyl chloride resin (polymerization degree 1700) 100 parts by mass alkyl ether ester compound (3) 40 parts by mass ※ 1,2-cyclohexanedicarbon by reaction of alcohol obtained by adding ethylene oxide to n-octanol and 1,2-cyclohexanedicarboxylic acid Acid diether ester: (has two ether bonds: equivalent to [Chemical Formula 3])
1,2-cyclohexanedicarboxylic acid diisononyl (alkyl ester compound 3) equivalent to [Chemical Formula 9] 20 parts by mass Tricresyl phosphate (flameproof plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / Zinc composite stabilizer 2 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Rutile-type titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 part by mass The above film (3) On the surface side surface, the following anti-fouling conductive layer (3) coating liquid (solid content concentration 17.7 mass%) was used, and the area occupation of 55.5% by 120 mesh square lattice pattern gravure roll coating grid-like continuous body having a ratio (grid width 5 mm, square holes 10 mm × 10 mm) to form antifouling conductive layer (3), to obtain a dustproof film mass 233 g / ^{m 2}
<Solution for antifouling conductive layer (3)>
Fluoroolefin resin (fluorinated resin: solid content 15% by mass) 100 parts by mass Triisocyanate compound 2 parts by mass * Isocyanurate-modified triisocyanate which is a trimer of xylylene diisocyanate (XDI): 100% active ingredient
Single-walled carbon nanotubes (diameter 1.5-2.5 nm) 0.2 parts by mass * The content of carbon nanotubes in the antifouling conductive layer is 0.89% by mass
Benzotriazole skeleton compound (ultraviolet absorber) 0.1 parts by mass Organosilica sol (nanoparticles of silica) 5 parts by mass ※ Particle diameter 10 to 15 nm: solid content 30% by mass: methyl ethyl ketone solvent methyltriethoxysilane (silane compound) 0. 3 parts by mass ※ Nanoparticle network of silica sol and methyltriethoxysilane in mass ratio 5: 1 is formed in the coating layer ※ Content ratio of nanoparticle network to coating layer 9.4 mass%

Example 4
A film (4) having a thickness of 0.2 mm was obtained in the same manner as in Example 2 except that the soft vinyl chloride resin compound (1) in Example 2 was changed to the soft vinyl chloride resin compound (2).
<Soft vinyl chloride resin compound (2)>
Suspension polymerization vinyl chloride resin (polymerization degree 1300) 100 parts by mass alkyl ether ester compound (4) 35 parts by mass ※ sebacic acid diether ester by reaction of sebacic acid with alcohol in which ethylene oxide is added to n-octanol: (ether 2 bonds: equivalent to [Chemical formula 4] diisononyl sebacate (alkyl ester compound 4): equivalent to [Chemical formula 10]
20 parts by mass Tricresyl phosphate (flameproof plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer / plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Rutile type Titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 part by mass On the surface side of the above film (4), a coating solution (solid) for the following antifouling conductive layer (4) Of a lattice continuum (grating width 5 mm, square hole 10 mm × 10 mm) having an area occupancy of 55.5% by coating 120 mesh square grid pattern gravure roll using a partial concentration of 18.2 mass%) An antifouling conductive layer (4) was formed to obtain a dustproof film having a mass of 247 g / m ² .
Solution for antifouling conductive layer (4)
Fluoroolefin resin (fluorine-based resin) 80 parts by mass Poly (N-methylpyrrole) (π-electron conjugated conductive polymer) 20 parts by mass Triisocyanate compound 5 parts by mass Isocyanate which is a trimer of xylylene diisocyanate (XDI) Nurate denatured tow rysocyanate: 100% active ingredient
Single-walled carbon nanotube (diameter: 1.5 to 2.5 nm) 0.8 part by mass * The content of carbon nanotube in the antifouling conductive layer is 0.75% by mass
Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Organosilica sol (nanoparticles of silica) 30 parts by mass ※ Particle diameter 10 to 15 nm: solid content 30% by mass: methyl ethyl ketone solvent methyltriethoxysilane (silane compound) 0. 9 parts by mass ※ A nano particle network of 10: 1 mass ratio of silica sol and methyltriethoxysilane is formed in the coating film layer ※ Content ratio of nanoparticle network to coating film layer 8.5 mass%
Cyclopentanone (diluting solvent) 200 parts by mass Toluene (diluting solvent) 150 parts by mass Methyl ethyl ketone (diluting solvent) 150 parts by mass

