JP7412014B2 - industrial composite sheet - Google Patents

Description

The present invention is applicable to greenhouses for agriculture and horticulture, simple clean booths for medical use, simple clean booths for industrial use, partitions for public facilities, protective coverings for automobiles and railway vehicles, protective coverings for floors and walls, and waterproofing for roofs and ceilings. Industrial material films used for covering materials, large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs for architectural spaces (membrane ceilings), visual facades, Tarpaulins used for flexible containers, elevating sheet shutters, floor sheets, partition sheets, etc.; Canvas used for truck hoods, outdoor waterproof sheets, house tents, etc.; architectural curing mesh sheets, windproof and snowproof nets, anti-glare nets, sunshade facades. This invention relates to industrial composite sheets such as mesh sheets used for etc. More specifically, it relates to a recyclable industrial material film made of soft vinyl chloride resin containing at least a plasticizer synthesized from a plant-derived substance, and also relates to a polyalkylene furanoate fiber yarn or an alkylene furanoate-containing copolymer fiber yarn. Regarding recycle-type industrial composite sheets such as tarpaulins, canvases, and mesh sheets, which are based on fabrics having woven or knitted elements, fabrics made from plant-derived materials, and soft vinyl chloride containing at least a plasticizer made from plant-derived materials. The present invention relates to a recycle-type industrial composite sheet comprising a resin layer. In this specification, biomass-derived means derived from animals and plants, and regenerative circulation type mainly means carbon neutral.

Large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs for architectural spaces (membrane ceilings), facade sheets, flexible containers, elevating sheet shutters, floor sheets, Industries such as tarpaulin used for partition sheets, canvas used for truck hoods, outdoor waterproof sheets, house tents, etc., and mesh sheets used for architectural curing mesh sheets, windproof and snowproof nets, anti-glare nets, facade meshes, etc. The base material of the composite sheet for use is a fabric whose weaving and knitting elements are polyester fiber threads spun from polyethylene terephthalate (hereinafter referred to as PET resin). In particular, tarpaulin is made by laminating thermoplastic resin composition films on both sides of a fabric (woven fabric) with a porosity of about 6 to 25%, and a liquid thermoplastic resin composition is laminated on both sides of a fabric with a porosity of about 0 to 10%. A canvas is obtained by impregnating and coating the resulting material into a film, and a liquid thermoplastic resin composition is impregnated and coating the entire surface of a coarse fabric with a porosity of about 15 to 70% to form a film. The thing is a mesh sheet. Converting the PET resin fabric synthesized using petroleum-based materials used as the base material of these industrial composite sheets to PET resin fabric synthesized using plants as the starting material is a low-carbon solution that does not increase the amount of carbon dioxide. This is one of the proposals for a low-carbon society with low environmental impact.

On the other hand, in recent years, businesses have become established that use PET bottle waste as raw material and recycle it into fibers (carpets, clothing), sheets, molded products (stationery, miscellaneous goods, containers), etc. However, the quality of recovered PET bottles varies widely. The quality and physical properties of recycled products were inferior. However, in recent years, there has been a widespread awareness of the idea of immediately recycling PET beverage bottles for resource recovery, and it has become possible to stably obtain high-quality recycled PET with little quality deterioration, making it impossible to achieve this goal in the past. , "bottle-to-bottle" horizontal recycling has been realized in which PET bottles are recycled into new beverage PET bottles. The background to this is the predicted depletion of oil, which is the raw material for plastics, global warming caused by carbon dioxide generated by incineration of plastics (abnormal weather, wind and flood damage, rising water levels, abnormal ecosystems, etc.), and the ocean caused by degraded plastics (microplastic particles). Problems such as pollution and damage to living organisms have become urgent, and various efforts are being made to go beyond simply reducing plastic waste, such as using natural products as substitutes and depolymerizing waste plastics to turn them into fuel. Recently, people have been advocating the conservation of the global environment by replacing plastics with products that have a lower environmental impact, and in particular, consideration has been given to replacing PET resin, which is widely used worldwide, with PET resin synthesized from plant-derived materials. This plant-based PET resin is synthesized from Biomass ethylene glycol and Biomass terephthalic acid. Biomass ethylene glycol is a diol obtained by dehydrating bioethanol produced by fermentation of sugarcane sludge sugar to ethylene, oxidizing this to ethylene oxide, and further hydrolyzing it. Isobutanol produced by fermentation is dehydrated to produce isobutylene, and paraxylene obtained by dimerization and cyclization through radical reactions is converted into terephthalic acid. However, as the manufacturing process for Biomass terephthalic acid becomes complicated and involves multiple steps, and the energy involved in the entire process increases, it is undeniable that the resulting plant-derived PET resin becomes expensive and irrational, including energy loss. (*Biomass and biomass are synonymous and mean ``renewable organic resources derived from living organisms.'' In this specification, biomass that appears before chemical substance nouns is referred to as ``biomass'' to avoid misunderstandings due to consecutive katakana notations.) , and the following paragraphs as well)

