JP7026937B2 - Dustproof film and canvas, mesh sheet, and tarpaulin using these - Google Patents

Description

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

Phthalate esters are widely used as plasticizers and molding aids for vinyl chloride resins, but in recent years there has been increasing suspicion that they are endocrine disruptors that affect human and animal hormones, and they are used mainly in Europe. As regulatory movements progressed, the European Chemical Organization listed three substances, DBP, DEHP (DOP), and BBP, on the REACH Regulation's Substance of Very High Concern Candidate List (SVHC), and then added 10 more phthalates to the SVHC List. Added to. Furthermore, under the RoHS Directive, which restricts the use of specific hazardous substances in electronic and electrical equipment set by the EU European Union, four substances, DEHP (DOP), BBP, DBP, and DIBP, have recently been additionally designated as specific hazardous substances, and electronic and electrical. Restrictions on use in equipment are being considered. In Japan and the United States, DEHP (DOP), DBP, BBP, DINP, DIDP, and DNOP have been 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 appliances. It is prohibited to use it for purposes such as containers. Therefore, recent soft vinyl chloride resin products are shifting to products that use safer plasticizers as a product design in accordance with the REACH regulation and the RoHS directive, but depending on the type of plasticizer to be replaced, the product There is a problem of deteriorating the moldability and physical properties of the product.

The trend of product design in accordance with the REACH regulation and the RoHS directive has spread to industries other than the industries such as toys, food utensils and containers, and the movement to voluntarily change plasticizers has begun to stand out. Manufacturers have begun to focus on proposing alternatives, but no alternatives have yet been proposed for the general-purpose phthalic acid dialkyl ether ester compound (Patent Document 1) known as a conductive plasticizer. The applicant of the present invention is a tarpaulin material used for a seat warehouse, a tent house, a pavilion, a flexible container, a water tank, etc., a sail cloth material used for a truck hood, a seat cover, etc., a building curing sheet, and breathability. Those who are engaged in the business of manufacturing industrial material sheets made of soft vinyl chloride resin that are mainly used outdoors for a long period of time, such as mesh sheet materials used for aging, and products that come into direct contact with the product by mouth or food. Although it is not closely related to the product, since it is used in a large area close to our daily lives, there is a concern that it may be slightly volatilized as a product odor and may be inhaled by exhaled breath. From the viewpoint of concern about contamination with groundwater, a soft vinyl chloride resin industrial material sheet that does not use a phthalate ester compound (Patent Documents 2 to 5) was proposed, but these soft vinyl chloride resin industrial material sheets bleed. Unless mixed with surfactants or waxes that may cause adverse effects such as contamination, printing defects, and poor bonding between sheets, it is difficult to impart dust resistance and conductivity while maintaining free coloring. Therefore, a dustproof and conductive soft vinyl chloride resin film having free coloring according to the REACH rule and the RoHS command, and a dustproof property according to the REACH rule and the RoHS command using these, and A conductive industrial material sheet has been desired.

Japanese Unexamined Patent Publication No. 2000-103017 JP-A-2015-217608 JP-A-2015-223700 Japanese Unexamined Patent Publication No. 2016-022708 Japanese Unexamined Patent Publication No. 2015-033179

The present invention provides free coloring in accordance with the REACH Regulation and the RoHS Directive without using surfactants or waxes that may cause adverse effects such as bleed contamination, printing defects, and bonding defects between sheets. Dust-proof and conductive soft vinyl chloride resin film, and dust-proof and conductive industrial material sheet (for sheet warehouse, tent house, pavilion) according to the REACH regulation and RoHS directive using these. , Tarpaulin material used for flexible containers, water tanks, canvas materials used for truck hoods, seat covers, etc., mesh sheet materials used for building curing sheets, breathable sunshades, etc.) Is.

As a result of research and study in view of the above situation, the present inventor mainly contains vinyl chloride resin and plasticizer, and at least isophthalic acid dialkyl ether esters and terephthalic acid dialkyl ether esters are used as plasticizers. 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 it, a dust-proof and conductive soft vinyl chloride resin film having free coloring property according to the REACH rule and the RoHS command can be obtained, and further, according to the REACH rule and the RoHS command using these. We have found that a dustproof and conductive industrial material sheet can be obtained, and have completed the present invention.

（〔化１〕～〔化３〕：式中、Ｒ_１ 、Ｒ_２は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２は炭素数２～４のアルキレン基を示す。ｍ、ｎは１～７の整数で、Ａ_１とＡ_２、Ｒ_１とＲ_２及びｍとｎは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２の合計炭素数は５～１７である。〔化３〕は１，２－シクロヘキサンジカルボン酸ジアルキルエーテルエステル、１，３－シクロヘキサンジカルボン酸ジアルキルエーテルエステル、１，４－シクロヘキサンジカルボン酸ジアルキルエーテルエステルの何れであってもよい。）

（〔化４〕：式中、Ｒ_１ 、Ｒ_２は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２は炭素数２～４のアルキレン基、Ａ_３は炭素数４～１２のアルキレン基を示す。ｍ、ｎは１～７の整数で、Ａ_１とＡ_２、Ｒ_１とＲ_２及びｍとｎは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２の合計炭素数は５～１７である。）

（〔化５〕：式中、Ｒ_１ 、Ｒ_２、Ｒ_３は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２とＡ_３は炭素数２～４のアルキレン基を示す。ｍ、ｎ、ｏは１～７の整数で、Ａ_１とＡ_２とＡ_３、Ｒ_１とＲ_２とＲ_３及びｍとｎとｏは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２及びＡ_３とＲ_３の合計炭素数は５～１７である。）

（〔化６〕：式中、Ｒ_１ 、Ｒ_２、Ｒ_３、Ｒ_４は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２とＡ_３とＡ_４は炭素数２～４のアルキレン基を示す。ｍ、ｎ、ｏ、ｐは１～７の整数で、Ａ_１とＡ_２とＡ_３とＡ_４、Ｒ_１とＲ_２とＲ_３とＲ_４及びｍとｎとｏとｐは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２及びＡ_３とＲ_３及びＡ_４とＲ_４の合計炭素数は５～１７である。）
That is, the dust-proof film of the present invention mainly contains a vinyl chloride resin and a plasticizing agent, and as the plasticizing agent, at least an isophthalic acid dialkyl ether ester (group of [Chemical formula 1]) and a terephthalic acid dialkyl ether ester ([Chemical compound 2]). ] Group), cyclohexanedicarboxylic acid dialkyl ether ester ([Chemical formula 3] group), dicarboxylic acid dialkyl ether ester ([Chemical formula 4] group), trimellitic acid tris (alkyl ether ester) ([Chemical formula 5] group). ), And a film containing one or more alkyl ether ester compounds selected from the pyromellitic acid tetrakis (alkyl ether ester) (group of [Chemical formula 6]), in which an antifouling conductive layer is provided on one or more sides of this film. The antifouling conductive layer was selected from carbon nanotubes, fullerene and π-electron-conjugated conductive polymers, which were 1) formed entirely or 2) formed of a reticulated continuum with an area occupancy of at least 20%. The antifouling conductive layer contains one or more kinds of nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound. Further, it is preferable to form a nanoparticle network of 1 to 10% by mass with respect to the coating layer.

([Chemical formula 1] to [Chemical formula 3]: In the formula, R ₁ and R ₂ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ and A ₂ have 2 to 4 carbon atoms. M and n are integers from 1 to 7, and A ₁ and A ₂ , R ₁ and R ₂ and m and n may be the same or different from _each other. The total carbon number of R ₁ , 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-. It may be any of cyclohexanedicarboxylic acid dialkyl ether esters.)

([Chemical formula 4]: In the formula, R ₁ and R ₂ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ and A ₂ are alkylene groups having 2 to 4 carbon atoms, A. ₃ indicates 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 different even if they are the same. The total number of carbon atoms of A ₁ and R ₁ and A ₂ and R ₂ may be 5 to 17).

