JP7025005B2 - Dust-proof film, dust-proof 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 and a film that do not contain a phthalic acid-based compound (ortho-form) as a plasticizer component, and in particular, 1) dust-proof and dust-proof using a soft vinyl chloride-based resin film. The present invention relates to a sail cloth for industrial materials having excellent environmental hygiene and a mesh sheet, and 2) a tarpaulin for industrial materials having excellent dust resistance and environmental hygiene using a 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 also begun to focus on proposing alternatives, but no alternative has yet been proposed for a 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. We have proposed soft vinyl chloride resin industrial material sheets that do not use phthalate ester compounds (Patent Documents 2 to 5) from the viewpoint of concerns about contamination with groundwater, but these soft vinyl chloride resin industrial material sheets bleed. Since it is difficult to impart dust resistance (antistatic property) unless a surfactant or wax that may cause adverse effects such as contamination, printing failure, or bonding failure between sheets is mixed in, the REACH Regulations and RoHS Directive are stipulated. A soft vinyl chloride resin film and a film having a dustproof property (antistatic property) and a dustproof (antistatic property) industrial material sheet according to the REACH regulation and the RoHS directive using these have 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 does not use surfactants or waxes that may cause adverse effects such as bleed contamination, printing defects, and bonding defects between sheets, and has dust resistance (antistatic properties) in accordance with the REACH regulation and the RoHS directive. (Effect by) soft vinyl chloride resin film and film, and dustproof (antistatic effect) industrial material sheet (for sheet warehouse, tent house, etc.) according to the REACH regulation and RoHS directive using these. To provide tarpaulin materials for pavilions, flexible containers, water tanks, canvas materials for truck hoods, seat covers, building curing sheets, mesh sheet materials for breathable sunshades, etc.) It is something to do.

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, an antistatic soft vinyl chloride resin film and a film according to the REACH regulation and the RoHS directive can be obtained, and further, dustproof (antistatic property) according to the REACH regulation and the RoHS directive using these can be obtained. The present invention has been completed by finding that an industrial material sheet can be obtained.

That is, the dust-proof film or dust-proof film of the present invention mainly contains a vinyl chloride resin and a plasticizing agent, and contains an alkyl ether ester compound and an alkyl ester compound as the plasticizing agent in a mass ratio of 3: 1 to 1: 3. Including, the combination of the plasticizer includes an isophthalic acid dialkyl ether ester (group of [chemical 1]), an isophthalic acid dialkyl ester (group of [chemical 7]), and a terephthalic acid dialkyl ether ester (group of [chemical 2]). Telephthalic acid dialkyl ester (group of [Chemical acid 8]), cyclohexanedicarboxylic acid dialkyl ether ester (group of [Chemical acid 3]) and cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical acid 9]), dicarboxylic acid dialkyl ether ester ([Chemical acid 3] group) 4] group) and dicarboxylic acid dialkyl ester ([Chemical acid 10] group), trimellitic acid tris (alkyl ether ester) ([Chemical acid 5] group) and trimellitic acid tris (alkyl ester) ([Chemical acid 11]). Group), and one or more selected from the pyromellitic acid tetrakis (alkyl ether ester) (group of [chemical 6]) and the pyromellitic acid tetrakis (alkyl ester) (group of [chemical 12]). preferable.

（〔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。）

（〔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。）

([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 of 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 number of carbon atoms 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 are 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.)

([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.)

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

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

According to the present invention, dustproof (antistatic) according to 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 soft vinyl chloride resin film and film (effect of antistatic property) and a dustproof (antistatic effect) industrial material sheet according to the REACH regulation and RoHS directive using these can be obtained. It can be widely used for seat warehouses, tent houses, pavilions, flexible containers, water tanks, truck hoods, seat covers, building curing sheets, breathable sunshades, etc.

The dust-proof film or dust-proof film of the present invention mainly contains a vinyl chloride resin and a plasticizing agent, and contains an alkyl ether ester compound and an alkyl ester compound as the plasticizing agent in a mass ratio of 3: 1 to 1: 3. , The combination of the plasticizers is an isophthalic acid dialkyl ether ester ([Chemical acid 1] group) and an isophthalic acid dialkyl ester ([Chemical acid 7] group), a terephthalic acid dialkyl ether ester ([Chemical acid 2] group) and terephthal. Acid dialkyl ester (group of [Chemical acid 8]), cyclohexanedicarboxylic acid dialkyl ether ester (group of [Chemical acid 3]) and cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical acid 9]), dicarboxylic acid dialkyl ether ester ([Chemical acid 4]). ] And dicarboxylic acid dialkyl esters (group of [chemical 10]), trimellitic acid tris (alkyl ether ester) (group of [chemical 5]) and trimellitic acid tris (alkyl ester) ([chemical 11] Group), and one or more selected from pyromellitic acid tetrakis (alkyl ether ester) (group of [chemical 6]) and pyromellitic acid tetrakis (alkyl ester) (group of [chemical 12]) .

