JP7545738B2 - Soft polyvinyl chloride resin composite sheet - Google Patents

Description

The present invention relates to industrial material films in general used for agricultural and horticultural vinyl greenhouses, simple medical clean booths, simple industrial clean booths, partitions for public facilities, protective covering materials for automobiles and railway cars, protective covering materials for floors and walls, waterproof covering materials for roofs and ceilings, etc., as well as industrial composite sheets in general, such as tarpaulins used for large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, negative pressure medical tents, architectural protection (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, visual facades, flexible containers, lift-up sheet shutters, floor sheets, partition sheets, etc., as well as canvas used for truck canopies, open-air waterproof sheets, roofed tents, etc., and mesh sheets used for architectural protection mesh sheets, wind and snow protection netting, anti-glare netting, sun protection facades, etc. More specifically, the present invention relates to a regenerative soft vinyl chloride resin film containing at least a biomass vinyl chloride resin synthesized from a plant-derived substance and/or a biomass plasticizer synthesized from a plant-derived substance, and also relates to a soft vinyl chloride resin composite sheet such as a tarpaulin, canvas, or mesh sheet based on a fabric having polyalkylene furanoate fiber yarn or an alkylene furanoate-containing copolymer fiber yarn as a weaving or knitting element, and further relates to a regenerative soft vinyl chloride resin composite sheet formed by compounding a biomass soft vinyl chloride resin film with a fabric using biomass fiber. In this specification, biomass means derived from animals and plants, and regenerative type mainly means carbon neutral (carbon recycling derived from animals and plants) and chemical recycling (polymer regeneration) using regenerated monomers by depolymerization of polymers.

The base material for industrial material sheets such as tarpaulins used for large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural protection (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, facade sheets, flexible containers, lift-up sheet shutters, floor sheets, and partition sheets, as well as canvas used for truck canopies, open-air waterproof sheets, and roofed tents, as well as mesh sheets used for architectural protection mesh sheets, wind and snow protection nets, anti-glare nets, and visual facades, mainly uses fabrics with polyester fiber yarns spun from polyethylene terephthalate (hereinafter referred to as PET resin) as the weaving and knitting elements. In particular, tarpaulin is made by laminating a thermoplastic resin composition film on both sides of a fabric (woven fabric) with a porosity of about 6 to 25%, canvas is made by impregnating and coating both sides of a fabric with a porosity of about 0 to 10% with a liquid thermoplastic resin composition and forming a film from the resulting fabric, and mesh sheet is made by impregnating and coating the entire surface of a coarse woven fabric with a porosity of about 15 to 70% with a liquid thermoplastic resin composition and forming a film from the coating. Soft polyvinyl chloride resins (polyvinyl chloride resins plasticized with a plasticizer) are mainly used as the thermoplastic resins for these industrial material sheets. Membrane structures made from these industrial material sheets, especially large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), are used for 10 to 20 years in conditions exposed to wind, rain, and ultraviolet rays, so the soft polyvinyl chloride resin layer deteriorates over time due to exposure to ultraviolet rays, and the PET fiber fabric base material loses strength due to hydrolysis caused by moist heat. Even if PET fiber fabric and soft polyvinyl chloride resin are recovered from waste industrial material sheets, they are of poor quality and cannot be reused. The incineration of waste industrial material sheets (membrane structures) that are not suitable for recycling, especially those made from soft polyvinyl chloride resin, poses serious environmental and health problems such as the emission of carbon dioxide gas and chlorine gas and the generation of dioxins, and the reality is that they are inevitably buried in landfills.

In recent years, issues such as global warming (abnormal weather, storm and flood damage, rising water levels, ecosystem abnormalities, etc.) caused by the increased carbon dioxide concentration from the incineration of plastic products, marine pollution caused by degraded plastics (microplastic particles), and damage to marine life have become urgent issues, raising awareness of plastic alternatives and plastic reduction, and efforts are now being made to build a carbon-neutral, recycling-oriented society that reduces the environmental burden by increasing the use of plants and plant-derived biomass resources. Carbon neutral is an effort to prevent global warming by using biomass fuels and resins derived from carbon dioxide absorbed by plants, which returns the carbon dioxide generated by burning these to nature, and this carbon dioxide is absorbed by plants, maintaining a cycle in which plant-derived fuels and resins are regenerated, thereby substantially not increasing the amount of carbon dioxide in the atmosphere. With the promotion of such non-petroleum products, the practical application of plant-derived biomass resins has been considered. For example, Patent Document 1 discloses an invention for a resin film made of a resin composition containing a carbon-neutral polyolefin using biomass-derived ethylene, and Patent Document 2 discloses an invention for a multilayer container using a carbon-neutral material and having gas barrier properties, the multilayer container having at least a layer containing polyethylene furanoate, which is a polycondensate of biomass-derived polyethylene glycol and biomass-derived furandicarboxylic acid. Applying this carbon neutrality to industrial material sheets, converting polyvinyl chloride resin to biomass polyvinyl chloride resin and even converting plasticizers to biomass plasticizers to produce high-biomass soft polyvinyl chloride resin films, and even converting the base PET fiber fabric to biomass PET fiber fabric to produce high-biomass soft polyvinyl chloride resin films, could contribute to the creation of a carbon-neutral recycling-oriented society with reduced environmental impact. However, currently no soft polyvinyl chloride resin composite sheets made of biomass polyvinyl chloride resin, biomass plasticizer, biomass PET fiber fabric, etc. exist.

On the other hand, as an effective use of petroleum-derived plastic products, flakes obtained by washing and crushing recovered PET bottles are used as raw materials for material recycling into carpet piles and clothing fibers, and further, chemical recycling is carried out in which crushed PET flakes are depolymerized to reduce their molecular weight, and impurities such as colorant components and metal ions of catalysts are removed from this to obtain refined monomers, which are then polymerized again to obtain high-quality PET resin. Specifically, Patent Document 3 discloses a chemical recycling technology for a polyester regeneration method in which polyester waste generated in the manufacturing process of polyester products is mixed with ethylene glycol and depolymerized to obtain low polymers whose main component is ester monomers, and the low polymers obtained are polycondensed to produce recycled polyester. This type of depolymerization is possible for polycondensation-type polymers such as polyurethane, polyamide, and polycarbonate in addition to polyester, but chemical recycling using PET bottles, which is the most established form of resource recovery, stands out. However, chemical recycling of biomass PET has not been established, and biomass PET fiber fabrics and their chemical recycling have not yet been considered. Therefore, if the development of biomass resins progresses widely, it will be possible to obtain recycled and recycled biomass fabrics made of fibers spun from biomass resins. At the same time, the use of biomass will be promoted for the constituent materials such as the thermoplastic resin composition film that covers the biomass fabric and the thermoplastic resin composition film that impregnates and covers the biomass fabric. In particular, if the main components of a flexible polyvinyl chloride resin composition, polyvinyl chloride resin and plasticizer, can be made biomass, a more recycled and recycled flexible polyvinyl chloride resin film will become a reality. As a flexible polyvinyl chloride resin composite sheet that can contribute to the construction of a carbon-neutral recycling-based society with reduced environmental load, ideally, a flexible polyvinyl chloride resin composite sheet that meets the carbon-neutral requirements for at least one of the elements of biomass polyvinyl chloride resin, biomass plasticizer, and fabric made of biomass fibers is desired, and further, the fabric is desired to be a chemically recycled fabric that can be chemically recycled.

JP 2012-251006 A JP 2018-199258 A Japanese Unexamined Patent Publication No. 48-61447

The present invention aims to provide a soft polyvinyl chloride resin film containing at least a biomass plasticizer and/or a biomass polyvinyl chloride resin, a tarpaulin formed by laminating this industrial material film on a fabric, a canvas impregnated with a soft polyvinyl chloride resin, and a soft polyvinyl chloride resin composite sheet such as a mesh sheet, and further, a form in which the fabric is made of biomass fiber, or further, a form in which the biomass fiber has been chemically recycled, all of which contain carbon neutral (regenerative circulation type) elements. The soft polyvinyl chloride resin film and soft polyvinyl chloride resin composite sheet of the present invention have a carbon neutral element (raw materials and products derived from carbon dioxide absorbed by plants are burned and returned to nature as carbon dioxide, which is then absorbed again by plants, resulting in a cycle that does not substantially increase carbon dioxide), and can contribute to the realization of a low-environmental-impact, low-carbon society that can suppress the increase in the amount of carbon dioxide in the global environment. In this invention, biomass means derived from plants and animals, and regenerative circulation type mainly means carbon neutral (recycling carbon derived from plants and animals) and chemical recycling (regeneration of polymers) using regenerated monomers obtained by depolymerization of polymers.

As a result of extensive research and consideration given to these points, the inventors discovered that a recyclable product that meets the carbon neutral requirements can be produced by 1) making a film that contains at least a specific biomass plasticizer and/or a biomass polyvinyl chloride resin, and 2) making a composite sheet in which a resin coating layer that contains at least a specific biomass plasticizer and/or a biomass polyvinyl chloride resin is laminated onto one or more sides of a fabric, leading to the completion of the present invention.

That is, the soft polyvinyl chloride resin film of the present invention (※Read as "soft polyvinyl chloride resin film for the soft polyvinyl chloride resin composite sheet of the present invention" and treat the same in the following notations in the specification) preferably contains at least a biomass plasticizer containing a plasticizer molecule having a radioactive carbon atom C-14 in part of its molecular structure, and/or a biomass polyvinyl chloride resin containing a vinyl chloride unit having a radioactive carbon atom C-14 in part of its molecular structure. C-14, an isotope of C-12, is a radioactive carbon atom with a mass number of 14 formed by nitrogen being changed by the action of cosmic rays from the sun and a half-life of 5,370 years due to β decay, and is always present in nature (especially in animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 and cannot be contained in fossil fuels that are hundreds of millions of years old. Therefore, a plasticizer and polyvinyl chloride resin in which C-14 is detected at a concentration of 1.2 x ^10-12 is proof that the biomass is mainly derived from animals and plants. In particular, the biomass vinyl chloride resin is preferably one obtained by radical polymerization of vinyl chloride monomers synthesized from plant-derived substances. The flexible vinyl chloride resin film of the present invention is most preferably composed of a biomass plasticizer and a biomass vinyl chloride resin, but may be a film composed of a biomass plasticizer and a non-biomass vinyl chloride resin, or a film composed of a non-biomass plasticizer and a biomass vinyl chloride resin. As a result, even if the flexible vinyl chloride resin film of the present invention and waste materials of the film construction are incinerated, the carbon dioxide generated from them can be carbon neutral (the biomass film derived from carbon dioxide absorbed by plants returns to nature, and the carbon is absorbed again by plants, which is a carbon recycling derived from animals and plants) by meeting the requirements for compliance, and can become a regenerative and circulating flexible vinyl chloride resin film.

The flexible polyvinyl chloride resin film of the present invention is preferably a flexible polyvinyl chloride resin film according to claim 1, wherein the biomass plasticizer is at least one selected from a dialkyl phthalate compound [Chemical Formula 1], a dialkyl sebacate compound [Chemical Formula 2], a furandicarboxylic acid alkyl ester compound [Chemical Formula 3], and a polyglycerin fatty acid ester compound [Chemical Formula 4]. The above [Chemical formula 1] is a 100% biomass plasticizer synthesized by an esterification reaction between phthalic acid and alcohol, and preferably the phthalic acid and the alcohol are both plant-derived substances. The above [Chemical formula 2] is a 100% biomass plasticizer synthesized by an esterification reaction between sebacic acid and alcohol, and preferably the sebacic acid and the alcohol are both plant-derived substances. The above [Chemical formula 3] is a 100% biomass plasticizer synthesized by an esterification reaction between furandicarboxylic acid and alcohol, and preferably the furandicarboxylic acid and the alcohol are both plant-derived substances. The above [Chemical formula 4] is a 100% biomass plasticizer synthesized by an esterification reaction between glycerin and fatty acid, and preferably the glycerin and the fatty acid are both plant-derived substances. As a result, even if the flexible polyvinyl chloride resin film of the present invention and waste materials from the film structure are incinerated, the carbon dioxide generated from them can become a regenerative and circular flexible polyvinyl chloride resin film because it satisfies the requirements for carbon neutrality (carbon recycling derived from plants and animals, in which the biomass film derived from carbon dioxide absorbed by plants returns to nature and is then absorbed again by plants).
In the formula, R is an alkyl group.