([Chemical formula 5]: In the formula, R ₁ , R ₂ , R ₃ represent a linear or branched alkyl group having 3 to 15 carbon atoms, and A ₁ , A ₂ and A ₃ have 2 to 15 carbon atoms. Indicates an alkylene group of 4. m, n, o are integers from 1 to 7, and A ₁ and A ₂ and A ₃ and R ₁ and R ₂ and R ₃ and m and n and o are the same, respectively. The total carbon number of A ₁ and R ₁ and A ₂ and R ₂ and A ₃ and R ₃ is 5 to 17).

([Chemical formula 6]: In the formula, R ₁ , R ₂ , R ₃ , and R ₄ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ , A ₂ , A ₃ , and A. ₄ represents an alkylene group having 2 to 4 carbon atoms. M, n, o and p are integers of 1 to 7, and A ₁ and A ₂ and A ₃ and A ₄ and R ₁ and R ₂ and R ₃ and R. ₄ and m, n, o and p may be the same or different, respectively. Total carbon of A ₁ and R ₁ and A ₂ and R ₂ and A ₃ and R ₃ and A ₄ and R ₄ . The number is 5 to 17.)

（〔化７〕～〔化９〕：式中、Ｒ_５ 、Ｒ_６は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ｒ_５ 、Ｒ_６は、それぞれが同一であっても異なっていてもよい。〔化９〕は１，２－シクロヘキサンジカルボン酸ジアルキルエステル、１，３－シクロヘキサンジカルボン酸ジアルキルエステル、１，４－シクロヘキサンジカルボン酸ジアルキルエステルの何れであってもよい。）

（〔化１０〕：式中、Ｒ_５ 、Ｒ_６は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ａ_４は炭素数４～１２のアルキレン基を示す。Ｒ_５ 、Ｒ_６は、それぞれが同一であっても異なっていてもよい。）

（〔化１１〕：式中、Ｒ_５ 、Ｒ_６、Ｒ_７は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ｒ_５とＲ_６とＲ_７は、それぞれが同一であっても異なっていてもよい。）

（〔化１２〕：式中、Ｒ_５ 、Ｒ_６、Ｒ_７、Ｒ_８は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ｒ_５とＲ_６とＲ_７、Ｒ_８は、それぞれが同一であっても異なっていてもよい。） In the dustproof film of the present invention, the plasticizer is further an isophthalic acid dialkyl ester ([Chemical formula 7] group), a terephthalic acid dialkyl ester ([Chemical formula 8] group), and a cyclohexanedicarboxylic acid dialkyl ester ([Chemical formula 9]). Group), dicarboxylic acid dialkyl ester ([Chemical formula 10] group), trimellitic acid tris (alkyl ester) ([Chemical formula 11] group), and pyromellitic acid tetrakis (alkyl ester) ([Chemical formula 12] group). ), It is preferable to use one or more alkyl ester compounds selected from the above in combination.

([Chemical acid 7] to [Chemical acid 9]: _In the _formula , R5 and R6 represent linear or branched alkyl groups having ₃ to 17 carbon atoms, and R5 and R6 are the _same , respectively. [Chemical formula 9] may be any of 1,2-cyclohexanedicarboxylic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, and 1,4-cyclohexanedicarboxylic acid dialkyl ester. .)

([Chemical formula 10]: In the formula, R ₅ and R ₆ indicate a linear or branched alkyl group having 3 to 17 carbon atoms, and A ₄ indicates an alkylene group having ₄ to 12 carbon atoms. , R ₆ may be the same or different.)

([Chemical formula 11]: In the formula, R ₅ , R ₆ and R ₇ represent linear or branched alkyl groups having 3 to 17 carbon atoms, and R ₅ and R ₆ and R ₇ are the same, respectively. It may be different.)

([Chemical formula 12]: In the formula, R ₅ , R ₆ , R ₇ , and R ₈ represent linear or branched alkyl groups having 3 to 17 carbon atoms, and R ₅ and R ₆ and R ₇ , R. ₈ may be the same or different from each other.)

In the dust-proof film of the present invention, it is preferable that the antifouling conductive layer contains at least one selected from carbon nanotubes, fullerenes and π-electron conjugated conductive polymers.

In the dust-proof film of the present invention, the antifouling conductive layer comprises one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound. It is preferable that a nanoparticle network of 1 to 10% by mass is formed with respect to the coating film layer.

The canvas or mesh sheet of the present invention is preferably made of a cloth as a base material, and the dust-proof film described in paragraph [0007] or [0008] is preferably provided on the entire surface of the cloth in a coated state.

The tarpaulin of the present invention is preferably made of a cloth as a base material, and the dust-proof film described in any paragraph of paragraphs [0007] to [0010] is laminated on the entire surface of the cloth.

According to the present invention, free coloring in accordance with the REACH regulation and the RoHS directive without using surfactants and waxes that may cause adverse effects such as bleed contamination, printing defects, and bonding defects between sheets. A dust-proof and conductive soft vinyl chloride resin film having properties and a dust-proof and conductive industrial material sheet conforming to the REACH regulation and the RoHS directive using these can be obtained. It can be widely used for warehouses, tent houses, pavilions, flexible containers, water tanks, truck hoods, seat covers, building curing sheets, breathable sunshades, etc.

（〔化１〕～〔化３〕：式中、Ｒ_１ 、Ｒ_２は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２は炭素数２～４のアルキレン基を示す。ｍ、ｎは１～７の整数で、Ａ_１とＡ_２、Ｒ_１とＲ_２及びｍとｎは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２の合計炭素数は５～１７である。〔化３〕は１，２－シクロヘキサンジカルボン酸ジアルキルエーテルエステル、１，３－シクロヘキサンジカルボン酸ジアルキルエーテルエステル、１，４－シクロヘキサンジカルボン酸ジアルキルエーテルエステルの何れであってもよい。）

（〔化４〕：式中、Ｒ_１ 、Ｒ_２は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２は炭素数２～４のアルキレン基、Ａ_３は炭素数４～１２のアルキレン基を示す。ｍ、ｎは１～７の整数で、Ａ_１とＡ_２、Ｒ_１とＲ_２及びｍとｎは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２の合計炭素数は５～１７である。）

（〔化５〕：式中、Ｒ_１ 、Ｒ_２、Ｒ_３は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２とＡ_３は炭素数２～４のアルキレン基を示す。ｍ、ｎ、ｏは１～７の整数で、Ａ_１とＡ_２とＡ_３、Ｒ_１とＲ_２とＲ_３及びｍとｎとｏは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２及びＡ_３とＲ_３の合計炭素数は５～１７である。）

（〔化６〕：式中、Ｒ_１ 、Ｒ_２、Ｒ_３、Ｒ_４は、炭素数３～１５の直鎖状または分岐状のアルキル基を示し、Ａ_１とＡ_２とＡ_３とＡ_４は炭素数２～４のアルキレン基を示す。ｍ、ｎ、ｏ、ｐは１～７の整数で、Ａ_１とＡ_２とＡ_３とＡ_４、Ｒ_１とＲ_２とＲ_３とＲ_４及びｍとｎとｏとｐは、それぞれが同一であっても異なっていてもよい。Ａ_１とＲ_１ 及びＡ_２とＲ_２及びＡ_３とＲ_３及びＡ_４とＲ_４の合計炭素数は５～１７である。） The dust-proof film of the present invention mainly contains a vinyl chloride resin and a plasticizer, and contains at least one alkyl ether ester compound (having one or more ether bonds in the alkyl chain) as the plasticizer. It is preferable that one or more kinds of alkyl ester compounds are further contained as needed, and the mass ratio of the alkyl ether ester compound and the alkyl ester compound is 3: 1 to 1: 3, particularly 2: 1 to 1: 1. .. The alkyl ether ester compounds are isophthalic acid dialkyl ether ester (group of [chemical 1]), terephthalic acid dialkyl ether ester (group of [chemical 2]), cyclohexanedicarboxylic acid dialkyl ether ester (group of [chemical 3]), and dicarbonate. From acid dialkyl ether esters (group of [chemical 4]), tristrimertic acid (alkyl ether ester) (group of [chemical 5]), and tetramellitic acid tetrakis (alkyl ether ester) (group of [chemical 6]) One or more selected species can be mentioned.