[Example 5]
Using a plain weave spun fabric comprising polyester (PET) staple fiber spun yarn as the fabric 1, a film of the soft vinyl chloride resin paste sol composition (1) of Example 1 was formed on both sides of the fabric 1.
<Fabric 1>
[Yarn density: 44 warps / twisting yarn (590 dtex) 44 / inch × 40 weft yarns / twisting (590 dtex) 40 / inch: porosity 4.2%: mass 228 g / m ² ]
The fabric 1 is dipped (dipped) in a liquid bath filled with the soft vinyl chloride resin paste sol composition (1), the fabric 1 is completely impregnated with the paste sol composition (1), and the fabric 1 is pulled up at the same time. The paste sol composition (1) was completely gelled in a hot air oven at 180 ° C. for 3 minutes by pressing with a rubber roll, and a soft vinyl chloride resin film was formed on both sides of the fabric 1 0.47 mm in thickness and 560 g in mass I got a canvas of / m ² .
Coating composition (example 1) for antifouling conductive layer (1) on one side (front side) of this canvas, and 55.5% area occupancy by square grid pattern gravure roll coating of 120 mesh An antifouling conductive layer (1) having a lattice-like continuum (lattice width 5 mm, square pores 10 mm × 10 mm) having a mass of 562 g / m ² was obtained.

[Example 6]
Polyester (PET) fiber plain weave fabric (warp 1111 dtex multifilament yarn: yarn density 22 / 2.54 cm × weft 1111 dtex multifilament yarn: yarn density 24 / 2.54 cm: porosity 21%: mass 165 g / m ² A film of 0.2 mm in thickness molded from a soft vinyl chloride resin compound (1) on both sides thereof as a fabric 2 by bridge melt lamination by thermocompression bonding, consisting of “film layer / fabric 2 / film layer” A tarpaulin having a thickness of 0.75 mm and a mass of 785 g / m ² was obtained.
Coating composition (example 2) for the antifouling conductive layer (2) on one side (front side) of this tarpaulin, and 55.5% area occupancy by square grid pattern gravure roll coating of 120 mesh An antifouling conductive layer (2) having a lattice-like continuum (lattice width: 5 mm, square pores: 10 mm × 10 mm) having a mass of 787 g / m ² was obtained.

[Example 7]
<Fabric 3>
Polyester (PET) fiber imitation twill cloth (3 warps 1111 dtex multifilament yarns: yarn density 6 / 2.54 cm × weft 1111 dtex multifilament yarns 3: yarn density 6 / 2.54 cm: porosity 27%: Hole 2.2 mm x 2.2 mm: mass 125 g / m ² )
The fabric 3 is dipped (dipped) in a liquid bath filled with the soft vinyl chloride resin paste sol composition (2), and the fabric 3 is completely impregnated with the paste sol composition (2), and the fabric 3 is pulled up at the same time. The paste sol composition (2) is completely gelled in a hot air oven at 180 ° C. for 3 minutes by pressing with a rubber roll, and this is pressed with a mirror surface roll so that the soft vinyl chloride resin film is flattened on the entire surface of the fabric 3 The formed mesh sheet of 364 g / m ² was obtained.
50% area occupancy by 100 mesh gravure roll (without handle) coating using the coating liquid (Example 3) for the antifouling conductive layer (3) on one side (front side) of this mesh sheet An antifouling conductive layer (3) having a mesh-tuned continuum (mesh width 2 mm, pores 2.2 mm × 2.2 mm) having a mass of 366 g / m ² was obtained.

[Example 8]
Using a fabric 2, a film of 0.2 mm in thickness molded from a soft vinyl chloride resin compound (2) on both sides by bridge melt lamination by thermocompression bonding, consisting of "film layer / fabric 2 / film layer", thickness A tarpaulin of 0.75 mm and a mass of 785 g / m ² was obtained.
Coating composition (example 4) for the antifouling conductive layer (4) on one side (front side) of this tarpaulin, and 55.5% area occupancy by square grid pattern gravure roll coating of 120 mesh An antifouling conductive layer (4) having a lattice-like continuum (lattice width: 5 mm, square pores: 10 mm × 10 mm) having a mass of 787 g / m ² was obtained.