The soft polyvinyl chloride resin composite sheet of the present invention is a soft polyvinyl chloride resin composite sheet comprising a resin coating layer, which comprises at least a biomass plasticizer containing a plasticizer molecule having a radioactive carbon atom C-14 in part of its molecular structure, and a biomass polyvinyl chloride resin (not including a copolymer) containing a vinyl chloride unit having a radioactive carbon atom C-14 in part of its molecular structure, laminated on one or more sides of a fabric, wherein the biomass plasticizer is one or more compounds selected from a dialkyl phthalate compound [Chemical formula 1], a dialkyl sebacate compound [Chemical formula 2], an alkyl furan dicarboxylate compound [Chemical formula 3], and a polyglycerin fatty acid ester compound [Chemical formula 4], and the fabric preferably comprises, as a weaving or knitting element, a multifilament yarn made of one or more polyalkylene furanoate fibers [Chemical formula 6] selected from polyethylene furanoate and polytrimethylene furanoate, and the polyalkylene furanoate is a biomass fiber having a radioactive carbon atom C-14 in part of its molecular structure . C-14, an isotope of C-12, is a radioactive carbon atom with a mass number of 14, which is formed by the action of cosmic rays from the sun, and a half-life of 5,370 years due to beta decay. It always exists in nature (especially in animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 , and cannot be contained in fossil fuels that are hundreds of millions of years old. Therefore, plasticizers and vinyl chloride resins in which C-14 is detected at a concentration of 1.2 x ^10-12 are proof of biomass mainly derived from animals and plants. In particular, biomass vinyl chloride resins are preferably those obtained by radical polymerization of vinyl chloride monomers synthesized from plant-derived substances. The soft vinyl chloride resin composite sheet of the present invention is most preferably composed of a biomass plasticizer and a biomass vinyl chloride resin, but may also be a composite sheet composed of a biomass plasticizer and a non-biomass vinyl chloride resin, or a composite sheet composed of a non-biomass plasticizer and a biomass vinyl chloride resin. As a result, even if the soft polyvinyl chloride resin composite sheet of the present invention and waste materials of the composite sheet construction are incinerated, the carbon dioxide generated from them can become a regenerative and recycled soft polyvinyl chloride resin composite sheet by satisfying the requirements for carbon neutrality (a cycle in which the biomass composite sheet, derived from carbon dioxide absorbed by plants, returns to nature and is then absorbed again by plants).

In the soft polyvinyl chloride resin composite sheet of the present invention, the biomass plasticizer is preferably one or more selected from a phthalic acid dialkyl ester compound [Chemical formula 1], a sebacic acid dialkyl ester compound [Chemical formula 2], a furandicarboxylic acid alkyl ester compound [Chemical formula 3], and a polyglycerin fatty acid ester compound [Chemical formula 4]. The above [Chemical formula 1] is a 100% biomass plasticizer synthesized by an esterification reaction between phthalic acid and alcohol, preferably a 100% biomass plasticizer in which both the phthalic acid and the alcohol are plant-derived substances, the above [Chemical formula 2] is a 100% biomass plasticizer synthesized by an esterification reaction between sebacic acid and alcohol, preferably a 100% biomass plasticizer in which both the sebacic acid and the alcohol are plant-derived substances, the above [Chemical formula 3] is a 100% biomass plasticizer synthesized by an esterification reaction between furandicarboxylic acid and alcohol, preferably a 100% biomass plasticizer in which both the furandicarboxylic acid and the alcohol are plant-derived substances, and the above [Chemical formula 4] is a 100% biomass plasticizer synthesized by an esterification reaction between glycerin and fatty acid, preferably a 100% biomass plasticizer in which both the glycerin and the fatty acid are plant-derived substances. As a result, even if the soft polyvinyl chloride resin composite sheet of the present invention and waste materials of the composite sheet construction are incinerated, the carbon dioxide generated from them can become a regenerative and recycled soft polyvinyl chloride resin composite sheet by satisfying the requirements for carbon neutrality (a cycle in which the biomass composite sheet, derived from carbon dioxide absorbed by plants, returns to nature and is then absorbed again by plants).
* Wherein n = 4 to 12
* Wherein n = 4 to 12
* Wherein n = 4 to 12
*In the formula, n = 2 to 10, R is an alkyl group having 2 to 10 carbon atoms.

In the soft polyvinyl chloride resin composite sheet of the present invention, the fabric preferably contains a multifilament yarn made of polyalkylene phthalate [Chemical 5] fiber (*The description of "polyalkylene phthalate [Chemical 5] fiber" is deleted, and the same is applied to the following notations in the specification) or polyalkylene furanoate [Chemical 6] fiber in the weaving and knitting elements. This makes it possible and easy to depolymerize the fibers of the fabric separated from the soft polyvinyl chloride resin composite sheet that is to be disposed of after use, and to obtain a monomer for regenerating polyalkylene phthalate [Chemical 5] fiber or polyalkylene furanoate [Chemical 6] fiber. The multifilament yarn means a non-twisted or twisted yarn made of an assembly of long fibers, or a spun yarn (single yarn, two-ply yarn, three-ply twisted yarn) made of an assembly of short fibers.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene phthalate [chemical 5] fiber is preferably one or more selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. This makes it possible and easy to depolymerize the fibers of the fabric separated from the soft polyvinyl chloride resin composite sheet that is to be disposed of after use, and makes it possible to obtain polymerization monomers for regenerating the polyalkylene phthalate [chemical 5] fiber.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene phthalate [chemical formula 5] fiber is a regenerated fiber obtained from a regenerated polyalkylene phthalate by polymerization of a regenerated monomer obtained by depolymerizing a polyalkylene phthalate, and it is preferable that the regenerated monomer contains one or more selected from terephthalic acid, dimethyl terephthalate, and bis 2-hydroxyethyl terephthalate. This makes it possible to make the fabric of the soft polyvinyl chloride resin composite sheet of the present invention a regenerated and recycled type.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene phthalate [Chemical formula 5] fiber is preferably a biomass fiber containing radioactive carbon atom C-14 in a part of the molecular structure of polyalkylene phthalate. This allows the fabric used in the soft polyvinyl chloride resin composite sheet of the present invention to be carbon neutral and regenerative. C-14, an isotope of C-12, is a radioactive carbon atom with a mass number of 14 and a half-life of 5,370 years due to beta decay, which is formed by the action of cosmic rays from the sun and is always present in nature (especially animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 , and cannot be contained in fossil fuels that are already hundreds of millions of years old. Therefore, polyalkylene phthalate [Chemical formula 5] fiber in which C-14 is detected at a concentration of 1.2 x ^10-12 is proof that it is biomass mainly derived from animals and plants.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene furanoate [chemical 6] fiber is preferably one or more selected from polyethylene furanoate, polypropylene furanoate, polybutylene furanoate, and polytrimethylene furanoate. This makes it possible and easy to depolymerize the fibers of the fabric separated from the soft polyvinyl chloride resin composite sheet that is to be disposed of after use, and makes it possible to obtain a polymerization monomer for regenerating the polyalkylene furanoate [chemical 6] fiber.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene furanoate [Chemical 6] fiber is a regenerated fiber obtained from regenerated polyalkylene furanoate by polymerization of a regenerated monomer obtained by depolymerizing polyalkylene furanoate, and it is preferable that the regenerated monomer contains one or more selected from furandicarboxylic acid, dimethyl furandicarboxylate, and bis 2-hydroxyethyl furandicarboxylate. This makes it possible to make the fabric of the soft polyvinyl chloride resin composite sheet of the present invention a regenerated and recycled type.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene furanoate [Chemical formula 6] fiber is preferably a biomass fiber containing radioactive carbon atom C-14 in a part of the molecular structure of polyalkylene furanoate. This allows the fabric used in the soft polyvinyl chloride resin composite sheet of the present invention to be carbon neutral and regenerative. C-14, an isotope of C-12, is a radioactive carbon atom with a mass number of 14 and a half-life of 5,370 years due to beta decay, which is formed by the action of cosmic rays from the sun, and is always present in nature (especially animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 , and cannot be contained in fossil fuels that are already hundreds of millions of years old. Therefore, polyalkylene furanoate [Chemical formula 6] fiber in which C-14 is detected at a concentration of 1.2 x ^10-12 is proof that it is biomass mainly derived from animals and plants.

The soft polyvinyl chloride resin composite sheet of the present invention is a composite sheet in which a resin coating layer containing at least a plasticizer and a polyvinyl chloride resin is laminated on one or more sides of a fabric, and the fabric preferably contains, as a weaving or knitting element, a biomass multifilament yarn made of polyalkylene phthalate [Chemical 7] fiber containing radioactive carbon atom C-14 in a part of its molecular structure, or polyalkylene furanoate [Chemical 8] fiber containing radioactive carbon atom C-14 in a part of its molecular structure. By depolymerizing the biomass fiber of the fabric separated from the soft polyvinyl chloride resin composite sheet that is disposed of after use, a carbon-neutral biomass monomer derived from animals and plants can be obtained for regenerating polyalkylene phthalate [Chemical 7] fiber or polyalkylene furanoate [Chemical 8] fiber, and the inclusion of C-14 (radioactive carbon atom) proves that the regenerated fiber is mainly biomass derived from animals and plants.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene phthalate [chemical 7] fiber is preferably one or more selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. This makes it possible and easy to depolymerize the fibers of the fabric separated from the soft polyvinyl chloride resin composite sheet that is to be disposed of after use, and makes it possible to obtain a polymerization monomer for regenerating the polyalkylene phthalate [chemical 7] fiber.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene phthalate [Chemical formula 7] fiber is a regenerated fiber obtained from a regenerated polyalkylene phthalate obtained by polymerization of a regenerated monomer obtained by depolymerizing a polyalkylene phthalate, and it is preferable that the regenerated monomer contains one or more selected from terephthalic acid, dimethyl terephthalate, and bis 2-hydroxyethyl terephthalate. This allows the fabric constituting the soft polyvinyl chloride resin composite sheet of the present invention to be a regenerated and recycled type.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene furanoate [chemical 8] fiber is preferably one or more selected from polyethylene furanoate, polypropylene furanoate, polybutylene furanoate, and polytrimethylene furanoate. This makes it possible and easy to depolymerize the fibers of the fabric separated from the soft polyvinyl chloride resin composite sheet that is to be disposed of after use, and makes it possible to obtain a polymerization monomer for regenerating the polyalkylene furanoate [chemical 8] fiber.

In the soft polyvinyl chloride resin composite sheet of the present invention, the polyalkylene furanoate [Chemical 8] fiber is a regenerated fiber obtained from regenerated polyalkylene furanoate by polymerization of a regenerated monomer obtained by depolymerizing polyalkylene furanoate, and it is preferable that the regenerated monomer contains one or more selected from furandicarboxylic acid, dimethyl furandicarboxylate, and bis 2-hydroxyethyl furandicarboxylate. This allows the fabric constituting the soft polyvinyl chloride resin composite sheet of the present invention to be a regenerated and recycled type.