([Chemical formula 1] to [Chemical formula 3]: In the formula, R ₁ and R ₂ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ and A ₂ have 2 to 4 carbon atoms. M and n are integers from 1 to 7, and A ₁ and A ₂ , R ₁ and R ₂ and m and n may be the same or different from _each other. The total carbon number of R ₁ , 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-. It may be any of cyclohexanedicarboxylic acid dialkyl ether esters.)

([Chemical formula 4]: In the formula, R ₁ and R ₂ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ and A ₂ are alkylene groups having 2 to 4 carbon atoms, A. ₃ indicates 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 different even if they are the same. The total number of carbon atoms of A ₁ and R ₁ and A ₂ and R ₂ may be 5 to 17).

([Chemical formula 5]: In the formula, R ₁ , R ₂ , R ₃ represent a linear or branched alkyl group having 3 to 15 carbon atoms, and A ₁ , A ₂ and A ₃ have 2 to 15 carbon atoms. Indicates an alkylene group of 4. m, n, o are integers from 1 to 7, and A ₁ and A ₂ and A ₃ and R ₁ and R ₂ and R ₃ and m and n and o are the same, respectively. The total carbon number of A ₁ and R ₁ and A ₂ and R ₂ and A ₃ and R ₃ is 5 to 17).

([Chemical formula 6]: In the formula, R ₁ , R ₂ , R ₃ , and R ₄ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ , A ₂ , A ₃ , and A. ₄ represents an alkylene group having 2 to 4 carbon atoms. M, n, o and p are integers of 1 to 7, and A ₁ and A ₂ and A ₃ and A ₄ and R ₁ and R ₂ and R ₃ and R. ₄ and m, n, o and p may be the same or different, respectively. Total carbon of A ₁ and R ₁ and A ₂ and R ₂ and A ₃ and R ₃ and A ₄ and R ₄ . The number is 5 to 17.)

（〔化７〕～〔化９〕：式中、Ｒ_５ 、Ｒ_６は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ｒ_５ 、Ｒ_６は、それぞれが同一であっても異なっていてもよい。〔化９〕は１，２－シクロヘキサンジカルボン酸ジアルキルエステル、１，３－シクロヘキサンジカルボン酸ジアルキルエステル、１，４－シクロヘキサンジカルボン酸ジアルキルエステルの何れであってもよい。）

（〔化１０〕：式中、Ｒ_５ 、Ｒ_６は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ａ_４は炭素数４～１２のアルキレン基を示す。Ｒ_５ 、Ｒ_６は、それぞれが同一であっても異なっていてもよい。）

（〔化１１〕：式中、Ｒ_５ 、Ｒ_６、Ｒ_７は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ｒ_５とＲ_６とＲ_７は、それぞれが同一であっても異なっていてもよい。）

（〔化１２〕：式中、Ｒ_５ 、Ｒ_６、Ｒ_７、Ｒ_８は、炭素数３～１７の直鎖状または分岐状のアルキル基を示し、Ｒ_５とＲ_６とＲ_７、Ｒ_８は、それぞれが同一であっても異なっていてもよい。） The alkyl ester compounds to be used in combination with the above alkyl ether ester compounds as needed are isophthalic acid dialkyl esters (group of [chemical 7]), terephthalic acid dialkyl esters (group of [chemical 8]), and cyclohexanedicarboxylic acid dialkyl esters ([]. Chemical acid 9] group), dicarboxylic acid dialkyl ester ([chemical 10] group), trimellitic acid tris (alkyl ester) ([chemical 11] group), and pyromellitic acid tetrakis (alkyl ester) ([chemical 12]. ] Group), one or more selected from.

([Chemical acid 7] to [Chemical acid 9]: _In the _formula , R5 and R6 represent linear or branched alkyl groups having ₃ to 17 carbon atoms, and R5 and R6 are the _same , respectively. [Chemical formula 9] may be any of 1,2-cyclohexanedicarboxylic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, and 1,4-cyclohexanedicarboxylic acid dialkyl ester. .)

([Chemical formula 10]: In the formula, R ₅ and R ₆ indicate a linear or branched alkyl group having 3 to 17 carbon atoms, and A ₄ indicates an alkylene group having ₄ to 12 carbon atoms. , R ₆ may be the same or different.)

([Chemical formula 11]: In the formula, R ₅ , R ₆ and R ₇ represent linear or branched alkyl groups having 3 to 17 carbon atoms, and R ₅ and R ₆ and R ₇ are the same, respectively. It may be different.)

([Chemical formula 12]: In the formula, R ₅ , R ₆ , R ₇ , and R ₈ represent linear or branched alkyl groups having 3 to 17 carbon atoms, and R ₅ and R ₆ and R ₇ , R. ₈ may be the same or different from each other.)

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 is an alkyl ether ester compound (one or more ether bonds in the alkyl chain). In the case of having), the amount is 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, and when an alkyl ester compound is used in combination, the mixing ratio of the alkyl ether ester compound and the alkyl ester compound is used. Is 3: 1 to 1: 3, preferably 2: 1 to 1: 1. For example, when the blending amount of the alkyl ether ester compound is 50 parts by mass, the blending amount of the alkyl ester compound is 25 parts by mass (mass ratio 2: 1), and when the blending amount of the alkyl ether ester compound is 35 parts by mass, the alkyl The blending amount of the ester compound is particularly preferably 35 parts by mass (mass ratio 1: 1). The dust-proof film of the present invention further includes a chlorinated paraffin compound and an aromatic phosphate ester such as tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, and cresyldiphenyl phosphate, if necessary to impart flame resistance. The compound can be used in combination as a flameproofing agent and a plasticizer in an amount of about 5 to 15% by mass based on the amount of the plasticizer. When heat resistance is imparted to the dust-proof film of the present invention, a reactive acrylic compound having two or more (meth) acryloyl groups at the molecular end or a side chain, and an allyl phthalate compound having two or more allyl groups. Etc. can be used in combination with the above plasticizer in an amount of about 5 to 15% by mass.

Examples of the dicarboxylic acid used for producing the alkyl ether ester compounds of the above 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. Dicarboxylic acids such as acids, isophthalic acids and terephthalic acids, trivalent or higher polyvalent carboxylic acids, divalent carboxylic acids with an epoxycyclohexane ring, aromatic polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, as well as these. An acid anhydride of a carboxylic acid or the like can be used. Specific examples of such an alkyl ether ester compound include diethyl cellosolve isophthalate, dibutyl cellosolve terephthalate, 1,2-cyclohexanedibutylcellosolve, 1,3-cyclohexanedibutylcellosolve, 1,4-cyclohexanedibutylcellosolve, and diethylcelloadipate. , Dibutyl cellosolve adipic acid, diethyl cellosolve sebacate, dibutyl cellosolve sebacate, trisdibutyl cellosolve trimellitic acid, tetrakisdibutyl cellosolve pyromellitic acid, etc., reaction of carboxylic acid with mono- and poly-alkylene glycol monoalkyl ethers. Things can be raised. Mono- and poly-alkylene glycol monoalkyl ethers are addition compounds of alcohol and ethylene oxide such as propanol, butanol, hexanol, heptanol, octanol and nonanol, addition compounds of alcohol and propylene oxide, and addition compounds of alcohol and butylene oxide. Alternatively, it is an addition compound of alcohol and two or more alkylene oxides selected from alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, and these are specifically ethylene glycol monooctyl ether, diethylene glycol monomethyl ether and diethylene glycol. Monobutyl Ether, Diethylene Glycol Monoheptyl Ether, Triethylene Glycol Monomethyl Ether, Triethylene Glycol Monopropyl Ether, Tetraethylene Glycol Monoethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monooctyl Ether, Dipropylene Glycol Monobutyl Ether, Butylene Glycol Monoethyl Others such as (mono-poly) alkylene glycol monoalkyl ethers such as ethers, diethylene glycol di-2-ethylhexonate, tetraethylene glycol di-2-ethylhexonate, hexaethylene glycol di-2-ethylhexonate , Triethylene glycol diethylbutyrate, polyethylene glycol diethylbutyrate, polypropylene glycol diethylhexonate, triethylene glycol dibenzoate, tetraethylene glycol dibenzoate, polyethylene glycol dibenzoate, polypropylene glycol dibenzoate, or polyethylene glycol-2-ethyl. Hexonate benzoate and the like.