[Effects of Embodiments 1 to 8]
A film containing an alkyl ether ester compound, in which an antifouling conductive layer is formed in a lattice form on one side or more of this film, a canvas using these, a mesh sheet, and a tarpaulin all have a surface resistivity of 10 ^{It was} about ⁷ to 10 ⁹ Ω / □, and was excellent in dust resistance. However, in the present invention, whether the surface resistivity is good or bad depends on the type and blending amount of the alkyl ether ester compound, the type and content of the conductive material of the antifouling conductive layer, and the occupied area ratio of the antifouling conductive layer. In particular, the higher the compounding amount of the alkyl ether ester compound, the higher the content ratio of the conductive material, and the higher the occupied area ratio of the antifouling conductive layer, the better the dust resistance (antistatic properties). Among the examples 1 to 8, the dust resistance (antistatic property) has a great effect width.

[Reference Example 1]
40 parts by mass of the alkyl ether ester compound (1): [Chemical Formula 1] of Example 1 is replaced with 40 parts by mass of the alkyl ester compound (1): [Chemical Formula 7], and the plasticizer is [Chemical Formula 7] by 60 parts by mass. A film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 except that. The obtained film had dust resistance (antistatic property), but the surface resistivity was reduced by about the first power as compared with Example 1.

[Reference Example 2]
35 parts by mass of the alkyl ether ester compound (2): [Chemical Formula 2] of Example 2 is replaced by 35 parts by mass of the alkyl ester compound (2): [Chemical Formula 8], and 55 parts by mass of [Chemical Formula 8] A film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 except that. The obtained film had dust resistance (antistatic property), but the surface resistivity was reduced by about the first power as compared with Example 2.

[Reference Example 3]
40 parts by mass of the alkyl ether ester compound (3): [Chemical Formula 3] of Example 3 is replaced with 40 parts by mass of the alkyl ester compound (3): [Chemical Formula 9], and the plasticizer is replaced by 60 parts by mass of [Chemical Formula 9]. A film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 except that. The obtained film had dust resistance (antistatic property), but the surface resistivity was reduced by about the first power as compared with Example 3.

[Reference Example 4]
The alkyl ether ester compound (4) of Example 4: [Chemical Formula 4] 35 parts by mass is replaced with 35 parts by mass of the alkyl ester compound (4): [Chemical Formula 10], and the plasticizer is represented by [Chemical Formula 10] 55 parts by mass. A film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 except that. The obtained film had dust resistance (antistatic property), but the surface resistivity was reduced by about the first power as compared with Example 4.

  As is clear from the above-mentioned Examples and Reference Examples, according to the present invention, surfactants or waxes that may cause adverse effects such as bleed contamination, printing defects, and poor bonding between sheets are used. There are not, and it is possible to obtain a film and a film made of soft vinyl chloride resin with dust resistance (effect due to antistatic properties) according to the REACH regulations and the RoHS directive, and industrial material sheets (for sheet storage, Tarpaulin materials used for tent houses, pavilions, flexible containers, aquariums, canvas materials used for truck hoods, seat covers, etc., mesh sheet materials used for building curing sheets, breathable sunshades, etc.) Are superior in dustproofness (effect by antistaticity) and are in compliance with the REACH regulation and the RoHS directive. Widely made possible deployment in developing.

Claims (6)