According to the present invention, it is possible to provide a soft polyvinyl chloride resin film and a soft polyvinyl chloride resin composite sheet that contain carbon neutral (recyclable) elements. In particular, the soft polyvinyl chloride resin film is widely useful for agricultural and horticultural vinyl greenhouses, medical clean booths, simple industrial clean booths, partitions for public facilities, protective covering materials for automobiles and railway cars, protective covering materials for floors and walls, and waterproof covering materials for roofs and ceilings. The soft polyvinyl chloride resin composite sheet is widely useful for large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural protection (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, visual facades, negative pressure medical tents, flexible containers, lift-up sheet shutters, floor sheets, tarpaulins used for partition sheets, etc., and canvas used for truck canopies, open-air waterproof sheets, and roofed tents, as well as mesh sheets used for architectural protection mesh sheets, wind and snow protection nets, anti-glare nets, sun protection facades, etc. Furthermore, the carbon dioxide generated during incineration is carbon neutral (raw materials and products derived from carbon dioxide absorbed by plants are returned to nature as carbon dioxide through combustion, and are then absorbed again by plants, resulting in a cycle that does not substantially increase carbon dioxide levels), and it is expected to contribute to the realization of a low-environmental-load, low-carbon society that can prevent an increase in the amount of carbon dioxide in the global environment. In this invention, regenerative circulation type mainly means carbon neutral (recycling carbon derived from plants and animals).

The soft polyvinyl chloride resin composite sheet of the present invention, which has a carbon-neutral element, can suppress an increase in the amount of carbon dioxide in the global environment, and contributes to the realization of a low-environmental-load, low-carbon society, is a composite sheet in which a resin coating layer containing at least a plasticizer and a polyvinyl chloride resin (not including a copolymer) is laminated on one or more sides of a fabric, and may be any of the following: 1) the resin coating layer has a biomass element, and the fabric does not have a biomass element, 2) the resin coating layer has a biomass element, and the fabric also has a biomass element, or 3) the resin coating layer does not have a biomass element, and the fabric has a biomass element, with 2) being the most preferred. Here, "having a biomass element in the resin coating layer" means that both the plasticizer and the polyvinyl chloride resin contained in the resin coating layer have a biomass element, and "having a biomass element in the fabric" means that the fibers constituting the woven or knitted fabric have a biomass element in the polymer constituting the fibers. That is, the soft vinyl chloride resin composite sheet of the present invention is a fabric having a resin coating layer laminated on one or more sides thereof, the resin coating layer including at least a biomass plasticizer including a plasticizer molecule having a radioactive carbon atom C-14 in a part of its molecular structure, and a biomass vinyl chloride resin (not including a copolymer) including a vinyl chloride unit having a radioactive carbon atom C-14 in a part of its molecular structure, and the biomass plasticizer is at least one selected from a dialkyl phthalate compound , a dialkyl sebacate compound, an alkyl furan dicarboxylate compound, and a polyglycerin fatty acid ester compound. The fabric includes a multifilament yarn made of polyalkylene furanoate fiber (preferably polyethylene furanoate) as a weaving or knitting element, and these fibers are regenerated fibers obtained by polymerization of a regenerated monomer obtained by depolymerization, and furthermore, these fibers are biomass fibers containing a radioactive carbon atom C-14 in a part of their molecular structure . In the present invention, the soft vinyl chloride resin film is a component of the soft vinyl chloride resin composite sheet.

The soft polyvinyl chloride resin film used in the soft polyvinyl chloride resin composite sheet of the present invention contains at least a biomass plasticizer containing a plasticizer molecule having a radioactive carbon atom C-14 in part of its molecular structure, and a biomass polyvinyl chloride resin (not including a copolymer) containing a vinyl chloride unit having a radioactive carbon atom C-14 in part of its molecular structure, and it is particularly preferred that the biomass plasticizer is one or more selected from a dialkyl phthalate compound [Chemical Formula 1], a dialkyl sebacate compound [Chemical Formula 2], an alkyl furan dicarboxylate compound [Chemical Formula 3], and a polyglycerin fatty acid ester compound [Chemical Formula 4]. In the above [Chemical formula 1], n is an integer of 4 to 12, and is synthesized by an esterification reaction between phthalic acid and a C4 to C12 alcohol, and is most preferably a 100% biomass plasticizer (containing C-14) in which both the phthalic acid and the C4 to C12 alcohol are plant-derived substances, but may also be a semi-biomass plasticizer (containing C-14) in which either the phthalic acid or the C4 to C12 alcohol is a plant-derived substance. In the above [Chemical formula 2], n is an integer of 4 to 12, and is synthesized by an esterification reaction between sebacic acid and a C4 to C12 alcohol, and is most preferably a 100% biomass plasticizer (containing C-14) in which both the sebacic acid and the C4 to C12 alcohol are plant-derived substances, but may also be a semi-biomass plasticizer (containing C-14) in which either adipic acid, sebacic acid, or the C4 to C12 alcohol is a plant-derived substance. In the above [Chemical formula 3], n is an integer of 4 to 12, and is synthesized by an esterification reaction between furandicarboxylic acid and a C4 to C12 alcohol, and is most preferably a 100% biomass plasticizer (containing C-14) in which both the furandicarboxylic acid and the C4 to C12 alcohol are plant-derived substances, but may also be a semi-biomass plasticizer (containing C-14) in which either the furandicarboxylic acid or the C4 to C12 alcohol is a plant-derived substance. In the above [Chemical formula 4], n is an integer of 2 to 10, and is synthesized by an esterification reaction between glycerin and a C2 to C10 fatty acid, and is most preferably a 100% biomass plasticizer (containing C-14) in which both the glycerin and the C2 to C10 fatty acid are plant-derived substances, but may also be a semi-biomass plasticizer (containing C-14) in which either the glycerin or the C2 to C10 fatty acid is a plant-derived substance. As a result, even if the soft polyvinyl chloride resin composite sheet of the present invention and waste materials of the composite sheet construction are incinerated, the carbon dioxide generated from them can be counted as carbon neutral (a cycle in which the biomass composite sheet derived from carbon dioxide absorbed by plants returns to nature and is again absorbed by plants), making it possible to become a regenerative and circulating soft polyvinyl chloride resin composite sheet. Here, a plasticizer molecule having C-14 in part of its molecular structure means a plasticizer molecule synthesized from a plant, and the plasticizer molecule having C-14 in a biomass plasticizer is at the same concentration as that contained in nature, about 1.2 x ^10-12 , and does not mean that all plasticizer molecules contained in a biomass plasticizer have C-14.
* Wherein n = 4 to 12
* Wherein n = 4 to 12
* Wherein n = 4 to 12
*In the formula, n = 2 to 10, R is an alkyl group having 2 to 10 carbon atoms.

In the phthalic acid dialkyl ester compound [Chemical formula 1], the plant-derived phthalic acid is, for example, obtained by dehydrating isobutanol produced by fermenting corn sugar to produce isobutylene, and then converting the orthoxylene obtained by dimerization and cyclization through a radical reaction into phthalic acid. In the sebacic acid dialkyl ester compound [Chemical formula 2], the plant-derived sebacic acid is, for example, synthesized from castor oil extracted from castor bean seeds. In the furandicarboxylic acid alkyl ester compound [Chemical formula 3], the plant-derived furandicarboxylic acid is, for example, synthesized by dehydrating fructose (producing an oxygen-containing five-membered ring structure) and oxidizing it. In the polyglycerol fatty acid ester compound [Chemical formula 4], the plant-derived glycerin is obtained, for example, by hydrolysis of triacylglycerol contained in biological fats and oils, or is a by-product obtained during soap production by saponifying biological fats and oils, while the plant-derived fatty acids are, for example, C2-10 saturated or unsaturated fatty acids such as safflower oil, corn oil, soybean oil, olive oil, coconut oil, and palm oil.

Specific examples of dialkyl phthalate compounds [Chemical formula 1] (n = integer from 4 to 12) include dibutyl phthalate (MW 278) and diisobutyl phthalate (MW 278) obtained by reacting phthalic acid with C4 alcohol, dipentyl phthalate (MW 306) obtained by reacting with C5 alcohol, dihexyl phthalate (MW 334) obtained by reacting with C6 alcohol, diheptyl phthalate (MW 362) obtained by reacting with C7 alcohol, and phthalic acid (MW 362) obtained by reacting with C8 alcohol. Di(2-ethylhexyl) (MW 390), dinonyl phthalate (MW 418) and diisononyl phthalate (MW 418) by reaction with C9 alcohol, didecyl phthalate (MW 446) and diisodecyl phthalate (MW 446) by reaction with C10 alcohol, diundecyl phthalate (MW 474) by reaction with C11 alcohol, dilauryl phthalate (MW 502) by reaction with C12 alcohol, etc., can be used in combination. The C4 to C12 alcohols used in the synthesis are also preferably compounds derived from plants, and can be obtained by dimerization and trimerization of biomass alcohols such as biomass ethanol and biomass butanol. The dialkyl phthalate compounds [chemical formula 1] obtained in this way have a biomass content of 100% and can be recycled and recycled.

Specific examples of sebacic acid dialkyl ester compounds [Chemical formula 2] (n = integer from 4 to 12) include dibutyl sebacate (MW 314) and diisobutyl sebacate (MW 314) obtained by reacting sebacic acid with C4 alcohol, dipentyl sebacate (MW 342) obtained by reacting with C5 alcohol, dihexyl sebacate (MW 370) obtained by reacting with C6 alcohol, diheptyl sebacate (MW 398) obtained by reacting with C7 alcohol, and sebacic acid (MW 370) obtained by reacting with C8 alcohol. Sebacate di(2-ethylhexyl) acid (MW 426), dinonyl sebacate (MW 454) and diisononyl sebacate (MW 454) by reaction with C9 alcohol, didecyl sebacate (MW 482) and diisodecyl sebacate (MW 482) by reaction with C10 alcohol, diundecyl sebacate (MW 510) by reaction with C11 alcohol, dilauryl sebacate (MW 538) by reaction with C12 alcohol, and the like, can be used in combination. The C4 to C12 alcohols used in the synthesis are also preferably compounds derived from plants, and can be obtained by dimerization or trimerization of biomass alcohols such as biomass ethanol and biomass butanol. The resulting furan dicarboxylic acid dialkyl ester compounds [chemical formula 2] have a biomass content of 100% and can be recycled.

The furandicarboxylic acid alkyl ester compound [Chemical formula 3] (n = an integer between 4 and 12) is preferably a 2,5-furandicarboxylic acid dialkyl ester compound synthesized by the reaction (esterification) of 2,5-furandicarboxylic acid (containing C-14) with a C4 to C12 alcohol (containing C-14). The coordination of the carboxylic acid in furandicarboxylic acid can be in positions other than 2,5, such as 2,3, 2,4, or 3,4, but 2,5-furandicarboxylic acid is the easiest to synthesize as a biomass compound. Specifically, 2,5-furandicarboxylic acid is reacted with a C4 alcohol to produce dibutyl 2,5-furandicarboxylate (MW 268), and diisobutyl 2,5-furandicarboxylate (MW 268), as well as with a C5 alcohol to produce dipentyl 2,5-furandicarboxylate (MW 296), as well as with a C6 alcohol to produce dihexyl 2,5-furandicarboxylate (MW 324), as well as with a C7 alcohol to produce diheptyl 2,5-furandicarboxylate (MW 352), and as well as with a C8 alcohol to produce di(2-ethylhexyl) 2,5-furandicarboxylate. (MW 380), 2,5-furandicarboxylic acid dinonyl (MW 408) and 2,5-furandicarboxylic acid diisononyl (MW 408) by reaction with C9 alcohol, 2,5-furandicarboxylic acid didecyl (MW 436) and 2,5-furandicarboxylic acid diisodecyl (MW 436) by reaction with C10 alcohol, 2,5-furandicarboxylic acid diundecyl (MW 464) by reaction with C11 alcohol, and 2,5-furandicarboxylic acid dilauryl (MW 492) by reaction with C12 alcohol, and multiple types can be used in combination. The C4 to C12 alcohol used in the synthesis is also preferably a plant-derived compound, and can be obtained by dimerization or trimerization of biomass alcohol such as biomass ethanol and biomass butanol. The resulting furandicarboxylic acid dialkyl ester compound [chemical formula 3] has a biomass content of 100% and can be recycled.