With respect to the above-mentioned alkyl ester compounds of the formulas [Chemical formula 7] to [Chemical formula 9], the plasticizer of the isophthalic acid dialkyl ester (group of [Chemical formula 7]) is synthesized, for example, by an esterification reaction of isophthalic acid and 2-ethylhexanol. Di (2-ethylhexyl) isophthalate is particularly preferable, and other dibutyl isophthalate, diisobutyl isophthalate, dihexyl isophthalate, diheptyl isophthalate, dinonyl isophthalate, diisononyl isophthalate, diisodecyl isophthalate, didecyl isophthalate, butylbenzyl isophthalate. Etc. are exemplified. As the plasticizer of the terephthalic acid dialkyl ester (group of [Chemical 8]), for example, di-2-ethylhexyl terephthalate (dioctyl terephthalate) synthesized by the esterification reaction of terephthalic acid and 2-ethylhexanol is particularly preferable. Other examples include dibutyl terephthalate, diisobutyl terephthalate, dihexyl terephthalate, diheptyl terephthalate, dinonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, didecyl terephthalate, and butylbenzyl terephthalate. The plasticizer for the cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical No. 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, diisobutyl cyclohexanedicarboxylate, dihexyl cyclohexanedicarboxylate, diheptyl cyclohexanedicarboxylate, dinonyl cyclohexanedicarboxylate, diisononyl cyclohexanedicarboxylate, diisodecylcyclohexanedicarboxylate, didecylcyclohexanedicarboxylate, butylbenzylcyclohexanedicarboxylate, etc. Is exemplified. In the above specific example, the cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical 9]) includes variations in which the coordination of the dialkyl ester is the 1,2-position, 1,3-position, and 1,4-position of the cyclohexane ring. do.

With respect to the above-mentioned alkyl ester compounds of the formulas [Chemical formula 10] to [Chemical formula 12], the plasticizer of the dicarboxylic acid dialkyl ester (group of [Chemical formula 10]) is synthesized, for example, by an esterification reaction of adipic acid and 2-ethylhexanol. Dibutyl adipate (2-ethylhexyl) is particularly preferable, and other dibutyl adipate, diisobutyl adipate, dihexyl adipate, diheptyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, didecyl adipate, butylbenzyl adipate Di (2-ethylhexyl) sebacate synthesized by the esterification reaction of sebacic acid and 2-ethylhexanol is particularly preferable, and other dibutyl sebacate, diisobutyl sebacate, dihexyl sebacate, diheptyl sebacate, dinonyl sebacate, etc. , Sebacate diisononyl, sebacate diisodecyl, sebacate didecyl, butylbenzyl sebacate and the like are exemplified. The plasticizing agent for trimellitic acid tris (alkyl ester) (group of [Chemical No. 11]) is, for example, trimellitic acid, or trimellitic acid tris synthesized by an esterification reaction of trimellitic acid anhydride and 2-ethylhexanol. (2-Ethylhexyl) is particularly preferable, and other tributyl trimellitic acid, tristrimeritate (isobutyl), trihexyl trimellitic acid, triheptyl trimellitic acid, trinonyl trimellitic acid, trisononyl trimellitic acid, triisodecyl trimellitic acid. , Tridecyl trimellitic acid, tristrimeritate (butylbenzyl) and the like are exemplified. The plasticizer for pyromellitic acid tetrakis (alkyl ester) (group of [Chemical No. 12]) is, for example, pyromellitic acid, or tetramellitic acid tetrakis synthesized by an esterification reaction between pyromellitic acid anhydride and 2-ethylhexanol. (2-Ethylhexyl) is particularly preferable, and other totetrabutyl pyromellitic acid, tetrakis pyromellitic acid (isobutyl), tetrahexyl pyromellitic acid, tetraheptyl pyromellitic acid, tetranonyl pyromellitic acid, tetrakis pyromellitic acid (isononyl), pyromerit. Examples thereof include tetraisodecyl acid acid, tetradecyl pyromellitic acid, and tetrakis pyromellitic acid (butylbenzyl).

The vinyl chloride resin contained in the dust-proof film of the present invention is a homopolymer of a vinyl chloride monomer (a homopolymer having a degree of polymerization of 1000 to 4000), and is an emulsified polymer (wheat powder) and a suspended polymer (granule sugar). (Shape) can be used. The vinyl chloride resin of the emulsified polymer forms a paste-like composition together with a plasticizer and an additive, is used for coating and dipping, and is subjected to heat gelation to form a dust-proof film (thickness 0.01 mm) of the present invention. ~ 1 mm) can be obtained in a coated state. A canvas impregnated with a coating film made of this paste-like composition and formed on the cloth is a canvas for industrial materials, and a mesh sheet impregnated with a coarse cloth and formed on the coarse cloth is a mesh sheet for industrial materials. The vinyl chloride resin of the suspended polymer forms a compound-like composition together with a plasticizer and an additive, is subjected to calender molding, and is subjected to heat kneading and heat rolling to obtain a dustproof film (thickness 0.1 mm or more) of the present invention. 1 mm) can be obtained. A tarpaulin for industrial materials is a dust-proof film made of vinyl chloride resin laminated 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 components include α-olefins having 2 to 30 carbon atoms, acrylic acid and the like. Examples thereof include the esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetates, vinyl propionates, vinyl compounds such as alkyl vinyl ethers and the like. Further, as the dustproof film, polyol compound, chlorinated polyethylene, butyl rubber, acrylic rubber, polyurethane, butadiene-styrene-methylmethacrylate copolymer, styrene-butadiene copolymer, etc. are used for improved workability, flexibility, and low temperature characteristics. It can be used in combination with a vinyl chloride resin in an amount of about 5 to 25% by mass for the purpose of improving, improving heat resistance, and mitigating impact. Further, a reactive compound such as a polyisocyanate compound, a carbodiimide compound, or an oxazoline compound is added to form a crosslinked structure on a dustproof film (including a coating film) to improve heat resistance, or to improve heat resistance, or to fabric, knit, etc. It is also possible to improve the adhesiveness to a cloth or the like.

Further, in the dustproof film, various known additives for synthetic resins can be blended as components other than the plasticizer in various arbitrary amounts, and as stabilizers for vinyl chloride resin, calcium-zinc composite system, barium-zinc composite system, etc. Stabilizers such as organic tin laurate, organic tin mercaptite, and epoxy-based stabilizers may be used alone or in combination of 1 to 10 parts by mass with respect to 100 parts by mass of vinyl chloride resin to suppress thermal discoloration during molding. Improves weather resistance. Furthermore, a light-resistant stabilizer (hindered amine compound, etc.), an ultraviolet absorber (benzotriazole compound, benzophenone compound, etc.) and an antioxidant (phenolic compound, vitamin E compound, etc.) are applied to 100 parts by mass of vinyl chloride resin. By using about 0.1 to 5 parts by mass, thermal discoloration during molding is synergistically suppressed, and weather resistance is synergistically improved. Further, in the dustproof film of the present invention, flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, and bromine-substituted organic compounds, and fillers such as calcium carbonate, barium sulfate, and silica are used as flameproof standards for various articles. It can be blended in an amount suitable for the above. Further, the dustproof film of the present invention may be a transparent one containing no flame retardant or a filler, or a translucent light film containing a flame retardant or a filler, and an inorganic pigment (titanium oxide, vengara). , Carbon black, etc.), transparent colored pigments (azo, quinacridone, phthalocyanine, nitro, perylene, etc.), colored light translucent, colored light-shielding, It may be either.