（〔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。）

（〔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。）

([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 of 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 number of carbon atoms 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 are 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.)

([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 dust-proof film and the dust-proof 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 in an alkyl chain). In the case of (having the above ether bond), 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 alkyl ether ester compound and the alkyl ester are used. The mixing ratio with the compound 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 and the dust-proof film of the present invention include chlorinated paraffin compounds, tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, etc., if necessary to impart flame resistance. The aromatic phosphoric acid ester 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 and 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 two or more allyl groups. The allyl phthalate compound and the like 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 for 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 an esterification reaction between 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 dust-proof film of the present invention and the vinyl chloride resin contained in the dust-proof film are homopolymers of vinyl chloride monomers (homomopolymers having a degree of polymerization of 1000 to 4000), and are suspended with an emulsified polymer (wheat powder). Two types of polymers (granule sugar-like) can be used. The emulsified polymer forms a paste-like composition together with a plasticizer and an additive, is used for coating and dipping, and is heated to gel to form the dust-proof film (thickness 0.01 mm to 1 mm) of the present invention. The dust-proof film impregnated in the cloth and formed on the cloth is a canvas for industrial materials, and the one impregnated in the coarse cloth and formed on the coarse cloth is a mesh sheet for industrial materials. 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 form the dust-proof film (thickness 0.1 mm to 1 mm) of the present invention. A tarpaulin for industrial materials is obtained by forming this dustproof film on both sides of a cloth. 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, for the dust-proof film and the dust-proof film, a polyol compound, chlorinated polyethylene, butyl rubber, acrylic rubber, polyurethane, butadiene-styrene-methylmethacrylate copolymer, styrene-butadiene copolymer, etc. are used to improve workability and flexibility. It can be used in combination with vinyl chloride resin in an amount of about 5 to 25% by mass for the purpose of improving properties, improving low temperature characteristics, improving heat resistance characteristics, mitigating impact, and the like. Further, a reactive compound such as a polyisocyanate compound, a carbodiimide compound, or an oxazoline compound is added to form a crosslinked structure in the dustproof film and the dustproof film to improve heat resistance, or fabrics such as woven fabrics and knitted fabrics. It is also possible to improve the adhesiveness to.

Further, in the dust-proof film and the dust-proof film, various known additives for synthetic resins can be blended as components other than the plasticizer in various arbitrary amounts, and as a stabilizer for vinyl chloride resin, a calcium-zinc composite system, Thermal discoloration during molding by using one or more stabilizers such as barium-zinc composite type, organic tin laurate, organic tin mercaptite, and epoxy type, and using about 1 to 10 parts by mass with respect to 100 parts by mass of vinyl chloride resin. And improve 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, the dust-proof film and the dust-proof film of the present invention include 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. It can be blended in an amount within a range that can meet each flame retardant standard. Further, the dust-proof film and the dust-proof film of the present invention may be a transparent film containing no flame retardant or a filler, or a light semitransparent film containing a flame retardant or a filler, and an inorganic pigment. (Titanium oxide, Bengara, carbon black, etc.), transparent pigments arbitrarily colored with organic pigments (azo, quinacridone, phthalocyanine, nitro, perylene, etc.), translucent colored light, It may be colored and light-shielded.

The composite of the fabric (woven fabric, knitted fabric, coarse fabric) and the dustproof film of the present invention is the canvas for industrial materials, and the one impregnated in the coarse fabric and formed on the coarse fabric is the mesh sheet for industrial materials. be. 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 yarns made of synthetic fibers, span yarns, and plain woven fabrics made of covering yarns, twill woven fabrics, red woven fabrics, woven fabrics, basket woven fabrics, triaxial woven fabrics, and quaternary woven fabrics 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 span 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 dustproof film on the fabric is, for example, a plasticizer (group of [chemical 1]) to (group of [chemical 6]) selected from (group of [chemical 1]) on an emulsion polymerization type vinyl chloride resin (100 parts by mass). 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 to determine the amount of plasticizer (40 to 80 parts by mass). Using the paste sol composition, a known coating method such as dipping (double-sided processing on the fabric), coating (single-sided or double-sided processing on the fabric, knife coating, gravure coating, clearance coating, etc.) is performed on the fabric. A dustproof film is formed on the front and back. 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 dust-proof 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 it to gel it, a dust-proof 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 with 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 with a certain degree of opening, is thermocompression bonded with a laminator to form the fabric. The dust-proof films on the front and back are partially bridge-fused together at the opening portion, 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.