Polyglycerol fatty acid ester compounds [Chemical formula 4] (n = integer between 2 and 10) are esters of polyglycerol (containing C-14) and fatty acids (containing C-14), and are either polyglycerol fatty acid monoester compounds, polyglycerol fatty acid diester compounds, polyglycerol fatty acid triester compounds, or mixtures thereof. Polyglycerol is a polymer obtained by dehydration condensation of glycerol as a monomer, and has an average degree of polymerization of 2 to 10, preferably 2, 4, or 6. In particular, preferred glycerols are those obtained by hydrolysis of triacylglycerol contained in fats and oils of living organisms (animals, fish, insects, etc.), glycerol obtained as a by-product during soap production by saponifying fats and oils (animal and plant-based), glycerol obtained as a by-product during the production of fatty acid methyl esters by transesterification of fats and oils with methanol, and glycerol obtained by converting biomass propylene to epichlorohydrin and hydrolyzing this. Biomass glycerol that does not depend on fossil fuels is preferred. The fatty acid is preferably a saturated or unsaturated fatty acid having 2 to 10 carbon atoms, which may be linear or branched. Specific examples include acetic acid, propionic acid, butyric acid, caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), and the like. From the viewpoint of plant origin, linoleic acid, linolenic acid, oleic acid, lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), and the like contained in safflower oil, corn oil, soybean oil, olive oil, coconut oil, and palm oil are preferred. Examples of polyglycerin fatty acid ester compounds [chemical formula 4] include polyglycerin/caprylic acid mono (or di, or tri) ester, polyglycerin/capric acid mono (or di, or tri) ester, polyglycerin/2-ethylhexanoic acid mono (or di, or tri) ester, polyglycerin/lauric acid mono (or di, or tri) ester, polyglycerin/palmitic acid mono (or di, or tri) ester, etc. (*"/" is used to avoid visual confusion caused by a series of katakana nouns for chemical substances. All are treated the same for polyglycerin fatty acid ester compounds.) Such polyglycerin made from biomass glycerin and polyglycerin fatty acid ester compounds [chemical formula 4] obtained by esterifying biomass fatty acids can be recyclable biomass plasticizers.

The (biomass) plasticizers of the above-mentioned [Chemical formula 1] to [Chemical formula 4] are preferably biomass plasticizers containing plasticizer molecules having C-14 as part of their molecular structure. C-14, an isotope of C-12, is a radioactive carbon atom with a mass number of 14, which is formed by the action of cosmic rays from the sun and a half-life of 5,370 years due to beta decay, and is always present in nature (especially animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 , and cannot be contained in fossil fuels that are already hundreds of millions of years old. Therefore, the above-mentioned plasticizers of the above-mentioned [Chemical formula 1] to [Chemical formula 4] in which C-14 is detected at a concentration of 1.2 x ^10-12 are proof that the biomass is mainly derived from animals and plants. Here, the plasticizer molecule having C-14 as part of its molecular structure does not mean that all plasticizer molecules have C-14.

On the other hand, the vinyl chloride resin on which the (biomass) plasticizers of [Chemical formula 1] to [Chemical formula 4] act is a biomass vinyl chloride resin containing a vinyl chloride unit having C-14. Examples of vinyl chloride resins include homopolymers of vinyl chloride monomers (emulsion polymerization type or suspension polymerization type with a degree of polymerization of 700 to 3800), crosslinked vinyl chloride resins, and chlorinated vinyl chloride resins . The vinyl chloride monomers generally used are those obtained by the direct chlorination method, in which ethylene obtained by pyrolyzing naphtha is reacted with chlorine obtained by electrolyzing salt to produce ethylene dichloride, and then pyrolyzing the ethylene dichloride, and those obtained by the oxychlorination method, in which ethylene obtained by pyrolyzing naphtha is reacted with hydrogen chloride, a by-product of the direct chlorination method, in the presence of oxygen to produce ethylene dichloride, and then pyrolyzing the ethylene dichloride. However, the vinyl chloride resin used in the present invention is preferably a biomass vinyl chloride resin (containing C-14) polymerized using vinyl chloride monomer (containing C-14) obtained by pyrolyzing ethylene dichloride (containing C-14) derived from biomass ethylene (containing C-14) obtained by dehydrating biomass ethanol (containing C-14) obtained by fermenting molasses from sugarcane (containing C-14). Here, the biomass vinyl chloride resin containing vinyl chloride units having C-14 in part of its molecular structure means a vinyl chloride resin synthesized from a plant (sugarcane), and the amount of C-14 in the vinyl chloride resin is about the same as the amount of C-14 contained in nature (about 1.2 x ^10-12) , and does not necessarily mean that all polymer chains contained in the vinyl chloride resin have C-14. By blending 30 to 100 parts by mass, particularly 50 to 80 parts by mass, of the (biomass) plasticizer of the above-mentioned [Chemical formula 1] to [Chemical formula 4] with 100 parts by mass of this biomass vinyl chloride resin, a soft vinyl chloride resin film having a carbon neutral element and capable of suppressing an increase in the amount of carbon dioxide in the global environment, and capable of contributing to the realization of a low-environmental-loading, low-carbon society, can be obtained. In addition, in the case where the biomass degree is particularly arbitrary, a plasticizer derived from a fossil fuel, such as a phthalate ester, an isophthalate ester, a terephthalate ester, a cyclohexane dicarboxylate ester, a cyclohexene dicarboxylate ester, an adipic acid, a chlorinated paraffin, a polyester, an ethylene-vinyl acetate-carbon monoxide terpolymer resin, or an ethylene-(meth)acrylic acid ester-carbon monoxide terpolymer resin, may be used in combination in an amount of up to 50% by mass based on the total amount of plasticizer. In particular, epoxidized soybean oil and epoxidized linseed oil are suitable for use in combination with a biomass plasticizer because the soybean oil and linseed oil portions of their chemical structures are derived from biomass.

The soft polyvinyl chloride resin film of the present invention, that is, a soft polyvinyl chloride resin film that has a carbon neutral element, can suppress an increase in the amount of carbon dioxide in the global environment, and can contribute to the realization of a low-environmental-load, low-carbon society, contains the above-mentioned (biomass) plasticizer and/or (biomass) polyvinyl chloride resin, and in addition, contains stabilizers such as calcium zinc complexes, barium zinc complexes, organotin laurates, organotin mercaptites, and epoxy systems, and is molded from a soft polyvinyl chloride resin compound that optionally contains pigments, flame retardants, fillers, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, crosslinking agents, and the like, as necessary. An example of the film molding is a mode in which the soft polyvinyl chloride resin compound is calender rolled or T-die extrusion molded to a thickness of 0.1 to 1 mm. Similarly, the soft polyvinyl chloride resin composite sheet of the present invention has a resin coating layer containing at least a biomass plasticizer containing a plasticizer molecule having C-14 in part of its molecular structure and/or a biomass polyvinyl chloride resin containing a vinyl chloride unit having C-14 in part of its molecular structure laminated on one or more sides of a fabric, and is in the form of: 1) a tarpaulin having a thickness of 0.4 to 1.5 mm, which is formed by laminating a soft polyvinyl chloride resin film on at least one side of a fabric substrate; 2) a canvas having a thickness of 0.3 to 1 mm, which is formed by using a fabric substrate as a substrate and forming soft polyvinyl chloride resin-impregnated coating layers on both sides of the substrate; or 3) a mesh sheet having a thickness of 0.3 to 1.5 mm, which is formed by using a coarse fabric substrate as a substrate and forming a soft polyvinyl chloride resin-impregnated coating layer on the entire exposed surface of the coarse fabric, and the soft polyvinyl chloride resin film for the tarpaulin is the same as the above-mentioned film. The soft vinyl chloride resin impregnated coating layer for canvas and mesh sheets is, for example, a soft vinyl chloride resin paste composition that mainly contains 30 to 100 parts by weight of plasticizer, 100 parts by weight of paste vinyl chloride resin (fine particles) by emulsion polymerization, and other stabilizers such as calcium zinc complex, barium zinc complex, organotin laurate, organotin mercaptite, and epoxy stabilizers, and optionally uses pigments, flame retardants, fillers, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, crosslinking agents, etc. as necessary. This paste composition is coated on fabric, or fabric is dipped in a liquid bath of the paste composition, and the resulting film is gelled by heat treatment.

The weaving and knitting elements of the fabric used in the soft polyvinyl chloride resin composite sheet of the present invention include multifilament yarns made of polyalkylene phthalate [Chemical 5] fibers or polyalkylene furanoate [Chemical 6] fibers, and are one type selected from warp/weft, warp/upper right 30-60° bias yarn/upper left 30-60° bias yarn, and warp/weft/upper right 30-60° bias yarn/upper left 30-60° bias yarn, where "warp/weft" means a biaxial fabric, "warp/upper right 30-60° bias yarn/upper left 30-60° bias yarn" means a triaxial fabric, and "warp/weft/upper right 30-60° bias yarn/upper left 30-60° bias yarn" means a quadriaxial fabric. In particular, by using triaxial and quadriaxial woven fabrics as the base material, the resulting soft polyvinyl chloride resin composite sheet has extremely excellent dimensional stability, breaking strength, penetration resistance, and tear resistance. Therefore, tarpaulins and canvas in particular can be used not only for tent structures and the like, but also for special purposes such as flexible security shutters, protective clothing and protective covers for riot police and the Self-Defense Forces, protection from flying debris at blasting construction sites, and equipment to catch falling objects at work sites. Specifically, the polyalkylene phthalate [Chemical Formula 5] fiber is one or more selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, and in particular is a regenerated fiber obtained from a regenerated polyalkylene phthalate obtained by polymerizing a regenerated monomer obtained by depolymerizing a polyalkylene phthalate, and the regenerated monomer may include one or more selected from terephthalic acid, dimethyl terephthalate, and bis 2-hydroxyethyl terephthalate. Furthermore, the regenerated polyalkylene phthalate obtained is preferably a biomass fiber containing a radioactive carbon atom C-14 as part of its molecular structure, as a sustainable circulatory material. Specifically, the polyalkylene furanoate [Chemical formula 6] fiber is one or more selected from polyethylene furanoate, polypropylene furanoate, polybutylene furanoate, and polytrimethylene furanoate, and in particular is a regenerated fiber obtained from a regenerated polyalkylene furanoate by polymerization of a regenerated monomer obtained by depolymerizing polyalkylene furanoate, and the regenerated monomer may include one or more selected from furandicarboxylic acid, dimethyl furandicarboxylate, and bis 2-hydroxyethyl furandicarboxylate, and the regenerated polyalkylene furanoate is preferably a biomass fiber containing C-14 as part of its molecular structure. In [Chemical formula 5] and [Chemical formula 6], "-( _CH2 ) _n- " represents an alkylene group, and n is an integer of 2 to 10, specifically ethylene, propylene, butylene, hexylene, heptylene, octylene, dodecylene, etc., and n is preferably 2, 3, or 4. The degree of polymerization m is in the range of about 300 to 1,000, and the molecular weight is in the range of 80,000 to 300,000.