A composite of a cloth (woven fabric, knitted fabric, coarse woven fabric) and a dustproof film (coating film state) of the present invention is a canvas for industrial materials, and a canvas impregnated with the coarse cloth and formed on the coarse cloth is an industrial material. It is a mesh sheet for. Further, a tarpaulin for industrial materials is obtained by combining a cloth (woven fabric, knitted fabric, coarse woven fabric) and the dustproof film of the present invention with the cloth. The fabric is a woven fabric having a mass of 50 to 500 g / m ² , preferably a mass of 65 to 280 g / m ² woven from synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or a mixed fiber composed of two or more of these. Knitting and coarse woven fabrics. Synthetic fibers include nylon fiber, vinylon fiber, polypropylene fiber, polysell fiber, total aromatic polyester fiber, ultrahigh molecular weight polyethylene fiber, total aromatic polyamide (aramid) fiber, and heterocyclic polymer fiber (polybenzoxazole fiber, poly). Benzimidazole fiber) and the like. Examples of natural fibers include cotton, linen and kenaf, and examples of semi-synthetic fibers include rayon and acetate. Examples of the inorganic fiber include glass fiber, silica fiber, alumina fiber, silica alumina fiber, carbon fiber and the like. In particular, in the present invention, known fabrics such as multifilament yarn and span yarn made of synthetic fibers, plain woven fabric made of covering yarn, twill woven fabric, twill woven fabric, woven fabric, basket woven fabric, triaxial woven fabric, and quadruaxial woven fabric can be used. If necessary, these fabrics may be subjected to water repellent treatment, water absorption prevention treatment, adhesive treatment, flame retardant treatment and the like. The cloth used in the present invention is preferably a plain woven fabric made of polysell fiber, aramid fiber, carbon fiber, glass fiber or the like.

Among the fabrics used in the present invention, the fabrics suitable for canvas are span yarns (short fiber spun yarns) in the range of 10th (591dtex) to 60th (97ddtex), particularly 10th (591dtex), 14th (422dtex), 16th. It is a plain weave fabric with a blank space ratio of less than 5% using spun yarns of count (370dtex), 20th (295dtex), 24th (246ddtex), and 30th (197dtex). Specifically, a spun plain woven fabric using a 20-count single yarn or a 20-count twin yarn with a weaving density of 50 to 70 warp yarns and 40 to 60 weft yarns in 1 inch is suitable. These span yarns include a core-sheath type, and an example thereof is one in which an aramid fiber multifilament thread is used as a core component and polysell fiber short fibers are entwined around the core component to form a sheath component. It is possible to dramatically improve the anti-drilling property. Further, the fabric suitable for the mesh sheet is a plain woven fabric or a woven fabric having a porosity of 20 to 60%, preferably a porosity of 25% to 40%, using a multifilament yarn of 277 to 2222 dtex, preferably 555 to 1666 dtex. , Triaxial woven fabric, etc. Further, the fabric suitable for tarpaulin is a plain woven fabric, a twill woven fabric, or a red woven fabric having a porosity of 5 to 30%, preferably a porosity of 10% to 25%, using a multifilament yarn of 277 to 2222 dtex, preferably 555 to 1666 dtex. Woven fabrics, basket woven fabrics, triaxial woven fabrics, quaternary woven fabrics, etc. These mesh and tarpaulin fabrics include ripstop base fabrics, for example, with polys L multifilament yarns that regularly or randomly replace some of the warps and / or wefts of the base fabric with aramid fiber multifilament yarns. The ones that have been placed are listed. With such specifications, tear strength and breakage prevention by protrusions can be dramatically improved.

The method for forming a dust-proof film (coating state) on the fabric is selected from (group of [chemical 1]) to (group of [chemical 6]) on an emulsion-polymerized vinyl chloride resin (100 parts by mass), for example. The amount of the plasticizer (40 to 80 parts by mass), and if necessary, the plasticizer selected from (the group of [Chemical 7]) to (the group of [Chemical 12]) was used in combination. Using a paste sol composition of 80 parts by mass), 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.) ) And the like to form a coating film on the front and back of the fabric. In the case of canvas for industrial materials, the gap between the fabrics (the gap between the fiber threads and the filaments constituting the fiber threads, and between the filaments constituting the fiber threads) are used by dipping or coating the fabric, or by means of dipping and coating in combination. The gap) is impregnated with the paste-like composition, and both sides of the canvas cloth are covered with the paste-like composition, which is heat-treated to 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 coarse cloth is impregnated with the paste-like composition in the gaps between the filaments constituting the fiber threads by dipping or coating means, and the entire surface of the blank cloth is covered with the paste-like composition. By coating with, and heat-treating this to gelate, a coating film is formed to obtain a mesh sheet having a thickness of about 0.5 mm to 2 mm. In the case of tarpaulin, a dustproof film having a thickness of 0.1 mm to 0.3 mm, which is molded by calendar rolling or T-die extrusion on both sides of the fabric having a certain degree of opening, is thermocompression bonded with a laminator. The dust-proof films on the front and back are partially bridge-fused together at the opening portion of the cloth, so that 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 formed on one or more sides 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]). It is formed in a network with an area occupancy rate of 20% or more. A canvas, mesh sheet, and tarpaulin manufactured by providing the antifouling conductive layer forming film, 3) or after manufacturing a canvas base material, a mesh sheet base material, and a tarpaulin base material, one side or more of these base materials. Examples thereof include a canvas, a mesh sheet, and a tarpaulin in which the antifouling conductive layer is formed on the entire surface or in a net shape with an area occupancy of 20% or more. This antifouling conductive layer is a). It contains one or more selected from carbon nanotubes, fullerenes and π-electron conjugated conductive polymers, and it is particularly preferable to contain a binder resin from the viewpoint of imparting antifouling property and wear durability. The content of carbon nanotubes and / or fullerenes 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 a single or acrylic-based. It can be used in combination with a resin, urethane resin, fluoropolymer resin (fluoroolefin copolymer resin obtained by copolymerizing a fluororesin monomer with a vinyl monomer), etc. at an arbitrary concentration, and these single resins or combined resins can be used in combination. Can also be used in combination with carbon nanotubes and / or fullerenes as a binder resin. The amount of 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 the organic compound and the inorganic compound. Examples of the organic compound 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, and polyester-based. Examples thereof include resins, vinyl acetate resins, vinyl chloride resins, vinyl chloride-vinyl vinegar copolymer resins, and fluorine-containing copolymer resins. Examples of the inorganic compound include metal oxide gels and / or metal hydroxide gels such as silica sol, alumina sol, zirconia sol, and niobium oxide, and sol gel thin films mainly composed of silicon compounds such as polysiloxane, colloidal silica, and silica. .. b). Further, the antifouling conductive layer of a) includes one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound (methyltrimethoxy). Silane, methyltriethoxysilane, etc.) are included in the mixing ratio of nanoparticles and the silane compound or its hydrolysis product in a mass% ratio of 20: 1 to 3: 1 and 1 to 10 with respect to the coating layer. By forming a mass% nanoparticle network, the antistatic effect can be further enhanced.

In particular, the antifouling conductive layer formed in a network is a continuum having an area occupancy of 20% or more, preferably 35 to 70%, per surface of a film, canvas, mesh sheet, tarpaulin, or the like. By attaching a conductive network of 0.05 to 20 g / m ² , preferably 0.5 to 10 g / m ² , the canvas, mesh sheet, tarpaulin and the like can be freely colored. Such an antifouling conductive layer (conductive network) is a regular continuum such as a square grid, a triangular grid, a honeycomb, a round hole punching, a mesh, an irregular continuum, or even a single stroke. Written characters or patterns, honeycombs, 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 aligned or randomly arranged. By type, 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, carbon oxide nanotubes, and functionalization. One or more selected from carbon nanotubes (terminal modification and / or side wall modification) and metal (deposited or sputtered) carbon nanotubes, and the hexagonal arrangement (chiral index) constituting the carbon nanotube is (n, n). It may be any of an armchair type, a (n, 0) zigzag type, and a (n, m) helical type. These carbon nanotubes can be used in combination with oxides of transition metals such as Ru, Ir, W, Mo, Mn, Ni, and Co to further improve the conductivity. In particular, a π-electron conjugated conductive polymer (described in paragraph [0029]) can also be used as a binder. In particular, metal (deposited or sputtered) carbon nanotubes are carbon nanotubes whose surface is metallized by vapor deposition or sputtering of Au, Ag, Cu, Al, Zn, Ti, etc., and have a two-layer structure in which the anchor is a Ti layer. Au / Ti, Ag / Ti, and Cu / Ti are effectively improved in conductivity.