On the other hand, polyalkylene furanoate resin is attracting attention as a substitute for PET resin. In particular, polyethylene furanoate resin (hereinafter referred to as PEF resin) is obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and these monomers can also be procured from plants. Monoethylene glycol is Biomass diol obtained by dehydrating Biomass ethanol produced by fermentation of sugarcane sludge and converting it into Biomass ethylene, which is then oxidized to Biomass ethylene oxide, and further hydrolyzed. Since it is Biomass 2,5-furandicarboxylic acid synthesized by dehydrating fructose (creating an oxygen-containing 5-membered ring structure) and oxidizing it, it is possible to achieve 100% biomass content. Specifically, PEF resin is used in a multilayer container provided with a gas barrier layer, and Patent Document 1 discloses an invention of a gas barrier multilayer container in which the PEF resin is a PEF resin obtained from Biomass polyethylene glycol and Biomass furandicarboxylic acid. There is. Patent Document 2 also discloses an invention of a lightweight and strong container (resin molded product) containing a terephthalate polyester resin and a PEF resin, in which the proportion of the PEF resin is 2 to 25% by mass. has been done. The multilayered polyester resin container of Patent Document 1 and the resin container made of polyester resin blend of Patent Document 2 are household items that are used for a short period of time, so they are hardly subject to resin deterioration and are resources with high reuse potential. Horizontal recycling is difficult due to the structure and resin blend.

Therefore, if a plant-based biomass resin that is easier to synthesize and has performance equivalent to or better than petroleum-based PET resin is developed, it would be possible to obtain a regenerated and recirculating biomass fabric using fibers spun from the plant-based resin. At the same time, high biomass is being promoted for constituent materials such as thermoplastic resin composition films that cover biomass fabrics and thermoplastic resin composition films that impregnate and coat biomass fabrics. If it is possible to rationally eliminate dependence on petroleum in the synthesis process of its main components, vinyl chloride resin, and plasticizer, a more recyclable industrial composite sheet will become a reality. Further, the above-mentioned thermoplastic resin composition film constituting the industrial composite sheet can also be widely utilized as a recycle-type industrial material film by itself. By converting to such recyclable industrial material films and industrial composite sheets, even if they are incinerated, the carbon dioxide generated is carbon neutral (bioresin derived from carbon dioxide absorbed by plants can be recycled). It is counted as a cycle in which carbon dioxide is returned to nature and then absorbed by plants again), and it is hoped that it will be developed and put into practical use as a campaign that can contribute to preserving the global environment.

JP2018-199258A Japanese Patent Application Publication No. 2018-104070

The present invention provides a recycleable industrial material film made of a soft vinyl chloride resin containing at least a specific plasticizer, a tarpaulin comprising a specific fabric, and a soft vinyl chloride resin layer containing at least a specific plasticizer; Our goal is to provide recyclable industrial composite sheets such as canvas and mesh sheets. According to the industrial material film and industrial composite sheet of the present invention, most of the carbon dioxide generated during incineration is carbon neutral (raw materials and products derived from carbon dioxide absorbed by plants are naturally converted into carbon dioxide). It is counted as a cycle in which carbon dioxide is returned to the earth and then absorbed by plants again), and can contribute to the realization of a low-environmental load and low-carbon society that can suppress the increase in the amount of carbon dioxide in the global environment. In the present invention, the recycle type mainly means carbon neutral.

As a result of repeated studies taking these points into consideration, the present invention has been developed to provide 1) an industrial material film comprising a composition containing at least a vinyl chloride resin and a specific furandicarboxylic acid dialkyl ester compound, and 2) a film based on a specific fabric. An industrial composite sheet in which a soft vinyl chloride resin layer made of a composition containing at least a vinyl chloride resin and a specific furandicarboxylic acid dialkyl ester compound is formed on one or more sides of a specific fabric as a material, We have completed the present invention by discovering that it can be made into a recyclable product that is carbon neutral.