Polyethylene terephthalate, which is preferred as polyalkylene phthalate [Chemical formula 5] fiber, is obtained by polycondensation of dimethyl terephthalate or terephthalic acid with ethylene glycol. In polymer synthesis using dimethyl terephthalate as a raw material, a catalyst is added to dimethyl terephthalate and ethylene glycol to carry out an ester exchange reaction, and the resulting reaction product consisting of bis 2-hydroxyethyl terephthalate and oligomers with a polymerization degree of about 4 or less is polycondensed to synthesize polyethylene terephthalate. On the other hand, in a direct polymerization method using terephthalic acid as a raw material, an esterification reaction is carried out between terephthalic acid and ethylene glycol, and the resulting oligomers with an average polymerization degree of 9 to 10 containing bis 2-hydroxyethyl terephthalate are polycondensed to synthesize polyethylene terephthalate. By depolymerizing the polyalkylene terephthalate [Chemical formula 5] obtained by these syntheses, individual monomers (polyhydric alcohol, polyvalent carboxylic acid) can be recovered. Here, the terephthalic acid is preferably a plant-derived terephthalic acid obtained by dehydrating isobutanol produced by fermenting corn sugar to produce isobutylene, and then converting the resulting paraxylene into terephthalic acid through dimerization and cyclization by radical reaction, and dimethyl terephthalate and bis 2-hydroxyethyl terephthalate are derived from this biomass terephthalic acid.The polyalkylene phthalate [Chemical Formula 5] fiber derived from such a plant is preferably a biomass fiber containing C-14 in a part of the molecular structure of the polyalkylene phthalate. C-14 is a radioactive carbon atom with a mass number of 14 and a half-life of 5,370 years, which is formed by the conversion of nitrogen by the action of cosmic rays from the sun, and it always exists in nature (especially in animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 , and cannot be contained in fossil fuels that are hundreds of millions of years old, so polyalkylene phthalate [Chemical formula 5] fibers in which C-14 is detected at a concentration of 1.2 x ^10-12 are proof that the biomass is mainly made of animals and plants. In addition, ethylene glycol is preferably ethylene glycol derived from plants, which is obtained by dehydrating bioethanol produced by fermenting sugarcane molasses to produce ethylene, which is then oxidized to produce ethylene oxide, and then hydrolyzed. Polypropylene terephthalate is synthesized by a synthesis method in which ethylene glycol is replaced with propylene glycol in the above-mentioned polyethylene terephthalate synthesis process. Propylene glycol is obtained by dehydrating biomass propanol produced by fermenting sugarcane molasses to produce biomass propylene, which is then oxidized to produce biomass propylene oxide, which is then further hydrolyzed to produce plant-derived propylene glycol. Similarly, polybutylene terephthalate is synthesized by a synthesis method in which ethylene glycol is replaced with butylene glycol in the above-mentioned polyethylene furanoate synthesis process. Similarly, polytrimethylene terephthalate is synthesized by a synthesis method in which ethylene glycol is replaced with trimethylene glycol in the above-mentioned polyethylene terephthalate synthesis process. Trimethylene glycol is 1,3-propanediol produced by fermentation using palm oil-derived glycerin as a raw material. Polyalkylene terephthalate (Chemical Formula 5) fibers are also intended to include copolymers obtained by substituting up to 50% by weight of the terephthalic acid used in the above synthesis process with isophthalic acid (a positional isomer of terephthalic acid).

Polyethylene furanoate, which is preferred as polyalkylene furanoate [Chemical formula 6] fiber, can be obtained by polycondensation of 2,5-dimethyl furandicarboxylate or 2,5-furandicarboxylic acid with ethylene glycol. In polymer synthesis using 2,5-dimethyl furandicarboxylate as a raw material, a catalyst is added to 2,5-dimethyl furandicarboxylate and ethylene glycol to carry out an ester exchange reaction, and the resulting reaction product consisting of bis-2-hydroxyethyl furandicarboxylate and an oligomer having a polymerization degree of about 4 or less can be polycondensed to synthesize polyethylene furanoate. On the other hand, in a direct polymerization method using 2,5-furandicarboxylic acid as a raw material, an esterification reaction of 2,5-furandicarboxylic acid and ethylene glycol is carried out, and the resulting oligomer having an average polymerization degree of 9 to 10 containing bis-2-hydroxyethyl furandicarboxylate can be polycondensed to synthesize polyethylene furanoate. By depolymerizing the polyalkylene furanoate [Chemical formula 6] obtained by these syntheses, individual monomers (polyhydric alcohol, polyvalent carboxylic acid) can be recovered. Here, 2,5-furandicarboxylic acid is preferably a biomass compound synthesized by dehydrating fructose (producing an oxygen-containing 5-membered ring structure) and oxidizing it, and 2,5-dimethylfurandicarboxylate and bis-2-hydroxyethylfurandicarboxylate are derived from this biomass 2,5-furandicarboxylic acid. Ethylene glycol is preferably a diol obtained by dehydrating bioethanol produced by fermenting sugarcane molasses to produce ethylene, oxidizing this to produce ethylene oxide, and further hydrolyzing the ethylene glycol. Such plant-derived polyalkylene furanoate [Chemical formula 6] fibers are preferably biomass fibers containing C-14 in part of the molecular structure of the polyalkylene furanoate. C-14 is a radioactive carbon atom with a mass number of 14 and a half-life of 5,370 years, which is formed by the conversion of nitrogen by the action of cosmic rays from the sun, and is always present in nature (especially in animals and plants) in an equilibrium state of C-14C/C-12 = 1.2 x ^10-12 , and cannot be contained in fossil fuels that are hundreds of millions of years old, so polyalkylene furanoate [Chemical formula 6] fibers in which C-14 is detected at a concentration of 1.2 x ^10-12 are proof that the biomass is mainly derived from animals and plants. Polypropylene furanoate is synthesized by a synthesis method in which ethylene glycol is replaced with propylene glycol in the above-mentioned polyethylene furanoate synthesis process, and propylene glycol is a plant-derived propylene glycol obtained by dehydrating biomass propanol produced by fermenting sugarcane waste molasses to produce biomass propylene, which is then oxidized to produce biomass propylene oxide, which is then hydrolyzed.
Similarly, polybutylene furanoate is synthesized by the above-mentioned polyethylene furanoate synthesis process, but replacing ethylene glycol with butylene glycol, and similarly, polytrimethylene furanoate is synthesized by the above-mentioned polyethylene furanoate synthesis process, but replacing ethylene glycol with trimethylene glycol. Polyalkylene furanoate [Chemical formula 6] fibers also include copolymers obtained by replacing up to 50% by mass of the 2,5-furandicarboxylic acid used in the above synthesis process with 2,4-furandicarboxylic acid or 3,4-furandicarboxylic acid (a positional isomer of furandicarboxylic acid).

The polyalkylene phthalate [Chemical Formula 5] fiber is particularly preferably a fiber melt-spun from a polyalkylene phthalate resin that satisfies at least one of the following conditions: density 1.35-1.37 g/cm ³ , melting point 250-270° C., and strength (E-modulus) 2.1-2.2 GPa. On the other hand, the polyalkylene furanoate [Chemical Formula 6] fiber is particularly preferably a fiber melt-spun from a polyalkylene furanoate resin that satisfies at least one of the following conditions: density 1.41-1.45 g/cm ³ , melting point 210-230° C., and strength (E-modulus) 3.1-3.3 GPa. The long fiber multifilament yarn constituting the woven fabric for tarpaulin (plain weave, basket weave, satin weave, twill weave, raschel weave, etc.) has a fineness of 250 to 2000 denier (278 to 2222 dtex), for example, the number of filaments for 278 dtex is 100 to 200, and for example, the number of filaments for 1111 dtex is about 400 to 800, and may be untwisted (with an elliptical or flat cross section) or twisted. Furthermore, the staple fiber spun (spun) multifilament yarns constituting canvas fabrics (plain weave, basket weave, satin weave, twill weave, etc.) have a cotton count of 10 (591 dtex) to 60 (97 dtex), particularly 10 (591 dtex), 14 (422 dtex), 16 (370 dtex), 20 (295 dtex), 24 (246 dtex), 30 (197 dtex), etc., and these single yarns, double yarns (single-twisted yarns), and twisted yarns (multi-twisted yarns) made of two or more single yarns can be used, as well as bulky processed yarns (taslan processed yarns, woolly processed yarns, etc.), and covered yarns (core-sheath composite yarns in which the same or different staple fibers are wrapped around the outer periphery of a multifilament yarn). Furthermore, the long-fiber multifilament yarn constituting the coarse woven fabric for the mesh sheet (plain weave fabric, imitation gauze fabric, stacked net, etc.) may have a fineness similar to that of a tarpaulin, and may in particular be a long-fiber multifilament yarn whose entirety is coated with resin (coated yarn).

The fabric used in the soft polyvinyl chloride resin composite sheet of the present invention is 1) a woven fabric (such as a plain weave, a basket weave, a satin weave, a twill weave, or a raschel weave) with a void ratio of about 6 to 25%, woven with long-fiber multifilament yarn, and having a basis weight of 100 to 500 g/m ^2. A tarpaulin using such a woven fabric as a substrate can be obtained by hot-press laminating on both sides of the substrate a film or sheet having a thickness of 0.1 to 1 mm, which is formed by calendar rolling, or T-die extrusion molding of a soft polyvinyl chloride resin composition, and has the characteristic that the films or sheets arranged on the front and back of the woven fabric are melted and integrated with each other, with a void ratio of 6 to 25% (voids generated by entanglement of axial yarns) interposed therebetween, so that the soft polyvinyl chloride resin layers on the front and back are firmly bonded to the woven fabric. Tarpaulins with a thickness of 0.4 to 1.5 mm and a mass of 500 to 2000 g/m are suitable for use as raw fabrics for membrane structures such as large tent structures (indoor sports facilities, pavilions, and event halls), circus tents, tent warehouses, and membrane roofs (membrane ceilings) in architectural spaces, and as raw fabrics for flexible containers. 2) Spun fabrics with a void ratio of about 0 to 10% (plain weave, basket weave, satin weave, twill weave, etc.) and a basis weight of 100 to 500 g/ ^m2 woven and knitted with short fiber spun (spun) multifilament yarns. Canvases using such spun fabrics as a substrate can be obtained by dip-coating or coating both sides of the substrate with a liquid soft vinyl chloride resin composition, drying the coating to form a film of 0.05 to 0.3 mm, and it is preferable that a portion of the coating is impregnated into the spun fabric. A canvas having a thickness of 0.4 to 1.0 mm and a mass of 400 to 1500 g/m is suitable for use as a raw material for truck hoods, tent warehouses, etc. 3) and a coarse weave fabric (plain weave, imitation weave, stacked net, etc.) for mesh sheets with a void ratio of about 10 to 70%, a coarse weave fabric with a basis weight of 30 to 200 g/ ^m2 woven and knitted with long-fiber multifilament yarns. A mesh sheet using such a coarse weave fabric as a base material can be obtained by dip-coating the entire base material with a liquid soft vinyl chloride resin composition, drying the coating to form a film of 0.05 to 0.3 mm, and it is preferable that a part of the coating is impregnated into the coarse weave fabric. Also, a mesh sheet obtained by weaving and knitting a long-fiber multifilament yarn (coated yarn) coated with a liquid soft vinyl chloride resin composition over the entire yarn, or a stacked fused mesh of coated yarns. A mesh sheet having a thickness of 0.4 to 1.0 mm and a mass of 100 to 500 g/m is suitable for use as a raw material for architectural protection mesh sheets, wind and snow protection nets, anti-glare nets, facade meshes, etc. The void ratio of fabrics, coarse woven fabrics, and mesh sheets is the sum of gaps caused by the entanglement and intersection of axial yarns such as warp yarns/weft yarns, warp yarns/upper right 30-60° bias yarns/upper left 30-60° bias yarns, and warp yarns/weft yarns/upper right 30-60° bias yarns/upper left 30-60° bias yarns, and can be calculated by subtracting the area of the yarns in a unit area of the fabric from 100 as a percentage. Specifically, the average yarn width can be calculated, and the void ratio can be calculated as a conversion value based on the void ratio per square inch from the relationship between the number of yarns per inch.