As the fullerene, C60 fullerene, _C70 fullerene, organically modified fullerene, inorganic modified fullerene, non-metal atom- _encapsulated fullerene, metal atom-encapsulated fullerene, and the like can be used. The C ₆₀ fullerene is a soccer ball-shaped cage composed of 20 faces of a 6-membered ring and 12 faces of a 5-membered ring, and the organically modified fullerene is one or more on the surface of the C ₆₀ or C ₇₀ fullerene. A polymer having a substituent and / or one or more functional groups, or a polymer side chain grafted with a functional group-substituted fullerene. The metal-encapsulated fullerene can be added to any of the above fullerenes by Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, lanthanoid, actinide atom, or It is the one in which metal ions are incorporated. The non-metal endohedral fullerene may be any of the above fullerenes, such as hydrogenated fullerene containing H, carbonized fullerene containing C, nitrogenized fullerene containing N, oxygenated fullerene containing O, and sulfurized fullerene containing S. be.

Specific examples of the π-electron-conjugated conductive polymer include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophenebinylenes, and copolymers and derivative polymers thereof. The chain is composed of a π-conjugated system, and the side chain, the presence or absence of a substituent, the side chain, and the type of the substituent are not particularly limited, but polypyrrole, polythiophene, poly (N-methylpyrrole), and poly (3-methylthiophene). ), Poly (3-methoxythiophene), poly (3,4-ethylenedioxythiophene), etc., polypyrrole and polythiophene are particularly preferable, especially poly (N-methylpyrrole), poly (3-methylthiophene). Alkyl-substituted compounds are preferable because they have excellent solubility in organic solvents. In addition, a polymer carboxylate (polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.) is doped into a π-electron-conjugated conductive polymer, or a polymer sulfonic acid (polyvinyl sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfone, etc.) is doped. Dope with acid, ethyl sulfonic acid polyacrylate, butyl sulfonic acid poly acrylate, poly (2-acrylamide-2-methyl-1-propanesulfonic acid), etc., or polymerized carboxylate and polymerized sulfone Higher conductivity can be achieved by combined doping with an acid at 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. The ratio of the ~ 1: 1, π-electron-conjugated conductive polymer to the polymer carboxylate and the polymer sulfonic acid is preferably 5: 1 to 1: 1, preferably the polymer carboxylate or the polymer. The 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, and the π-electron-conjugated system during the oxidative polymerization of the π-electron-conjugated conductive polymer synthesis. It is preferably doped in a conductive polymer.

In order to process the dust-proof film of the present invention and the canvas, mesh sheet, and tarpaulin provided with the dust-proof film into a sheet shutter, a partition, a floor sheet, an equipment cover, a flexible container, etc., these same base materials are used. Bonding and these dissimilar base materials (ends overlapped and bonded facing the same surface) can be joined by high-frequency vibration using a high-frequency welder machine. Specifically, a film material is placed between two electrodes (one electrode is a weld bar), and a potential difference oscillating at a high frequency (1 to 200 MHz) is applied while pressurizing with the weld bar to prevent dust from the substrate. The film is melted and softened by molecular frictional heat to fuse the films at the interface between the substrates, and then cooled and solidified in that state to obtain a bonded body. Further, an ultrasonic fusion method in which the amplitude of the ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator is amplified and fusion is performed by utilizing the frictional heat generated at the boundary surface of the base material, or the electric of the heater. A hot air fusion method in which hot air set steplessly at 100 to 700 ° C. is blown between the base materials through a nozzle to melt and soften the surface of the base material, and the base materials are crimped and fused immediately after passing through the nozzle. Bonding is possible by a hot plate fusion method in which the adherend is crimped and fused using a mold (iron) that has a built-in heater and is heated above the melting temperature of the dustproof film. In the above joining method, when the area occupancy 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 of the softening temperature is large. The larger the value, the insufficient the bonding adhesive force between the obtained base materials. Therefore, the continuous body having an area occupancy of 20% or more, preferably 35 to 70% of the antifouling conductive layer. As a conductive network of 0.05 to 20 g / m ² , preferably 0.5 to 10 g / m ² , an area other than the antifouling conductive layer, that is, a dust-proof film under the surface exposed, and the other base material. It is desirable to provide a state in which the dust-proof film substrate surfaces on the back surface of the film are at least thermally melted and can be firmly adhered to each other.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these examples. In the following examples and comparative examples, the dustproof effect was evaluated by the surface resistivity. In addition, after paragraph [0032], Examples 1, 2, 5 and 6 shall be read as Reference Examples 1, 2, 5 and 6, respectively, and the same shall apply in Tables 1 and 2.
1) Surface resistivity measurement (based on JIS K7194)
After allowing the film material piece to stand at 23 ° C. and a relative humidity of 50% RH for 24 hours, the surface resistivity was measured three times using the following resistivity meter (JIS K7194 compliant), and the average value was taken as the surface resistivity. For the high resistance / resistivity meter, "High Resta UP MCP-HT800 (range 10 ³ to 10 ¹⁴ Ω) manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used.
2) Dustproof
After a quantitative amount of commercially available weak wheat flour (Nisshin Flour Milling Co., Ltd.) is evenly sprinkled on the surface of the test piece that is not charged with static electricity, the test piece is inverted downward to fix the test piece in a tense state, and the weak wheat flour is released. In a state where it could fall freely, the weak wheat flour was evaluated for its ability to fall off by tapping it strongly with the index finger from the back surface five times.
1: Residual amount less than 10% by mass: Good dust resistance
2: Residual amount 10% by mass to less than 25% by mass: Slightly inferior in dust resistance
3: Residual amount exceeds 25% by mass: Poor 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 PET sheet is heated in an electric heating furnace at 180 ° C. for 1 minute. The gelation treatment was carried out to obtain a film (1) having a film thickness of 0.2 mm.
<Soft vinyl chloride resin paste sol composition (1)>
Emulsified polymerized 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 between alcohol with ethylene oxide added to n-octanol and isophthalic acid: (ether bond (Has two) Equivalent to [Chemical formula 1] Diisononyl isophthalate (alkyl ester compound 1) Equivalent to [Chemical formula 7] 20 parts by mass Tricredil 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 Antimon trioxide (flame retardant) 10 parts by mass Rutyl type titanium oxide (white pigment) 5 parts by mass Bentriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Using the coating liquid for the following antifouling conductive layer (1) (solid content concentration 17.3% by mass) on the surface side surface of the film (1), by coating with a 120-mesh square lattice pattern gravure roll, 55. An antifouling conductive layer (1) of a lattice-like continuum (lattice width 5 mm, square pores 10 mm × 10 mm) having an area occupancy of 5% was formed, and a dust-proof film having a mass of 235 g / m ² was obtained.
<Solution for antifouling conductive layer (1)>
Fluoroolefin resin (Fluorine resin: solid content 15% by mass) 100 parts by mass Triisocyanate compound 2 parts by mass * Isocyanurate-modified triisocyanate, which is a trimerate of xylylene diisocyanate (XDI): 100% active ingredient
Single-walled carbon nanotubes (1.5-2.5 nm in diameter) 0.2 parts by mass * The content of carbon nanotubes in the antifouling conductive layer is 1.15% by mass.
Benzotriazole skeleton compound (ultraviolet absorber) 0.1 part by mass