That is, the film used for the industrial composite sheet of the present invention is preferably made of a composition containing at least a vinyl chloride resin and a furandicarboxylic acid dialkyl ester compound [Chemical formula 1], and the composition is a polyglycerin fatty acid ester compound. It can further contain one or more kinds of compounds [Formula 2]. The furandicarboxylic acid dialkyl ester compound [Chemical formula 1] is a plasticizer synthesized by the reaction (esterification) of furandicarboxylic acid and alcohol, and it is particularly preferable that furandicarboxylic acid and alcohol are synthesized from plant-derived substances. . Polyglycerin fatty acid ester compound [Chemical formula 2] is a plasticizer synthesized by the reaction (esterification) of glycerin and fatty acid.In order from the top, it is a monoester compound, a diester compound, and a triester compound.In particular, glycerin and fatty acid are Those synthesized from plant-derived substances are preferred. The vinyl chloride resin is obtained by radical polymerization of a vinyl chloride monomer, and it is particularly preferable that the vinyl chloride monomer is synthesized from a plant-derived material. [Chemical formula 1] and the vinyl chloride resin, or [Chemical formula 1], [Chemical formula 2], and the vinyl chloride resin are all synthesized from plant-derived substances, but at least [Chemical formula 1] It is preferably a compound synthesized from a plant-derived substance, and [Formula 2] is also preferably a compound synthesized from a plant-derived substance. As a result, even if the industrial material film of the present invention and the waste material of the film construction are incinerated, the carbon dioxide generated from it is carbon neutral (the biomass film derived from the carbon dioxide absorbed by plants returns to nature, By meeting the requirements for the film to be counted as part of the cycle of re-absorption by plants, it can theoretically become a recyclable industrial material film.

The industrial composite sheet of the present invention has a fabric as a base material containing multifilament yarns made of polyalkylene furanoate fibers or alkylene/furanoate/terephthalate copolymer fibers as weaving/knitting elements, vinyl chloride resin, and flanges. It is preferable that a soft vinyl chloride resin layer made of a composition containing at least a carboxylic acid dialkyl ester compound [Chemical formula 1] is formed on one or more surfaces of the fabric, and the composition is a polyglycerol fatty acid ester compound [Chemical formula 1]. It may further contain one or more of the following. The furandicarboxylic acid dialkyl ester compound [Chemical formula 1] is a plasticizer synthesized by the reaction (esterification) of furandicarboxylic acid and alcohol, and it is particularly preferable that furandicarboxylic acid and alcohol are synthesized from plant-derived substances. . Polyglycerin fatty acid ester compound [Chemical formula 2] is a plasticizer synthesized by the reaction (esterification) of glycerin and fatty acid.In order from the top, it is a monoester compound, a diester compound, and a triester compound.In particular, glycerin and fatty acid are Those synthesized from plant-derived substances are preferred. The vinyl chloride resin is obtained by radical polymerization of a vinyl chloride monomer, and it is particularly preferable that the vinyl chloride monomer is synthesized from a plant-derived material. [Chemical formula 1] and the vinyl chloride resin, or [Chemical formula 1], [Chemical formula 2], and the vinyl chloride resin are all synthesized from plant-derived substances, but at least [Chemical formula 1] It is preferably a compound synthesized from a plant-derived substance, and [Formula 2] is also preferably a compound synthesized from a plant-derived substance. As a result, even if the industrial composite sheet of the present invention and the waste material of the sheet construction are incinerated, the carbon dioxide generated is carbon neutral (the biomass film derived from the carbon dioxide absorbed by plants returns to nature, By meeting the requirements for the material to be counted as re-absorbed by plants (re-absorbed by plants), it can theoretically become a regenerative and cyclical industrial composite sheet.