By forming a fluororesin layer on the dust-proof film and on the dust-proof film, and on the sail cloth, mesh sheet, and tarpaulin using these, the fluororesin layer is a plasticizer, particularly, an alkyl ether ester compound component. As a barrier layer of bleed volatilization, it exhibits excellent antifouling property and excellent dirt removal property at the same time as maintaining dustproof property due to antistatic effect for a long period of time. The fluororesins forming the fluororesin layer include polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), polytrifluoroethylene (PTREE), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), and the like. Polyhexafluoropropylene (PHFP), VdF-TFE copolymer resin, VdF-CTFE copolymer resin, VdF-HFP copolymer resin, TFE-CTFE copolymer resin, TFE-HFP copolymer resin, CTFE- HFP copolymer resin, VdF-TFE-CTFE copolymer resin, VdF-TFE-HFP copolymer resin, TFE-CTFE-HFP copolymer resin, VdF-CTFE-HFP copolymer resin, VdF-TFE- A film (10 μm to 100 μm) such as CTFE-HFP copolymer resin can be used. As for the fluororesin film, the two-layer type of "fluororesin / acrylic resin" and the three-layer type of "fluororesin / acrylic resin / vinyl chloride resin" are particularly base materials (on the dust-proof film and on the dust-proof film). , And the adhesiveness to the sail cloth, mesh sheet, and tarpaulin using these is excellent and preferable.

A fluoroolefin copolymer resin obtained by copolymerizing a fluororesin monomer with a vinyl monomer, and a soluble resin having solubility in an organic solvent, is a base material (dustproof) by a known coating such as gravure coating or knife coating. It is preferable to form a fluororesin layer with a thickness of 1 μm to 20 μm on the film, on the dust-proof film, and on the surface of the sail cloth, mesh sheet, and tarpaulin using these. These fluoroolefin copolymer resins have reactive groups such as hydroxyl groups and carboxyl groups contained in the copolymerized vinyl component as known curing agents (crosslinking agents) such as isocyanate compounds, aziridine compounds, oxazoline compounds, carbodiimide compounds, and melamine compounds. ) Is reacted with the fluoroolefin copolymer resin (solid content) using 1 to 20% by mass, preferably 3 to 15% by mass in terms of solid content, to obtain abrasion resistance and acid resistance of the coating film. Rain resistance, weather resistance, etc. can be improved. Among them, an isocyanate compound is particularly preferable because of its excellent reactivity with a hydroxyl group, and an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound are particularly preferable from the viewpoint of weather resistance.

Further, it is on a base material (on a dustproof film and a dustproof film, and a sail cloth, a mesh sheet, and a tarpaulin using these), or on a fluororesin layer described in paragraphs [0023] and [0024]. An antifouling layer may be provided in which an inorganic colloidal substance having a primary particle diameter of 3 to 150 nm is supported on a binder component containing a hydrolyzed condensate of a silane coupling agent. This antifouling layer serves as a barrier layer for bleeding volatilization of the plasticizer, especially the alkyl ether ester compound component, and maintains dustproofness due to the antistatic effect for a long period of time, as well as excellent antifouling property and excellent dirt removal property. Is expressed. The inorganic colloidal substances used are photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalyst tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and composite. One or more metal oxides selected from oxide (zinc oxide-antimonium pentoxide complex or tin oxide-antimonite pentoxide complex) sol can be used, especially photocatalyst active titanium oxide sol, photocatalyst active zinc oxide sol, photocatalyst. Active tin oxide sol and the like are preferable because of their excellent antifouling effect. The binder component is a silane coupling agent (vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. alone. , Or in combination with these), and hydrolyzates thereof, co-hydrolyzed compounds with an alkoxysilane compound, and the like can be used. The content of the inorganic colloidal substance in the antifouling layer is not limited, but is particularly preferably 25 to 50% by mass. These antifouling layers are formed by applying and drying a solution of a resin soluble in a solvent or water, or an emulsion liquid by a coating method such as a spray coat or a gravure coat.