[Example 2]
The following soft vinyl chloride resin compound (1) was subjected to calendar molding (mirror surface roll at 190 ° C.) to obtain a film (2) having a thickness of 0.2 mm.
<Soft vinyl chloride resin compound (1)>
Suspended Polymerized 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 between alcohol with ethylene oxide added to n-octanol and terephthalic acid: (ether bond) 20 parts by mass of tricresyl phosphate (flameproof plasticizer) 10 parts by mass epoxidized soybean oil (stabilizer and plasticizer) Agent) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimon trioxide (flame retardant) 10 parts by mass Rutyl-type titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass On the surface side surface of the film (2) of the above, the coating liquid for the following antifouling conductive layer (2) (solid content concentration 17.5% by mass) was used, and the square lattice pattern gravure roll coating of 120 mesh was applied to 55. An antifouling conductive layer (2) of a lattice-like continuum (lattice width 5 mm, square pores 10 mm × 10 mm) having an area occupancy of 5.5% was formed, and a dust-proof film having a mass of 244 g / m ² was obtained. ..
<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-modified triisocyanate: 100% active ingredient
Single-walled carbon nanotubes (1.5-2.5 nm in diameter) 0.8 parts by mass * The content of carbon nanotubes in the antifouling conductive layer is 0.75% by mass.
Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by 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 3]
A film (3) 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) of Example 1 was changed to the soft vinyl chloride resin paste sol composition (2). ) Was obtained.
<Soft vinyl chloride resin paste sol composition (2)>
Emulsified Polymerized Vinyl Chloride Resin (Polymerization Degree 1700) 100 parts by mass Alkyl Ether Ester Compound (3) 40 parts by mass * 1,2-Cyclohexanedicarboxylic acid by reaction of alcohol with ethylene oxide added to n-octanol and 1,2-cyclohexanedicarboxylic acid Acid diether ester: (has two ether bonds: equivalent to [polymerization 3])
1,2-Cyclohexanedicarboxylate diisononyl (alkyl ester compound 3) Equivalent to [Chemical formula 9] 20 parts by mass Trickresyl phosphate (flameproof plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass / Zinc composite stabilizer 2 parts by mass Antimon trioxide (flame retardant) 10 parts by mass Rutyl type titanium oxide (white pigment) 5 parts by mass Bentriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Of the above film (3) A coating liquid for the following antifouling conductive layer (3) (solid content concentration 17.7% by mass) was used on the surface surface surface, and a 120-mesh square lattice pattern gravure roll coating was applied to occupy an area of 55.5%. An antifouling conductive layer (3) of a lattice-like continuous body having a ratio (lattice width 5 mm, square pores 10 mm × 10 mm) was formed, and a dust-proof film having a mass of 233 g / m ² was obtained.
<Solution for antifouling conductive layer (3)>
Fluoroolefin resin (Fluorine resin: solid content 15% by mass) 100 parts by mass Triisocyanate compound 2 parts by mass * Isocyanurate-modified triisocyanate, which is a trimerate of xylylene diisocyanate (XDI): 100% active ingredient
Single-walled carbon nanotubes (1.5-2.5 nm in diameter) 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 part by mass Organosilica sol (silica nanoparticles) 5 parts by mass * Particle size 10 to 15 nm: Solid content 30% by mass: Methylethylketone solvent Methyltriethoxysilane (silane compound) 0. 3 parts by mass * A nanoparticle network with a mass ratio of 5: 1 between silica sol and methyltriethoxysilane is formed in the coating layer * The content of the nanoparticle network with respect to the coating layer is 9.4% by 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) of Example 2 was changed to the soft vinyl chloride resin compound (2).
<Soft vinyl chloride resin compound (2)>
Suspended Polymerized 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 between alcohol with ethylene oxide added to n-octanol and sebacic acid: (ether) Has two bonds: Corresponds to [Chemical formula 4] Diisononyl sebacate (alkyl ester compound 4): Corresponds to [Chemical formula 10]
20 parts by mass Tricredil phosphate (flameproof plasticizer) 10 parts by mass Evaporated soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimon trioxide (flame retardant) 10 parts by mass Rutyl type Titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass On the surface side surface of the above film (4), a coating liquid (solid) for the following antifouling conductive layer (4) A grid-like continuum (lattice width 5 mm, square pores 10 mm × 10 mm) having an area occupancy of 55.5% by coating with a 120-mesh square lattice pattern gravure roll using a component concentration of 18.2% by 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-modified triisocyanate: 100% active ingredient
Single-walled carbon nanotubes (1.5-2.5 nm in diameter) 0.8 parts by mass * The content of carbon nanotubes in the antifouling conductive layer is 0.75% by mass.
Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Organosilica sol (silica nanoparticles) 30 parts by mass * Particle size 10 to 15 nm: Solid content 30% by mass: Methylethylketone solvent Methyltriethoxysilane (silane compound) 0. 9 parts by mass * A nanoparticle network with a mass ratio of 10: 1 between silica sol and methyltriethoxysilane is formed in the coating layer * The content of the nanoparticle network with respect to the coating layer is 8.5% by 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]
A plain weave spun cloth made of polyester (PET) short fiber spun yarn was used as the cloth 1, and a film was formed on both sides of the cloth 1 by the soft vinyl chloride resin paste sol composition (1) of Example 1.
<Cloth 1>
[Yarn density: 44 warp twin yarns (590dtex) / inch x 40 weft yarns (590dtex) / inch: void ratio 4.2%: mass 228 g / m ² ]
The cloth 1 is dipped (dipping) in a liquid bath filled with the soft vinyl chloride resin paste sol composition (1), the cloth 1 is completely impregnated with the paste sol composition (1), and the cloth 1 is pulled up at the same time. It was squeezed with a rubber roll and gelled in a hot air furnace at 180 ° C. for 3 minutes to complete the gelation of the paste sol composition (1). Obtained a / m ² canvas.
An area occupancy of 55.5% was applied to one side (front side) of this canvas by applying a coating liquid for the antifouling conductive layer (1) (Example 1) and applying a 120-mesh square lattice pattern gravure roll. An antifouling conductive layer (1) of a lattice-like continuous body (lattice width 5 mm, square pores 10 mm × 10 mm) having a lattice-like continuum was formed, and a canvas having a mass of 562 g / m ² was obtained.

[Example 6]
Polyester (PET) fiber plain weave fabric (warp 1111dtex multifilament yarn: yarn density 22 / 2.54 cm × weft 1111dtex multifilament yarn: yarn density 24 / 2.54 cm: void ratio 21%: mass 165 g / m ² ) Is used as the cloth 2, and a film having a thickness of 0.2 mm molded from the soft vinyl chloride resin compound (1) is formed on both sides thereof by a bridge melt laminating by thermal pressure bonding to form a “film layer / cloth 2 / film layer”. A tarpaulin having a thickness of 0.75 mm and a mass of 785 g / m ² was obtained.
An area occupancy of 55.5% was applied to one side (front side) of this tarpaulin by applying a coating liquid for the antifouling conductive layer (2) (Example 2) and applying a 120-mesh square lattice pattern gravure roll. An antifouling conductive layer (2) of a lattice-like continuous body (lattice width 5 mm, square pores 10 mm × 10 mm) having a lattice-like continuum was formed, and a tarpaulin having a mass of 787 g / m ² was obtained.

[Example 7]
<Cloth 3>
Polyester (PET) fiber imitation fabric (warp 1111dtex multifilament yarn 3 yarns: yarn density 6 yarns / 2.54 cm x warp yarn 1111dtex multifilament yarns 3 yarns: yarn density 6 yarns / 2.54 cm: void ratio 27%: Holes 2.2 mm x 2.2 mm: Mass 125 g / m ² )
The cloth 3 is dipped (dipping) in a liquid bath filled with the soft vinyl chloride resin paste sol composition (2), the cloth 3 is completely impregnated with the paste sol composition (2), and the cloth 3 is pulled up at the same time. Squeeze with a rubber roll to complete the gelation of the paste sol composition (2) in a hot air furnace at 180 ° C. for 3 minutes, and press this with a mirror roll to flatten the soft vinyl chloride sap on the entire surface of the cloth 3. A formed mesh sheet having a mass of 364 g / m ² was obtained.
50% area occupancy rate by 100 mesh gravure roll (no handle) coating using the coating liquid for the antifouling conductive layer (3) (Example 3) on one side (front side) of this mesh sheet. The antifouling conductive layer (3) of the mesh tuning continuum (mesh width 2 mm, pores 2.2 mm × 2.2 mm) having the above was formed, and a mesh sheet having a mass of 366 g / m ² was obtained.