The polyalkylene phthalate [Chemical formula 5] fiber is a regenerated fiber obtained from a regenerated polyalkylene phthalate by polymerization of a regenerated monomer obtained by depolymerizing a polyalkylene phthalate, the regenerated monomer containing at least one selected from terephthalic acid, dimethyl terephthalate, and bis-2-hydroxyethyl terephthalate, and a polyhydric alcohol (ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol), and the polyalkylene phthalate [Chemical formula 5] fiber before and after regeneration is preferably a biomass fiber containing radioactive carbon atom C-14 in a part of the molecular structure of the polyalkylene phthalate. That is, the C-14 is contained at a concentration of 1.2×10 −12 in a part of monomers such as terephthalic acid, dimethyl terephthalate, and bis-2-hydroxyethyl terephthalate, and/or ^polyhydric alcohol (ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol). The polyalkylene furanoate [Chemical formula 6] fiber is preferably a regenerated fiber obtained from a regenerated polyalkylene furanoate by polymerization of a regenerated monomer obtained by depolymerizing polyalkylene furanoate, the regenerated monomer containing at least one selected from furandicarboxylic acid, dimethyl furandicarboxylate, and bis 2-hydroxyethyl furandicarboxylate, and a polyhydric alcohol (ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol), and the polyalkylene furanoate [Chemical formula 6] fiber before and after regeneration is preferably a biomass fiber containing radioactive carbon atom C-14 in a part of the molecular structure of the polyalkylene furanoate. That is, the C-14 is contained at a concentration of 1.2×10 ⁻¹² in a monomer such as furandicarboxylic acid, dimethyl furandicarboxylate, or bis 2-hydroxyethyl furandicarboxylate, and/or a part of the polyhydric alcohol (ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol). The depolymerization of polyalkylene phthalate [Chemical formula 5] fibers and polyalkylene furanoate [Chemical formula 6] fibers is preferably carried out by nucleophilic substitution reaction under basic conditions, such as the glycolysis method in which polyhydric alcohol (such as ethylene glycol) is used as a solvent for depolymerization, followed by ester exchange reaction with alcohol to obtain the above-mentioned regenerated monomer, or the hydrolysis method by hydrolysis, in which the nucleophilic reagent is alcohol or water, and the oxygen atom of the hydroxyl group attacks the carbon of the ester carbonyl group to irreversibly separate the alkoxyl group from the polymer main chain. In order to proceed with this depolymerization under mild heating conditions, catalysts such as alkali metal carbonates, alkali metal acetates, alkali metal oxides, alkali metal alkoxides, alkali metal hydroxides, alkaline earth metal carbonates, alkaline earth metal acetates, alkaline earth metal oxides, alkaline earth metal alkoxides, and alkaline earth metal hydroxides are required. The above-mentioned regenerated monomer is obtained by removing impurities such as metal ions, colorants, and dirt from the low molecular weight obtained by depolymerization, and then purifying it by molecular distillation.

On the surface of the soft vinyl chloride resin film and the soft vinyl chloride resin composite sheet of the present invention, if necessary, an anti-stain layer consisting of a coating film such as an acrylic resin, a urethane resin, an acrylic/silicon copolymer resin, a fluorine copolymer resin, a blend of an acrylic resin and a fluorine copolymer resin, a urethane/silicon graft copolymer resin, and a urethane/fluorine graft copolymer resin may be formed on one or more sides of the surface. In addition, a multi-layered fluorine resin film such as a fluorine resin layer/aminoethylated acrylic resin epoxy cured product adhesive layer, a fluorine resin layer/acrylic resin adhesive layer, a fluorine resin layer/acrylic resin layer/aminoethylated acrylic resin epoxy cured product adhesive layer, and a fluorine resin layer/acrylic resin layer/vinyl chloride resin adhesive layer can be laminated as an anti-stain layer. By applying these anti-stain layers to membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and monuments, the durability during outdoor use is dramatically improved. In particular, as the anti-soiling layer for the soft polyvinyl chloride resin film and the soft polyvinyl chloride resin composite sheet of the present invention, an inorganic anti-soiling thin film layer is preferred in which nanoparticles made of an inorganic colloidal substance with a primary particle diameter of 3 nm to 150 nm are supported on a binder component containing a hydrolysis condensate of a silane coupling agent. The inorganic colloidal substance is preferably a metal oxide such as photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic 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 oxide (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol.

The present invention will be further described with reference to the following examples and comparative examples, but the present invention is not limited to the scope of these examples.
*Hereinafter, Examples 1 to 4, 6, 7, and 9 to 16 shall be read as Reference Examples 1 to 4, 6, 7, and 9 to 16, respectively, and Reference Example 1 in paragraph [0060] shall be read as Reference Example 17.
Biomass content (proof of biomass origin)
The concentration of the radioactive carbon atom C-14 contained in the total carbon atoms that make up the polymer (the detection ratio of C-14 to C-12 in the polymer) is determined using an accelerator mass spectrometry, and the detection ratio of the radioactive carbon atom C-14 proves the bio-based content.
The amount of carbon isotope C-14 in the atmosphere is almost constant due to the equilibrium between the production of C-14 by cosmic rays and radioactive decay (half-life of about 5,730 years). Atmospheric C-14 accumulates in plants through photosynthesis, and is then distributed to animals through the food chain, so the C-14 concentration (detection ratio of C-14 to C-12) of all living organisms on Earth is almost constant. On the other hand, since petroleum is a biological substance from 100 to 200 million years ago, the "C-14" concentration in petroleum is considered to be virtually zero because it has long since passed its half-life, so biomass-derived products contain a certain concentration of C-14, while petroleum-derived products do not contain C-14. Therefore, measuring the C-14 concentration (detection ratio of C-14 to C-12) can prove that a product is biomass-derived.

[Example 1]
<Tarpaulin made from woven fabric (1)>
The fabric (1) used is a 1000d (1111 dtex) multifilament yarn (192 filaments) made of polyethylene terephthalate (PEF) fiber melt-spun from polyethylene terephthalate resin (density 1.36 g/cm ³ , melting point 250-270°C, glass transition temperature Tg 76°C, strength: E-modulus 2.1-2.2 GPa), with an S-twist of 200 T/m for the warp and weft groups, and a weaving density of 19 warp threads/inch x 20 weft threads/inch. The fabric (1) has a mass of 190 g/m ² and a void ratio of 10%.
*Polyethylene terephthalate (PET) fibers are melt-spun from polyethylene terephthalate (PET) resin obtained by the esterification reaction of terephthalic acid and ethylene glycol. Both polymerization monomers are biomass-derived compounds. Ethylene glycol is obtained by dehydrating biomass ethanol produced by fermenting sugarcane molasses to produce biomass ethylene, which is then oxidized to produce biomass ethylene oxide, which is then hydrolyzed to produce plant-derived ethylene glycol. Terephthalic acid is obtained by dehydrating isobutanol produced by fermenting corn sugar to produce isobutylene, which is then dimerized and cyclized by a radical reaction to produce paraxylene, which is then converted to terephthalic acid. The resulting polyethylene terephthalate (PET) fibers are 100% biomass, and the fabric (1) made from this fiber yarn as a weaving or knitting element is also 100% biomass.
<Production of tarpaulin>
A 0.16 mm thick film is formed on both sides of the fabric (1) by calendaring the soft vinyl chloride resin compound of the following [Formulation 1] under heat conditions of 165°C to 180°C, and then laminated in a softened state under heat roll conditions of 170°C using a laminator to obtain a tarpaulin-like soft vinyl chloride resin composite sheet (1) having a thickness of 0.75 mm and a mass of 915 g/ ^m2 . The biomass ratio of this soft vinyl chloride resin composite sheet (1) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and UV absorbers).
*The molded film having a thickness of 0.16 mm made from [Blend 1] can be used separately as the soft polyvinyl chloride resin film of the present invention.
[Formula 1] Flexible polyvinyl chloride resin compound composition Polyvinyl chloride resin (polymerization degree 1,300) by suspension polymerization 100 parts by weight * Biomass polymer by radical polymerization of vinyl chloride monomer chlorinated from biomass ethylene obtained by dehydrating biomass ethanol obtained by fermenting sugarcane waste molasses Diisononyl phthalate (plasticizer) as phthalate dialkyl ester compound [chemical formula 1]
*Synthesized by the reaction (esterification) of phthalic acid with biomass isononyl alcohol. Phthalic acid is a 100% biomass compound that is made by dehydrating isobutanol produced by fermenting corn sugar to produce isobutylene, which is then dimerized and cyclized by a radical reaction to produce orthoxylene, which is then converted to phthalic acid. Epoxidized soybean oil (partial biomass plasticizer) 10 parts by weight Antimony trioxide (flame retardant) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Rutile titanium dioxide (white pigment) 5 parts by weight Benzotriazole-based compound (ultraviolet absorbing agent) 0.3 parts by weight

[Example 2]
By changing the fabric (1) of Example 1 to fabric (2) and further changing the phthalic acid dialkyl ester compound [chemical formula 1] in [blending 1] to 60 parts by mass of diisononyl phthalate (plasticizer) in [blending 2] as the sebacic acid dialkyl ester compound [chemical formula 2] in [blending 1], a tarpaulin-type soft vinyl chloride resin composite sheet (2) having a thickness of 0.75 mm and a mass of 915 g/ ^m2 is obtained. The biomass degree of this soft vinyl chloride resin composite sheet (2) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and UV absorbers).
*The molded film having a thickness of 0.16 mm made from [Blend 2] can be used separately as the soft polyvinyl chloride resin film of the present invention.
<Fabric (2)>
A fabric (2) is used, which has a mass of 190 g/m2 and a void ratio of 10%, and is made of 1000 ^d (1111 dtex) multifilament yarn (192 filaments) made of polypropylene terephthalate (PPT) fiber melt-spun from polypropylene terephthalate resin, with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp yarns/inch × 20 weft yarns/inch.
*Polypropylene terephthalate (PPT) fiber is melt-spun from polypropylene terephthalate (PPT) resin obtained by the esterification reaction of terephthalic acid and propylene glycol. Both polymerization monomers are biomass-derived compounds. Propylene glycol is derived from plants, and is made by dehydrating biomass propanol to biomass propylene, which is then oxidized to biomass propylene oxide, which is then hydrolyzed. Terephthalic acid is derived from plants, and is made by dehydrating isobutanol produced by fermenting corn sugar to isobutylene, which is then dimerized and cyclized by radical reaction to obtain paraxylene, which is then converted to terephthalic acid. The resulting polypropylene terephthalate (PPT) fiber has a biomass content of 100%, and the fabric (2) made from this fiber yarn as a weaving or knitting element also has a biomass content of 100%.
*Diisononyl sebacate (plasticizer) is synthesized by reacting (esterifying) sebacic acid with biomass isononyl alcohol. Sebacic acid is a 100% biomass compound synthesized from castor oil extracted from castor beans.