In the industrial composite sheet of the present invention, the fabric includes multifilament yarns made of polyalkylene furanoate [Chemical formula 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical formula 4] fibers in the weaving and knitting elements. Preferably, 1) the polyalkylene furanoate fiber is one or more selected from polyethylene furanoate fiber, polypropylene furanoate fiber, polybutylene furanoate fiber, and polytrimethylene furanoate fiber, and 2) the polyalkylene furanoate fiber is /furanoate/terephthalate copolymer fibers include polyethylene/furanoate/terephthalate copolymer fibers, polypropylene/furanoate/terephthalate copolymer fibers, polybutylene/furanoate/terephthalate copolymer fibers, and polytrimethylene/furanoate/terephthalate copolymer fibers. It is preferable that the fiber is one or more selected from the combined fibers. The polyalkylene furanoate [Chemical formula 3] is obtained by polycondensation of alkylene glycol and furandicarboxylic acid, and it is particularly preferable that the alkylene glycol and furandicarboxylic acid are synthesized from plant-derived substances. The alkylene/furanoate/terephthalate copolymer [Chemical formula 4] is an alternating or random copolymer [Chemical formula 4 above] obtained by polycondensation of alkylene glycol, furandicarboxylic acid, and terephthalic acid, or a block copolymer [Chemical formula 4] 4 below], and in particular, those in which alkylene glycol, furandicarboxylic acid, and terephthalic acid are synthesized from plant-derived substances are most preferred. Preferably, at least alkylene glycol and furandicarboxylic acid are synthesized from plant-derived substances. As a result, even if the industrial material sheet of the present invention and the waste material of the sheet construction are incinerated, the carbon dioxide generated is carbon neutral (the biomass film derived from the carbon dioxide absorbed by plants returns to nature, By meeting the requirements for it to be counted as part of the cycle of re-absorption by plants, it can theoretically become a recycle-type industrial composite sheet.

In the industrial composite sheet of the present invention, the weaving and knitting elements of the fabric are warp/weft, warp/upper right 30-60° bias yarn/upper left 30-60° bias yarn, warp/weft/ It is preferable to use one type selected from upper right 30-60° bias yarn/upper left 30-60° bias yarn. Here, "warp/weft" is a biaxial fabric, "warp/upper right 30~60° bias yarn/upper left 30~60° bias yarn" is a triaxial fabric, and "warp/weft/upper right 30 ~60° bias yarn/30~60° bias yarn on the upper left represents a four-axis fabric. In particular, by using triaxial fabrics and quadriaxial fabrics as the base material, the resulting industrial composite sheet has extremely excellent dimensional stability, breaking strength, penetration resistance, and tear resistance, so it is especially suitable for tarpaulins and canvases. In addition to applications such as tent structures, it can also be used for special purposes such as flexible security shutters, protective clothing and covers for riot police and the Self-Defense Forces, protection against flying debris at explosion construction sites, and falling object catch equipment at work sites. can.

According to the industrial material film and industrial composite sheet of the present invention, most of the carbon dioxide generated during incineration is carbon neutral (raw materials and products derived from carbon dioxide absorbed by plants are naturally converted into carbon dioxide). In particular, industrial material films are useful for agriculture and agriculture because they can contribute to the realization of a low-environmental load and low-carbon society that can suppress the increase in carbon dioxide emissions. Widely used in greenhouses for gardening, simple clean booths for medical use, simple clean booths for industrial use, partitions for public facilities, protective coverings for automobiles and railway vehicles, protective coverings for floors and walls, waterproof coverings for roofs and ceilings, etc. It is expected that industrial composite sheets will be used in large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs of architectural spaces (membrane ceilings), and visual facades. , tarpaulin used for flexible containers, elevating sheet shutters, floor sheets, partition sheets, etc., canvas used for truck hoods, open-air waterproof sheets, house tents, etc., architectural curing mesh sheets, windproof and snowproof nets, anti-glare nets, sunshades. It is expected that it will be widely used in mesh sheets used for facades, etc.

A) Industrial material film of the present invention is an embodiment (Aa) consisting of a composition containing at least a vinyl chloride resin and a furandicarboxylic acid dialkyl ester compound, and this composition further contains a polyglycerol fatty acid ester compound. (Ab). In addition, B) the recycle-type industrial composite sheet of the present invention has a fabric as a base material, and a soft vinyl chloride resin layer made of a composition containing at least a vinyl chloride resin and a furandicarboxylic acid dialkyl ester compound. An embodiment (Ba) in which the composition further contains a polyglycerin fatty acid ester compound, and an embodiment (Bb) in which the composition is formed on one or more sides of This is an embodiment (Bc) in which the weaving and knitting elements include multifilament yarns made of terephthalate copolymer fibers, and the weaving and knitting elements of the fabric include warp threads/weft threads, warp threads/upper right 30 to 60° bias threads/ Embodiment (Bd) is one selected from upper left 30-60° bias yarn, warp/weft/upper right 30-60° bias yarn/upper left 30-60° bias yarn.