[Example 8]
A film having a thickness of 0.2 mm molded from a soft vinyl chloride resin compound (2) on both sides of the cloth 2 is subjected to a bridge melt laminating by thermocompression bonding to form a "film layer / cloth 2 / film layer". A tarpaulin having a weight of 0.75 mm and a mass of 785 g / m ² was obtained.
An area occupancy of 55.5% was applied to one side (front side) of this tarpaulin by applying a coating liquid for the antifouling conductive layer (4) (Example 4) and applying a 120-mesh square lattice pattern gravure roll. An antifouling conductive layer (4) of a lattice-like continuous body (lattice width 5 mm, square pores 10 mm × 10 mm) having a lattice-like continuum was formed, and a tarpaulin having a mass of 787 g / m ² was obtained.

[Effects of Examples 1 to 8]
A film containing an alkyl ether ester compound in which an antifouling conductive layer is formed in a lattice pattern on one side or more of this film, and a canvas, a mesh sheet, and a tarpaulin using these are all having a surface resistivity of 10. It had about ⁷ to ¹⁰⁹ Ω / □ and was excellent in dust resistance. However, in the present invention, the quality of the surface resistivity depends on the type and amount of the alkyl ether ester compound, the type and content of the conductive substance in the antifouling conductive layer, and the occupied area ratio of the antifouling conductive layer. In particular, the larger the amount of the alkyl ether ester compound, the larger the ratio of the content of the conductive substance, and the larger the occupied area ratio of the antifouling conductive layer, the better the dust resistance (antistatic property). Among Examples 1 to 8, it has a wide range of effects on its dustproof property (antistatic property).

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

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

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

[Reference example 4]
The alkyl ether ester compound (4): [Chemical formula 4] 35 parts by mass of Example 4 was replaced with the alkyl ester compound (4): [Chemical formula 10] 35 parts by mass, and the plasticizer was replaced with [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. The obtained film had dust resistance (antistatic property), but the surface resistivity was reduced by about 1st power as compared with Example 4.

As is clear from the above Examples and Reference Examples, according to the present invention, surfactants and waxes that may cause adverse effects such as bleed contamination, printing defects, and poor bonding between sheets are used. It is possible to obtain a soft vinyl chloride resin film and film with dust resistance (effect due to antistatic property) in accordance with the REACH regulation and the RoHS directive. Tarpaulin material used for tent houses, pavilions, flexible containers, water tanks, etc., canvas material used for truck hoods, seat covers, etc., mesh sheet material used for building curing sheets, breathable sunshades, etc.) Is excellent in dustproof property (effect due to antistatic property) and conforms to the REACH regulation and the RoHS directive, so that it can be widely deployed in applications other than the above.

Claims (4)

It mainly contains a vinyl chloride resin and a plasticizing agent, and as the plasticizing agent, at least an isophthalic acid dialkyl ether ester (group of [Chemical compound 1]), a terephthalic acid dialkyl ether ester (group of [Chemical compound 2]), and a cyclohexanedicarboxylate dialkyl. Ether esters (group of [Chemicals 3]), dicarboxylic acid dialkyl ether esters (group of [Chemicals 4]), tristrimertic acid (alkyl ether esters) (group of [Chemicals 5]), and tetramellitic acid tetrakis (alkyl). A film containing one or more alkyl ether ester compounds selected from (ether ester) (group of [Chemical formula 6]), in which an antifouling conductive layer is formed on one or more sides of this film, or 1) is formed on the entire surface or 2). ) The antifouling conductive layer is formed of a reticulated continuum having an area occupancy of at least 20%, and the antifouling conductive layer contains one or more selected from carbon nanotubes, fullerene and π-electron conjugated conductive polymers. The conductive layer further contains one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound, with respect to the coating layer. A dust-proof film characterized by constituting a nanoparticle network of 1 to 10% by mass.

([Chemical formula 1] to [Chemical formula 3]: In the formula, R ₁ and R ₂ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ and A ₂ have 2 to 4 carbon atoms. M and n are integers from 1 to 7, and A ₁ and A ₂ , R ₁ and R ₂ and m and n may be the same or different from _each other. The total carbon number of R ₁ , 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-. It may be any of cyclohexanedicarboxylic acid dialkyl ether esters.)

([Chemical formula 4]: In the formula, R ₁ and R ₂ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ and A ₂ are alkylene groups having 2 to 4 carbon atoms, A. ₃ indicates 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 different even if they are the same. The total number of carbon atoms of A ₁ and R ₁ and A ₂ and R ₂ may be 5 to 17).

([Chemical formula 5]: In the formula, R ₁ , R ₂ , R ₃ represent a linear or branched alkyl group having 3 to 15 carbon atoms, and A ₁ , A ₂ and A ₃ have 2 to 15 carbon atoms. Indicates an alkylene group of 4. m, n, o are integers from 1 to 7, and A ₁ and A ₂ and A ₃ and R ₁ and R ₂ and R ₃ and m and n and o are the same, respectively. The total carbon number of A ₁ and R ₁ and A ₂ and R ₂ and A ₃ and R ₃ is 5 to 17).

([Chemical formula 6]: In the formula, R ₁ , R ₂ , R ₃ , and R ₄ represent linear or branched alkyl groups having 3 to 15 carbon atoms, and A ₁ , A ₂ , A ₃ , and A. ₄ represents an alkylene group having 2 to 4 carbon atoms. M, n, o and p are integers of 1 to 7, and A ₁ and A ₂ and A ₃ and A ₄ and R ₁ and R ₂ and R ₃ and R. ₄ and m, n, o and p may be the same or different, respectively. Total carbon of A ₁ and R ₁ and A ₂ and R ₂ and A ₃ and R ₃ and A ₄ and R ₄ . The number is 5 to 17.) The plasticizer further comprises an isophthalic acid dialkyl ester (group of [chemical 7]), a terephthalic acid dialkyl ester (group of [chemical 8]), a cyclohexanedicarboxylic acid dialkyl ester (group of [chemical 9]), and a dicarboxylic acid dialkyl ester. (Group of [Chemical Acid 10]), Trimellitic Acid Tris (alkyl Ester) (Group of [Chemical Acid 11]), and Pyromellitic Acid Tetrax (alkyl Ester) (Group of [Chemical Acid 12]). The dustproof film according to claim 1, wherein the above alkyl ester compound is used in combination.

([Chemical acid 7] to [Chemical acid 9]: _In the _formula , R5 and R6 represent linear or branched alkyl groups having ₃ to 17 carbon atoms, and R5 and R6 are the _same , respectively. [Chemical formula 9] may be any of 1,2-cyclohexanedicarboxylic acid dialkyl ester, 1,3-cyclohexanedicarboxylic acid dialkyl ester, and 1,4-cyclohexanedicarboxylic acid dialkyl ester. .)

([Chemical formula 10]: In the formula, R ₅ and R ₆ indicate a linear or branched alkyl group having 3 to 17 carbon atoms, and A ₄ indicates an alkylene group having ₄ to 12 carbon atoms. , R ₆ may be the same or different.)

([Chemical formula 11]: In the formula, R ₅ , R ₆ and R ₇ represent linear or branched alkyl groups having 3 to 17 carbon atoms, and R ₅ and R ₆ and R ₇ are the same, respectively. It may be different.)

([Chemical formula 12]: In the formula, R ₅ , R ₆ , R ₇ , and R ₈ represent linear or branched alkyl groups having 3 to 17 carbon atoms, and R ₅ and R ₆ and R ₇ , R. ₈ may be the same or different from each other.) A canvas or mesh sheet using a cloth as a base material, wherein the dust-proof film according to claim 1 or 2 is provided on the entire surface of the cloth in a coated state. A tarpaulin having a cloth as a base material and having the dustproof film according to claim 1 or 2 laminated on at least one surface of the cloth.