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.
1) Surface resistivity measurement (JIS K7194 compliant)
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. However, in the present invention, the quality of the surface resistivity depends on the blending amount of the alkyl ether ester compound, and the larger the blending amount, the better the dustproof property (antistatic property), but the texture of the obtained film or film is increased accordingly. Since there is a concern about adverse effects on practical use such as softening and promoting bleeding of excess plasticizer, the total amount of plasticizer in Examples and Comparative Examples was the same.
The criteria for antistatic properties in the following examples were surface resistivity 10 ¹⁰ Ω / □ to 10 ¹² Ω / □, and surface resistivity less than 10 ¹³ Ω / □ was used as a comparative example.
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. A gelation treatment was carried out to obtain a film having a thickness of 0.2 mm.
<Soft vinyl chloride resin paste sol composition (1)>
Emulsified Polymerized Vinyl Chloride Resin (Degree of Polymerization 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: (2 ether bonds) Equivalent to [Chemical formula 1] Diisononyl isophthalate (alkyl ester compound 1) Equivalent to [Chemical formula 7] 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 Antimone trioxide (flame retardant) 10 parts by mass rutile type titanium oxide (white pigment) 5 parts by mass benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts 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 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 (Has two) Equivalent to [Chemical 2] Equivalent to diisononyl terephthalate (alkyl ester compound 2) [Chemical 8] 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 Antimon trioxide (flame retardant) 10 parts by mass rutile type titanium oxide (white pigment) 5 parts by mass benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass

[Example 3]
A film having a thickness of 0.2 mm was obtained 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). ..
<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 by reaction of alcohol with ethylene oxide added to n-octanol and 1,2-cyclohexanedicarboxylic acid Acid diether ester: (Has two ether bonds: Corresponds to [Chemical compound 3])
1,2-Cyclohexanedicarboxylate 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 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

[Example 4]
A film 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 * n Sebacic acid diether ester by reaction of alcohol with ethylene oxide added to octanoll and sebacic acid: (ether bond Has two: Corresponds to [Chemical formula 4] Diisononyl sebacate (alkyl ester compound 4): Corresponds to [Chemical formula 10]
20 parts by mass tricresyl phosphate (flame retardant 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 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.

[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.

[Example 7]
The cloth 1 is dipped (dipping) in a liquid bath filled with the soft vinyl chloride resin paste sol composition (2), the cloth 1 is completely impregnated with the paste sol composition (2), 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 (2). Obtained a / m ² canvas.

[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.

[Examples 9 to 10]
A two-layer film of polyvinylidene fluoride (PVdF) 20 μm / acrylic resin 30 μm (containing a benzotriazole compound as an ultraviolet absorber) is attached to one surface of the tarpaulin of Examples 6 and 8 as an adhesive (aminoethyl). Acrylic resin / epoxy resin) was laminated to form an antifouling layer.

[Effects of Examples 1 to 8]
The soft vinyl chloride resin film and film containing the alkyl ether ester compound, as well as the canvas, mesh sheet, and tarpaulin using these, all had a surface resistivity of about 10 ¹¹ to 10 ¹² Ω / □. ..

[Comparative Example 1]
The alkyl ether ester compound (1): [Chemical formula 1] 40 parts by mass of Example 1 was replaced with the 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.

[Comparative 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.

[Comparative 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.

[Comparative 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.

As is clear from the above Examples and Comparative 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 (3)

It mainly contains a vinyl chloride resin and a plasticizing agent, and contains an alkyl ether ester compound and an alkyl ester compound as the plasticizing agent in a mass ratio of 3: 1 to 1: 3, and the combination of the plasticizing agents is an isophthalic acid dialkyl ether ester. (Group of [Chemical Acid 1]) and isophthalic acid dialkyl ester (group of [Chemical Acid 7]), terephthalic acid dialkyl ether ester (group of [Chemical Acid 2]) and terephthalic acid dialkyl ester (group of [Chemical Acid 8]), cyclohexane Dicarboxylic acid dialkyl ether ester (group of [Chemical acid 3]) and cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical acid 9]), dicarboxylic acid dialkyl ether ester (group of [Chemical acid 4]) and dicarboxylic acid dialkyl ester ([Chemical acid 10]). ], Trimellitic acid tris (alkyl ether ester) (group of [chemical 5]) and trimellitic acid tris (alkyl ester) (group of [chemical 11]), and tetramellitic acid tetrakis (alkyl ether ester). A dust-proof film or a dust-proof film, which is one or more selected from (group of [chemical 6]) and tetramellitic acid tetrakis (alkyl ester) (group of [chemical 12]) .

([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 of 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 number of carbon atoms 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 are 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.)

([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 is provided on the entire surface of the cloth. A tarpaulin using a cloth as a base material, wherein the dust-proof film according to claim 1 is laminated on at least one surface of the cloth.