The industrial material film of the present invention is a soft vinyl chloride resin (plasticizer-containing) composition, consisting mainly of 100 parts by mass of straight vinyl chloride resin (fine particles) obtained by suspension polymerization and 30 to 100 parts by mass of plasticizer. As the stabilizer for the vinyl chloride resin, stabilizers such as a calcium zinc composite system, a barium zinc composite system, an organic tin laurate, an organic tin mercaptite, and an epoxy system can be optionally used. If necessary, pigments, flame retardants, fillers, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, crosslinking agents, and the like can be optionally used. This soft vinyl chloride resin composition is preferably calender-rolled or T-die extruded to a thickness of 0.1 to 1 mm. The main plasticizer in such a resin composition is a furandicarboxylic acid dialkyl ester compound [Chemical formula 1], and the plasticizer that can be additionally included in this composition is a polyglycerol fatty acid ester compound [Chemical formula 2] One or more of the following. Similarly, the recyclable industrial material sheet of the present invention includes 1) a tarpaulin made of a fabric as a base material and a soft vinyl chloride resin film laminated on one or more sides thereof; , a canvas formed with a soft vinyl chloride resin-impregnated coating layer, 3) a mesh sheet made of a coarse fabric as a base material and a soft vinyl chloride resin-impregnated coating layer formed on both sides, and a soft chloride resin for tarpaulins. The vinyl resin film is the same as the above film, and the soft vinyl chloride resin impregnated coating layer for canvas and mesh sheets consists of 100 parts by mass of paste vinyl chloride resin (fine particles) obtained by emulsion polymerization, and 30 to 100 parts by mass of plasticizer. As stabilizers for vinyl chloride resins, stabilizers such as calcium zinc composite system, barium zinc composite system, organotin laurate, organotin mercaptite, and epoxy system can be optionally used. If necessary, pigments, flame retardants, fillers, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, crosslinking agents, and the like can be optionally used. A film obtained by coating a fabric with this paste-like material, or dipping the fabric in a liquid bath of the paste-like material, and then heat-treating and gelling the resultant film is preferable. The main plasticizer in such a resin composition is a furandicarboxylic acid dialkyl ester compound [Chemical formula 1], and the plasticizer that can be additionally included in this composition is a polyglycerol fatty acid ester compound [Chemical formula 2] One or more of the following.

Furandicarboxylic acid dialkyl ester compound [Chemical formula 1] is a plasticizer synthesized by reaction (esterification) of furandicarboxylic acid and alcohol, and n=4 to 20, especially 2,5-furandicarboxylic acid and C4 to C12 ( A 2,5-furandicarboxylic acid dialkyl ester compound synthesized by reaction (esterification) with an alcohol (which may be C13 to C20) is preferred. 2,5-furandicarboxylic acid is a recyclable biomass compound that is synthesized by, for example, dehydration (generation of an oxygen-containing five-membered ring structure) and oxidation of fructose. Regenerative circulation means that the carbon dioxide emitted from the combustion of biomass products is absorbed by plants, and the sugars produced by plants are converted into biomass compounds to synthesize biomass compounds (in this paragraph, the plasticizer of [Chemical 1]). It means the cycle of The coordination of the carboxylic acid of furandicarboxylic acid is possible in other than the 2,5-position, the 2,3-position, the 2,4-position, and the 3,4-position, but as a biomass compound, 2,5-furandicarboxylic acid is It is the easiest to synthesize. Specific examples of [Chem. 1] include dibutyl 2,5-furandicarboxylate (MW268) and diisobutyl 2,5-furandicarboxylate (MW268) produced by the reaction of 2,5-furandicarboxylic acid and C4 alcohol, as well as Dipentyl 2,5-furandicarboxylate (MW 296) by reaction with C5 alcohol, dihexyl 2,5-furandicarboxylate (MW 324) also by reaction with C6 alcohol, 2,5-furandicarboxylate (MW 324) also by reaction with C7 alcohol. Diheptyl furandicarboxylate (MW 352), di(2-ethylhexyl) 2,5-furandicarboxylate (MW 380), also by reaction with C8 alcohol, dinonyl 2,5-furandicarboxylate (MW 380), also by reaction with C9 alcohol. MW408) and diisononyl 2,5-furandicarboxylate (MW408), as well as didecyl 2,5-furandicarboxylate (MW436) and diisodecyl 2,5-furandicarboxylate (MW436) by reaction with C10 alcohol. For example, diundecyl 2,5-furandicarboxylate (MW464) obtained by reaction with C11 alcohol and dilauryl 2,5-furandicarboxylate (MW492) obtained by reaction with C12 alcohol 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 alcohols such as Biomass ethanol and Biomass butanol. These furandicarboxylic acid dialkyl ester compounds [Formula 1] obtained by this process have a biomass degree of 100% and can be recycled and recycled.