It mainly contains a vinyl chloride resin and a plasticizer, and as the plasticizer, at least a dialkyl ether ester of isophthalic acid (group of [Chemical Formula 1]), a dialkyl ether ester of terephthalic acid (Group of Chemical Formula 2), a dialkyl cyclohexanedicarboxylate Ether esters (group of [Chemical formula 3], dicarboxylic acid dialkyl ether esters (group of [chemical formula 4], trimellitic acid tris (alkyl ether ester) (group of [chemical formula 5]), and pyromellitic acid tetrakis (alkyl) Ether ester) (a group of [Chemical group 6]) containing one or more alkyl ether ester compounds, and an antifouling conductive layer is formed on one side or more of the film. ) Dustproof characterized in that it is formed by a reticulated continuum having an area occupancy of at least 20% Film.
(Wherein R ₁ and R _{2 each} represent a linear or branched alkyl group having 3 to 15 carbon atoms, and A ₁ and A _{2 each} have 2 to 4 carbon atoms) .m showing an alkylene group, n is an integer of 1 to 7, _{a 1} and _a 2, _{R 1} and _{R 2,} and m and n each is a good .A ₁ be different even in the same The total carbon number of R ₁ and A ₂ and R ₂ is 5 to 17. [Chemical formula 3] is 1,2-cyclohexanedicarboxylic acid dialkyl ether ester, 1,3-cyclohexanedicarboxylic acid dialkyl ether ester, 1,4-dicarboxylic acid Any of cycloalkyldicarboxylic acid dialkyl ether esters may be used.)
([Chemical Formula 4]: wherein R ₁ and R ₂ represent a linear or branched alkyl group having 3 to 15 carbon atoms, A ₁ and A ₂ represent an alkylene group having 2 to 4 carbon atoms, A ₃ represents an alkylene group having 4 to 12 carbon atoms, m and n are integers of 1 to 7, and A ₁ and A ₂ , R ₁ and R _2, and m and n are the same or different. The total carbon number of A ₁ and R ₁ and A ₂ and R ₂ is 5 to 17.)
(Wherein R ₁ , R ₂ and R _{3 each} represent a linear or branched alkyl group having _{3 to} 15 carbon atoms, and A ₁ , A ₂ and A _{3 each} have 2 to 2 carbon atoms) And m, n and o each represents an integer of 1 to 7, and A ₁ and A ₂ and A ₃ , R ₁ and R ₂ and R _3, and m and n and o are respectively the same. The total carbon number of A ₁ and R _1, A ₂ and R _2, and A ₃ and R ₃ is 5 to 17.)
(Wherein R ₁ , R ₂ , R ₃ and R _{4 each} represent a linear or branched alkyl group having ₃ to 15 carbon atoms, and A ₁ , A ₂ , A ₃ and A 4 ₄ represents an alkylene group having 2 to ₄ carbon atoms, m, n, o and p each represents an integer of 1 to 7, and A ₁ , A ₂ , A ₃ and A ₄ , R ₁ , R ₂ , R ₃ and R ₄ and m, n, o and p may be the same or different from each other: A ₁ and R _1, A ₂ and R _2, A ₃ and R _3, and A ₄ and R ₄ The number is 5 to 17.) The above-mentioned plasticizer further includes isophthalic acid dialkyl ester (group of [Chemical formula 7], terephthalic acid dialkyl ester (group of [chemical formula 8], cyclohexanedicarboxylic acid dialkyl ester (group of [chemical formula 9]), dicarboxylic acid dialkyl ester (Group of [Chemical 10]), trimellitic acid tris (alkyl ester) ([Chemical group 11]), and pyromellitic acid tetrakis (alkyl ester) ([Chemical group 12]) The dustproof film according to claim 1, wherein the alkylester compound is used in combination.
(Wherein R ₅ and R _{6 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ and R ₆ are each identical to each other) [Chem. 9] may be any of 1,2-cyclohexanedicarboxylic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, 1,4-cyclohexanedicarboxylic acid dialkyl ester .)

([Chemical Formula 10]: wherein R ₅ and R ₆ represent a linear or branched alkyl group having 3 to 17 carbon atoms, and A ₄ represents an alkylene group having 4 to 12 carbon atoms. R ₅ , R ₆ may be identical to or different from each other.)
(Wherein R ₅ , R ₆ and R _{7 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ , R ₆ and R ₇ are each identical to each other) Or may be different.)
(Wherein R ₅ , R ₆ , R ₇ and R _{8 each} represent a linear or branched alkyl group having 3 to 17 carbon atoms, and R ₅ , R ₆ and R ₇ , R ₇ Each ₈ may be the same or different.)   The dustproof film according to claim 1 or 2, wherein the antifouling conductive layer contains one or more selected from carbon nanotubes, fullerenes, and π-electron conjugated conductive polymers.   The antifouling conductive layer further comprises one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound, and the coating film The dustproof film according to claim 3 constituting a nanoparticle network of 1 to 10 mass% with respect to the layer.   A canvas and a mesh sheet, characterized in that the dust-proof film according to any one of claims 1 to 4 is provided in a coated state on the entire surface of the fabric, using the fabric as a base material.   A tarpaulin, wherein a dustproof film according to any one of claims 1 to 4 is laminated on at least one surface of a fabric using the fabric as a base material.