[Example 3]
By using the same method as in Example 1 except that the fabric (1) in Example 1 is changed to fabric (3) and further that 60 parts by mass of diisononyl phthalate (plasticizer) as the dialkyl phthalate compound [chemical formula 1] in [blending 1] is changed to 60 parts by mass of diisononyl furandicarboxylate (plasticizer) as the alkyl furandicarboxylate compound [chemical formula 3] in [blending 3] is used, a soft vinyl chloride resin composite sheet (3) in the form of a tarpaulin having a thickness of 0.75 mm and a mass of 915 g/ ^m2 is obtained. The biomass degree of this soft vinyl chloride resin composite sheet (3) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*The molded film having a thickness of 0.16 mm made from [Blend 3] can be used separately as the soft polyvinyl chloride resin film of the present invention.
<Fabric (3)>
A fabric (3) is used, which has a mass of 190 g/m2 and a void ratio of 10%, and is made of 1000 ^d (1111 dtex) multifilament yarn (192 filaments) made of polybutylene terephthalate (PBT) fiber melt-spun from polybutylene terephthalate resin, with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp yarns/inch × 20 weft yarns/inch.
*Polybutylene terephthalate (PBT) fiber is melt-spun from polybutylene terephthalate (PBT) resin obtained by the esterification reaction of terephthalic acid and butylene glycol. Both polymerization monomers are biomass-derived compounds. Butylene glycol is derived from plants, which are made by dehydrating biomass butanol to produce biomass butylene, which is then oxidized to produce biomass butylene oxide, which is then hydrolyzed. Terephthalic acid is derived from plants, which are made by dehydrating isobutanol produced by fermenting corn sugar to produce isobutylene, which is then dimerized and cyclized by radical reaction to produce paraxylene, which is then converted to terephthalic acid. The resulting polypropylene terephthalate (PBT) fiber has a biomass content of 100%, and the fabric (3) made from this fiber yarn as a weaving or knitting element also has a biomass content of 100%.
*Diisononyl furandicarboxylate (plasticizer) is synthesized by reacting (esterifying) 2,5-furandicarboxylic acid with biomass isononyl alcohol. 2,5-Furandicarboxylic acid is a 100% biomass compound synthesized by the dehydration (production of an oxygen-containing five-membered ring structure) and oxidation of fructose.

[Example 4]
By changing the fabric (1) of Example 1 to fabric (4) and further changing 60 parts by mass of diisononyl phthalate (plasticizer) as the dialkyl phthalate compound [chemical formula 1] in [blending 1] to 60 parts by mass of polyglycerin/myristic acid triester (plasticizer) as the polyglycerin fatty acid ester compound [chemical formula 4] in [blending 4], the same procedure as in Example 1 is followed, and a soft vinyl chloride resin composite sheet (4) in the form of a tarpaulin having a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass degree of this soft vinyl chloride resin composite sheet (4) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*The molded film having a thickness of 0.16 mm made from [Blend 4] can be used separately as the soft polyvinyl chloride resin film of the present invention.
<Fabric (4)>
A fabric (4) is used, which has a mass of 190 g/m2 and a void ratio of 10%, and is made of 1000 ^d (1111 dtex) multifilament yarn (192 filaments) made of polytrimethylene terephthalate (PtMT) fiber melt-spun from polytrimethylene terephthalate resin, with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp yarns/inch × 20 weft yarns/inch.
*Polytrimethylene terephthalate (PtMT) fiber is melt-spun from polytrimethylene terephthalate (PtMT) resin obtained by the esterification reaction of terephthalic acid and trimethylene glycol. Both polymerization monomers are biomass-derived compounds. Trimethylene glycol is derived from plants, which are made by dehydrating biomass 1,3-propanol to make biomass 1,3-propane, which is then oxidized to make biomass trimethylene oxide, which is then hydrolyzed. Terephthalic acid is derived from plants, which are made by dehydrating isobutanol produced by fermenting corn sugar to make isobutylene, which is then dimerized and cyclized by radical reaction to obtain paraxylene, which is then converted to terephthalic acid. The resulting polytrimethylene terephthalate (PtMT) fiber has a biomass content of 100%, and the fabric (4) made from this fiber yarn as a weaving or knitting element also has a biomass content of 100%.
*Polyglycerin/myristic acid triester (plasticizer) is a 100% biomass triester made by esterifying polyglycerin and myristic acid. Polyglycerin is a biomass-derived glycerin dimer (average degree of polymerization n = 2) obtained by isolating glycerin, a by-product during the production of fatty acid methyl esters through the transesterification reaction of fats and oils with methanol, and then dehydrating and condensing this. Myristic acid ( _CH3 ( _CH2 ) _12COOH ) is a 100% biomass-derived compound of plant origin refined from palm oil.

[Example 5]
By following the same procedure as in Example 1 except that the fabric (1) in Example 1 is changed to the fabric (5), a tarpaulin-type soft polyvinyl chloride resin composite sheet (5) having a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. The biomass ratio of this soft polyvinyl chloride resin composite sheet (5) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (5)>
A fabric (5) is used, which has a mass of 200 g/m ² and a void ratio of 10%, and is made of 1000 d (1111 dtex) multifilament yarn (192 filaments) made of polyethylene phenolate (PEF) fiber melt-spun from polyethylene phenolate resin (density 1.43 g/cm 3 , melting point 210-230°C, glass transition temperature Tg 88°C, strength: E-modulus 3.1-3.3 GPa), with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp yarns/ ^inch x 20 weft yarns/inch.
*Polyethylene phenolate (PEF) fibers are melt-spun from polyethylene phenolate (PEF) resin obtained by the esterification reaction of 2,5-furandicarboxylic acid and ethylene glycol. Both polymerization monomers are biomass-derived compounds. Ethylene glycol is produced by dehydrating biomass ethanol produced by fermenting sugarcane molasses to produce biomass ethylene, which is then oxidized to produce biomass ethylene oxide, which is then hydrolyzed to produce plant-derived ethylene glycol. 2,5-furandicarboxylic acid is a compound synthesized by the dehydration (production of an oxygen-containing five-membered ring structure) and oxidation of fructose. The resulting polyethylene phenolate (PEF) fibers have a biomass content of 100%, and the fabric (5) made from this fiber yarn as a weaving or knitting element also has a biomass content of 100%.

[Example 6]
By following the same procedure as in Example 2 except that the fabric (2) in Example 2 is changed to the fabric (6), a tarpaulin-type soft polyvinyl chloride resin composite sheet (6) having a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. The biomass ratio of this soft polyvinyl chloride resin composite sheet (6) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (6)>
A fabric (6) is used, which has a mass of 200 g/m2 and a void ratio of 10%, and is made of 1000 d (1111 dtex) multifilament yarn (192 filaments) made of polypropylene furanoate (PPF) fiber melt-spun from polypropylene furanoate resin, with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp yarns/ ^inch × 20 weft yarns/inch.
*Polypropylene furanoate (PPF) fiber is melt-spun from polypropylene furanoate (PPF) resin obtained by the esterification reaction of 2,5-furandicarboxylic acid and propylene glycol. Both polymerization monomers are biomass-derived compounds. Propylene glycol is produced by dehydrating biomass propanol to produce biomass propylene, which is then oxidized to produce biomass propylene oxide, which is then hydrolyzed to produce plant-derived propylene glycol. 2,5-furandicarboxylic acid is a compound synthesized by dehydrating fructose (producing an oxygen-containing five-membered ring structure) and oxidizing it. The resulting polypropylene furanoate (PPF) fiber has a biomass content of 100%, and the fabric (6) made from this fiber yarn as a weaving or knitting element also has a biomass content of 100%.

[Example 7]
By following the same procedure as in Example 3 except for changing the fabric (3) to fabric (7), a tarpaulin-type soft polyvinyl chloride resin composite sheet (7) having a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. The biomass ratio of this soft polyvinyl chloride resin composite sheet (7) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and UV absorbers).
<Fabric (7)>
A fabric (7) is used, which has a mass of 200 g/m2 and a void ratio of 10%, and is made of 1000 d (1111 dtex) multifilament yarn (192 filaments) made of polybutylene furanoate (PBF) fiber melt-spun from polybutylene furanoate (PBF) resin, with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp yarns/ ^inch x 20 weft yarns/inch.
*Polybutylene furanoate (PBF) fiber is melt-spun from polybutylene furanoate (PBF) resin obtained by the esterification reaction of 2,5-furandicarboxylic acid and butylene glycol. Both polymerization monomers are biomass-derived compounds. Butylene glycol is produced by dehydrating biomass butanol to produce biomass butylene, which is then oxidized to produce biomass butylene oxide, which is then hydrolyzed to produce butylene glycol derived from plants. 2,5-furandicarboxylic acid is a compound synthesized by dehydrating fructose (producing an oxygen-containing five-membered ring structure) and oxidizing it. The resulting polypropylene furanoate (PBF) fiber has a biomass content of 100%, and the fabric (7) woven or knitted using this fiber yarn also has a biomass content of 100%.

[Example 8]
By following the same procedure as in Example 4 except for changing the fabric (4) to fabric (8), a tarpaulin-type soft polyvinyl chloride resin composite sheet (8) having a thickness of 0.75 mm and a mass of 925 g/ ^m2 can be obtained. The biomass ratio of this soft polyvinyl chloride resin composite sheet (8) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and UV absorbers).
<Fabric (8)>
A fabric (8) is used, which has a mass of 200 g/m2 and a void ratio of 10%, and is made of 1000 d (1111 dtex) multifilament yarn (192 filaments) made of polytrimethylene furanoate (PtMF) fiber melt-spun from polytrimethylene furanoate resin, with an S-twist of 200 T/m for the warp group and weft group, and a weaving density of 19 warp threads/inch x 20 weft threads/ ^inch .
*Polytrimethylene lanoate (PtMF) fiber is melt-spun from polytrimethylene lanoate (PtMf) resin obtained by the esterification reaction of 2,5-furandicarboxylic acid and trimethylene glycol. Both polymerization monomers are biomass-derived compounds. Trimethylene glycol is obtained by dehydrating biomass 1,3-propanol to biomass 1,3-propane, which is then oxidized to biomass trimethylene oxide, which is then hydrolyzed to produce plant-derived trimethylene glycol. 2,5-furandicarboxylic acid is a compound synthesized by dehydrating fructose (producing an oxygen-containing five-membered ring structure) and oxidizing it. The resulting polytrimethylene furanoate (PtMF) fiber has a biomass content of 100%, and the fabric (4) made from this fiber yarn as a weaving or knitting element also has a biomass content of 100%.

[Example 9]
<Tarpaulin made from woven fabric (1)>
A 0.16 mm thick film is formed on both sides of a fabric (1) having a biomass degree of 100% by calendering the soft vinyl chloride resin compound of the following [Formulation 5] under heat conditions of 165°C to 180°C, and then laminated in a softened state using a laminator under heat roll conditions of 170°C, to obtain a tarpaulin-like soft vinyl chloride resin composite sheet (9) having a thickness of 0.75 mm and a mass of 915 g/ ^m2 . Theoretically, the biomass degree of this soft vinyl chloride resin composite sheet (9) is approximately 23% (fabric and epoxidized soybean oil).
[Formulation 5] Flexible polyvinyl chloride resin compound composition Polyvinyl chloride resin by suspension polymerization (non-biomass: degree of polymerization 1300) 100 parts by weight Diisononyl phthalate (non-biomass plasticizer) 60 parts by weight Epoxidized soybean oil (partial biomass plasticizer) 10 parts by weight Antimony trioxide (flame retardant) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Rutile type titanium dioxide (white pigment) 5 parts by weight Benzotriazole-based compound (ultraviolet absorbing agent) 0.3 parts by weight

[Example 10]
<Tarpaulin made from woven fabric (2)>
By following the same procedure as in Example 9, except that a film made of fabric (2) with a biomass degree of 100% and [Blend 6] in which 60 parts by mass of diisononyl phthalate (non-biomass plasticizer) in [Blend 5] was changed to 60 parts by mass of diisononyl sebacate (non-biomass plasticizer) was used, a tarpaulin-type soft polyvinyl chloride resin composite sheet (10) with a thickness of 0.75 mm and a mass of 915 g/m ² was obtained. Theoretically, the biomass degree of this soft polyvinyl chloride resin composite sheet (10) is approximately 23% (fabric and epoxidized soybean oil).