Polyglycerol fatty acid ester compounds [Chemical formula 2] are obtained by esterifying polyglycerin and fatty acids. Either a triester compound [Chemical formula 2 below] or a mixture thereof. Polyglycerin is a polymer obtained by dehydration condensation using glycerin as a monomer, and the degree of polymerization n=2 to 10, particularly preferably n=2, 4, or 6. In particular, glycerin is obtained by hydrolyzing triacylglycerol contained in the fats and oils of living things (animals, fish, insects, etc.), and by-products from the soap manufacturing process obtained by saponifying fats and oils (animal-based, plant-based). Non-petroleum derived Biomass glycerin is preferred, such as Biomass glycerin), a by-product (glycerin) from the production of fatty acid methyl esters through the transesterification reaction of fats and oils with methanol, and Biomass glycerin obtained by converting Biomass propylene to epichlorohydrin and hydrolyzing this. In addition, the fatty acid is preferably a saturated or unsaturated fatty acid having 2 to 10 carbon atoms, and these fatty acids may be linear or branched. Specifically, acetic acid, propionic acid, butyric acid, caproic acid (hexanoic acid), caprylic acid 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), etc.; however, from the viewpoint of non-petroleum derived substances, linoleic acid and linolenic acid contained in safflower oil, corn oil, soybean oil, olive oil, coconut oil, palm oil, etc. Preferred acids include oleic acid, lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), and the like. Examples of the polyglycerin fatty acid ester compound [Chemical formula 2] include polyglycerin/caprylic acid mono (or di, or tri) ester, polyglycerin/caprylic acid mono (or di, or tri) ester, and polyglycerin 2-ethylhexanoate monoester. (or di, or tri) ester, polyglycerin/lauric acid mono(or di, or tri) ester, polyglycerin/palmitic acid mono(or di, or tri) ester, and the like. (* "/" was used to avoid visual confusion due to consecutive katakana nouns for chemical substances. All polyglycerin fatty acid ester compounds are treated the same way.) The polyglycerol fatty acid ester compound [Chemical formula 2] obtained by esterifying the fatty acid derived from the above can be a recyclable biomass compound. The combined use of the polyglycerin fatty acid ester compound [Chemical formula 2] is 1 to 50% by mass based on the blended mass of the furandicarboxylic acid dialkyl ester compound [Chemical formula 1]. The larger the amount of the compound [Chemical formula 2] used, the better the filler dispersion and filling effect for the soft vinyl chloride resin film and the soft vinyl chloride resin impregnated coating layer, and especially the branched structure of the compound [Chemical formula 2] improves the plasticizer migration. It has an excellent deterrent effect and does not easily cause the surface of the article to become sticky due to plasticizer, reducing the adhesion of soot and dust, thereby preventing stains, and maintaining long-term texture by inhibiting volatilization of the plasticizer. becomes possible.
*In the formula, R is an alkyl group

The vinyl chloride resin used in the industrial material film and industrial material sheet of the present invention is a homopolymer of vinyl chloride monomer (emulsion polymerization type, suspension polymerization type, with a degree of polymerization of 700 to 3800). ), crosslinked vinyl chloride resins, chlorinated vinyl chloride resins, and copolymers containing more than 60% by mass of vinyl chloride, such as vinyl chloride/vinyl acetate copolymers and vinyl chloride/acrylic graft polymers. Vinyl chloride monomer is produced 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 the ethylene dichloride is then pyrolyzed. An oxychlorination method in which ethylene obtained by thermal decomposition of ethylene is reacted with hydrogen chloride, a by-product of the direct chlorination method, in the presence of oxygen to produce ethylene dichloride, which is then dehydrated and thermally decomposed. is general purpose. However, the vinyl chloride resin used in the present invention is preferably a biomass vinyl chloride resin polymerized using a vinyl chloride monomer derived from Biomass ethylene obtained by dehydrating Biomass ethanol produced by fermentation of sugarcane sludge. This biomass vinyl chloride resin is manufactured using a composition that uses a dialkyl furandicarboxylic acid ester compound [Chemical formula 1] as a plasticizer, and further contains a Biomass polyglycerin fatty acid ester compound [Chemical formula 2] as a plasticizer, if necessary. The produced industrial material film and industrial composite sheet can be carbon-neutral biomass industrial material film and industrial composite sheet. If the biomass degree is arbitrary, epoxidized soybean oil, epoxidized linseed oil, phthalate esters, isophthalate esters, terephthalate esters, cyclohexanedicarboxylic acid esters, cyclohexenedicarboxylic esters, adipic acid esters, etc. , sebacic acid type, chlorinated paraffin type, polyester type, ethylene/vinyl acetate/carbon monoxide terpolymer resin, ethylene/(meth)acrylic acid ester/carbon monoxide terpolymer resin, etc. plasticizers. may be used in combination in an amount of 1 to 50% by mass based on the total amount of plasticizer. In particular, epoxidized soybean oil and epoxidized linseed oil are ideal for use as a plasticizer in the present invention because the soybean oil and linseed oil portions of their chemical structures are derived from biomass.

The fabric used as the base material of the industrial composite sheet of the present invention is a weaving element made of multifilament yarns made of at least polyalkylene furanoate [Chemical formula 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical formula 4] fibers. Included in 1) Woven fabrics for tarpaulins (plain fabrics, diagonal fabrics, satin fabrics, twill fabrics, raschel fabrics, etc.) with a porosity of about 6 to 25%, and are woven and knitted with long fiber multifilament yarns. Woven fabric with a weight of 100 to 500 g/ ^m2 , 2) Canvas fabric with a porosity of about 0 to 10% (plain fabric, diagonal fabric, satin fabric, twill fabric, etc.), short fiber spun (spun) multifilament yarn. Spun fabrics with a basis weight of 100 to 500 g/ ^m2 that are woven and knitted in strips, 3) and coarse fabrics for mesh sheets (plain fabrics, patterned fabrics, stacked nets, etc.) with a porosity of about 10 to 70%. Coarse woven fabric with a basis weight of 30 to 200 g/ ^m2 made of long fiber multifilament yarn, long fiber multifilament yarn (coated yarn) whose entire yarn is coated with resin, and a basis weight of 25 to 350 g/m2. Examples include ^woven /knitted mesh and stacked mesh. The porosity is warp/weft, warp/upper right 30~60° bias yarn/upper left 30~60° bias yarn, warp/weft/upper right 30~60° bias yarn/upper left 30~60 ° It is the sum total of gaps caused by intertwining and crossing of axis yarns such as bias yarns, and can be calculated as a value subtracted from 100 by calculating the area of the yarns in the unit area of the fabric as a percentage. Specifically, it is possible to calculate the average value of the yarn width and convert it into a value based on the porosity per inch squared from the relationship of the number of yarns driven/inch.

These woven fabrics, spun fabrics, coarse woven fabrics, and meshes are composed of polyalkylene furanoate fiber multifilament yarns or alkylene/furanoate/terephthalate copolymer fibers, but other fibers include polyester (polyethylene One or more types of multifilament yarn (long fiber, short fiber spun yarn) selected from terephthalate: PET, polybutylene terephthalate: PBT, polynaphthalene terephthalate: PNF) fiber, polyethylene fiber, polypropylene fiber, nylon fiber, vinylon fiber. ) can be used in combination, and the mixing ratio of these yarns is preferably 50% by mass or less from the viewpoint of biomass degree. Mixed yarns can be arranged regularly or randomly at arbitrary driving intervals (n alternating, n aligned alternately, n straddling: n is an integer) to create a lattice or geometric pattern in appearance. It may be. The weaving and knitting elements of the fabric using the above threads are warp thread/weft thread, warp thread/upper right 30-60° bias thread/upper left 30-60° bias thread, warp thread/weft thread/upper right 30-60° One type selected from bias yarn/upper left 30~60° bias yarn. Here, "warp/weft" is a biaxial fabric, "warp/upper right 30~60° bias yarn/upper left 30~60° bias yarn" is a triaxial fabric, and "warp/weft/upper right 30 ~60° bias yarn/30~60° bias yarn on the upper left represents a four-axis fabric. (*In the explanation of weaving and knitting elements of fabrics, "/" means a combination of yarn directions, that is, and. The same applies to all weaving and knitting elements of fabrics.) In particular, triaxial fabrics and quadriaxial fabrics are used as the base material. As a result, the resulting industrial composite sheet has excellent dimensional stability, breaking strength, penetration resistance, and tear resistance, so in addition to applications such as tent structures, it can also be used as flexible security shutters, protective clothing for riot police and the Self-Defense Forces, etc. It can also be used for special purposes such as protective covers, preventing debris from flying off at blasting construction sites, and as equipment to catch fallen objects at work sites. Tarpaulin is made by laminating a thermoplastic resin composition film on both sides of a woven fabric with a porosity of about 6 to 25%, and canvas is made by laminating a liquid thermoplastic resin film on both sides of a fabric with a porosity of about 0 to 10%. The composition is impregnated and coated to form a film, and the mesh sheet is obtained by impregnating and coating the entire surface of a coarse fabric with a porosity of about 10 to 70% with a liquid thermoplastic resin composition. This is an embodiment in which the film is formed into a film.