[Example 11]
<Tarpaulin made from woven fabric (3)>
By following the same procedure as in Example 9, except that a film made of a fabric (3) with a biomass degree of 100% and [Blend 7] in which 60 parts by mass of diisononyl phthalate (non-biomass plasticizer) in [Blend 5] was changed to 60 parts by mass of diisononyl furandicarboxylate (non-biomass plasticizer) was used, a soft polyvinyl chloride resin composite sheet (11) in the form of a tarpaulin having a thickness of 0.75 mm and a mass of 915 g/m ² was obtained. The biomass degree of this soft polyvinyl chloride resin composite sheet (11) is theoretically approximately 23% (fabric and epoxidized soybean oil).

[Example 12]
<Tarpaulin made from woven fabric (4)>
By following the same procedure as in Example 9, except for using a fabric (4) with a biomass degree of 100% and a film made of [Blend 8] in which 60 parts by mass of diisononyl phthalate (non-biomass plasticizer) in [Blend 5] was changed to 60 parts by mass of polyglycerin/myristate triester (non-biomass plasticizer), a soft polyvinyl chloride resin composite sheet (12) in the form of a tarpaulin having a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass degree of this soft polyvinyl chloride resin composite sheet (12) is theoretically approximately 23% (fabric and epoxidized soybean oil).

[Example 13]
<Tarpaulin made from woven fabric (5)>
By following the same procedure as in Example 9, except that a fabric (5) with a biomass degree of 100% and a film made of [Blend 5] are used, a tarpaulin-type soft polyvinyl chloride resin composite sheet (13) with a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. The biomass degree of this soft polyvinyl chloride resin composite sheet (13) is theoretically approximately 23.5% (fabric and epoxidized soybean oil).

[Example 14]
<Tarpaulin made from woven fabric (6)>
By following the same procedure as in Example 9, except that a fabric (6) having a biomass degree of 100% and a film made of [Blend 6] are used, a tarpaulin-type soft polyvinyl chloride resin composite sheet (14) having a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. Theoretically, the biomass degree of this soft polyvinyl chloride resin composite sheet (14) is approximately 23.5% (fabric and epoxidized soybean oil).

[Example 15]
<Tarpaulin made from woven fabric (7)>
By following the same procedure as in Example 9, except that a fabric (7) having a biomass degree of 100% and a film made of [Blend 7] are used, a tarpaulin-type soft polyvinyl chloride resin composite sheet (15) having a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. Theoretically, the biomass degree of this soft polyvinyl chloride resin composite sheet (15) is approximately 23.5% (fabric and epoxidized soybean oil).

[Example 16]
<Tarpaulin made from woven fabric (8)>
By following the same procedure as in Example 9, except that a fabric (8) with a biomass degree of 100% and a film made of [Blend 8] are used, a tarpaulin-type soft polyvinyl chloride resin composite sheet (16) with a thickness of 0.75 mm and a mass of 925 g/ ^m2 is obtained. The biomass degree of this soft polyvinyl chloride resin composite sheet (16) is theoretically approximately 23.5% (fabric and epoxidized soybean oil).

The biomass content of the soft polyvinyl chloride resin composite sheets (1) to (8) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and UV absorbers), and since the polyvinyl chloride resins that make up each of these soft polyvinyl chloride resins are synthesized from plants, they have the radioactive carbon atom C-14 in part of their molecular structure at a concentration equivalent to that found in nature, and since the plasticizers are also synthesized from plants, they contain plasticizer molecules with the radioactive carbon atom C-14 in a concentration equivalent to that found in nature in part of their molecular structure, and furthermore, the synthetic fibers that make up the fabric also have the radioactive carbon atom C-14 in part of their polymer structure at a concentration equivalent to that found in nature. Therefore, detection of radioactive carbon atom C-14 from the components of the polyvinyl chloride resin, plasticizer, and fabric by accelerator mass spectrometry proves that the soft polyvinyl chloride resin composite sheets (1) to (8) of the present invention are derived from biomass, and the carbon dioxide generated during incineration has a carbon neutral element (raw materials and products derived from carbon dioxide absorbed by plants are returned to nature as carbon dioxide upon combustion, and this is then absorbed by plants again, resulting in a cycle that does not substantially increase carbon dioxide), making it possible to contribute to the realization of a low-environmental-load, low-carbon society that can suppress the increase in the amount of carbon dioxide in the global environment. In addition, the biomass degree of the soft polyvinyl chloride resin composite sheets (9) to (16) is theoretically approximately 23%, and in particular, there is a possibility that part of the polymer structure of the synthetic fibers that make up the fabric contains C-14, which exists in nature. Therefore, detection of C-14 from the components of the fabric by accelerator mass spectrometry proves that it is derived from biomass, and the carbon dioxide generated during incineration of the fabric separated from the soft polyvinyl chloride resin composite sheets (9) to (16) that have been disposed of has a carbon neutral element, making it possible to contribute to the realization of a low-environmental-load, low-carbon society that can suppress the increase in the amount of carbon dioxide in the global environment. Also, each of the biomass fabrics (1) to (8) separated from the soft polyvinyl chloride resin composite sheets (1) to (16) is depolymerized using ethylene glycol as a solvent, and then subjected to an ester exchange reaction with alcohol to obtain regenerated monomers such as terephthalic acid, dimethyl terephthalate, and bis 2-hydroxyethyl terephthalate, as well as regenerated monomers such as furandicarboxylic acid, dimethyl furandicarboxylate, and bis 2-hydroxyethyl furandicarboxylate, as well as regenerated monomers such as ethylene glycol, propylene glycol, butylene glycol, and trimethylene glycol. These recycled monomers are subjected to a polycondensation reaction to regenerate the fibers that make up each of the biomass fabrics (1) to (8), and this regeneration is repeated as necessary.

[Reference Example 1]
The acrylic resin coating material of the following [Formulation 9] was applied to both sides of the soft polyvinyl chloride resin composite sheet (1) of Example 1 using a 100 mesh gravure roll, and then heated and dried for 2 minutes in a hot air oven at 120°C to form acrylic resin coating layers (5 g/ ^m2 /one side) on both sides to form intermediate A (1).
[Formula 9] Acrylic resin paint: Alkyl methacrylate ester/alkyl acrylate ester copolymer
100 parts by weight Methyl ethyl ketone (MEK diluent) 250 parts by weight Toluene (diluent) 250 parts by weight Next, a solution of the aminoethylated acrylic resin epoxy composition shown below in [Formula 10] is applied to one surface of this intermediate A (1) using a 100 mesh gravure roll, and heated and dried in a hot air oven at 120°C for 2 minutes to produce intermediate B (1) with an acrylic resin coating layer (5 g/ ^m2 /one side) attached in a semi-cured state to the surface side.
[Formulation 10] Aminoethylated acrylic resin epoxy composition Polyethylenimine is grafted onto the carboxyl group of a copolymer of alkyl methacrylate, alkyl acrylate and methacrylic acid,
The amine value (per 1 g of solids) of a compound whose side chain is represented by the chemical formula -COO(CH ₂ CH ₂ NH) _n H
(Number of mmol of amines contained in) 0.7 to 1.3 mmol/g of primary amino group-containing acrylic resin
100 parts by weight Epoxy resin (bisphenol A skeleton-containing trifunctional epoxy resin with epoxy equivalent of 260 g/eq) 20 parts by weight Methyl ethyl ketone (MEK diluent) 150 parts by weight Toluene (diluent) 150 parts by weight Next, the corona-treated side of a polyvinylidene fluoride (PVdF) film with a thickness of 25 μm and 53 g/m ² is placed against the aminoethylated acrylic resin epoxy semi-cured layer side of this intermediate B (1), and passed through a laminator under hot roll conditions at 150 ° C., and heat-pressed to laminate a fluorine-based resin film to form an anti-stain layer, thereby obtaining a soft vinyl chloride-based resin composite sheet (17) that has excellent soot dust stain resistance and rain streak stain resistance and can restore a beautiful appearance by wiping and cleaning. The biomass degree of this soft vinyl chloride-based resin composite sheet (17) is theoretically about 93%.

According to the present invention, it is possible to provide a soft polyvinyl chloride resin film and a soft polyvinyl chloride resin composite sheet containing carbon neutral (recyclable) elements. In particular, the soft polyvinyl chloride resin film is widely useful for agricultural and horticultural vinyl greenhouses, medical clean booths, simple industrial clean booths, partitions for public facilities, protective covering materials for automobiles and railway cars, protective covering materials for floors and walls, and waterproof covering materials for roofs and ceilings. The soft polyvinyl chloride resin composite sheet is widely useful for large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, negative pressure medical tents, architectural protection (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, visual facades, flexible containers, lift-up sheet shutters, floor sheets, tarpaulins used for partition sheets, etc., and canvas used for truck hoods, open-air storage waterproof sheets, and house-shaped tents, as well as mesh sheets used for architectural protection mesh sheets, wind and snow protection nets, anti-glare nets, sunshade facades, etc. Furthermore, the carbon dioxide generated during incineration is carbon neutral (raw materials and products derived from carbon dioxide absorbed by plants are returned to nature as carbon dioxide through combustion, and then absorbed again by plants, resulting in a cycle that does not substantially increase carbon dioxide), and it is expected to contribute to the realization of a low-environmental-load, low-carbon society that can curb the increase in the amount of carbon dioxide in the global environment.Biomass refers to materials derived from plants and animals, and regenerative circulation mainly refers to carbon neutral (carbon recycling derived from plants and animals) and chemical recycling (polymer regeneration) using regenerated monomers obtained by depolymerization of polymers.

Claims (2)

A soft polyvinyl chloride resin composite sheet comprising a resin coating layer, laminated on one or more sides of a fabric, the resin coating layer containing at least a biomass plasticizer containing a plasticizer molecule having a radioactive carbon atom C-14 in part of its molecular structure, and a biomass polyvinyl chloride resin (not including a copolymer) containing a vinyl chloride unit having a radioactive carbon atom C-14 in part of its molecular structure, wherein the biomass plasticizer is one or more compounds selected from the group consisting of a dialkyl phthalate compound [Chemical formula 1], a dialkyl sebacate compound [Chemical formula 2], a furandicarboxylic acid alkyl ester compound [Chemical formula 3], and a polyglycerin fatty acid ester compound [Chemical formula 4], the fabric comprising a multifilament yarn as a weaving or knitting element, the multifilament yarn being made of one or more polyalkylene furanoate fibers [Chemical formula 6] selected from polyethylene furanoate and polytrimethylene furanoate, the polyalkylene furanoate being a biomass fiber having a radioactive carbon atom C-14 in part of its molecular structure .
* Wherein n = 4 to 12
* Wherein n = 4 to 12
* Wherein n = 4 to 12
*In the formula, n = 2 to 10, R is an alkyl group having 2 to 10 carbon atoms.
*In the formula, n = 2 to 10, m = 300 to 1000 The soft polyvinyl chloride resin composite sheet according to claim 1, wherein the polyalkylene furanoate [Chemical Formula 6] fiber is a regenerated fiber obtained from a regenerated polyalkylene furanoate by polymerization of a regenerated monomer obtained by depolymerizing polyalkylene furanoate, and the regenerated monomer includes one or more selected from furandicarboxylic acid, dimethyl furandicarboxylate, and bis 2-hydroxyethyl furandicarboxylate.