The fabric used as the base material of the industrial composite sheet of the present invention is a weaving element made of multifilament yarns made of at least polyalkylene furanoate [Chemical formula 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical formula 4] fibers. 1) Polyalkylene furanoate fibers include one or more selected from polyethylene furanoate fibers, polypropylene furanoate fibers, polybutylene furanoate fibers, and polytrimethylene furanoate fibers. . "-(CH ₂ ) _n -" in [Chemical formula 3] represents an alkylene group, where n is an integer of 2 or more and 10 or less, specifically ethylene, propylene, butylene, hexylene, heptylene, octylene, dodecylene, etc. In particular, n is preferably 2, 3, or 4. Further, the preferable degree of polymerization m is 500 to 1000.
These polyalkylene furanoate fibers are polyalkylene furanoate fibers that satisfy at least one of the following criteria: density 1.41 to 1.45 g/cm ³ , melting point 210 to 230°C, and strength (E-modulus) 3.1 to 3.3 GPa. Particularly preferred are fibers melt-spun from ate resins. Polyethylene furanoate fibers are specifically fibers melt-spun from PEF resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and polypropylene furanoate fibers are specifically fibers made from monopropylene glycol and PEF resin. Polyethylene furanoate fibers are fibers melt-spun from PPF resin obtained by polycondensation with 2,5-furandicarboxylic acid. Polytrimethylene furanoate fibers are specifically fibers melt-spun from PtMF resin obtained by polycondensation of trimethylene glycol and 2,5-furandicarboxylic acid. . In particular, polyethylene furanoate fiber is preferred because it is easy to convert into 100% biomass, and monoethylene glycol that achieves 100% biomass is produced by, for example, dehydrating Biomass ethanol produced by fermenting sugarcane sludge sugar to ethylene, and oxidizing this. These are plant-derived diols that have been converted to ethylene oxide and further hydrolyzed, making them renewable and sustainable. In addition, 2,5-furandicarboxylic acid is preferably a plant-derived compound synthesized by dehydration (generation of an oxygen-containing five-membered ring structure) and oxidation of fructose, which can be continuously regenerated. In all of the polyalkylene furanoate fibers mentioned above, the carboxylic acid of the furandicarboxylic acid serving as the raw material may be in a configuration other than the 2,5-position, the 2,3-position, the 2,4-position, or the 3,4-position. As a plant-derived compound, 2,5-furandicarboxylic acid is the easiest to synthesize. Regenerative and sustainable means a cycle in which carbon dioxide emitted from the combustion of biomass products is absorbed by plants, converting the sugars produced by the plants into biomass monomers, and thereby synthesizing biomass products.

In addition, the alkylene/furanoate/terephthalate copolymer fiber [Chemical formula 4] includes polyethylene/furanoate/terephthalate copolymer fiber, polypropylene/furanoate/terephthalate copolymer fiber, polybutylene/furanoate/terephthalate copolymer fiber, and polytriethylene/furanoate/terephthalate copolymer fiber. One or more types selected from methylene/furanoate/terephthalate copolymer fibers can be exemplified. "-(CH ₂ ) _n -" in [ Chemical formula 4 ] represents an alkylene group, where n is an integer of 2 or more and 10 or less, specifically ethylene, propylene, butylene, hexylene, heptylene, octylene, dodecylene, etc. In particular, n is preferably 2, 3, or 4.
These alkylene/furanoate/terephthalate copolymer fibers have at least one of the following properties: a density of 1.38 to 1.42 g/cm ³ , a melting point of 220 to 250°C, and a strength (E-modulus) of 2.5 to 3.0 GPa. Particularly preferred are fibers melt spun from satisfying alkylene/furanoate/terephthalate copolymer resins. Embodiments of this alkylene (Alk)/furanoate (F)/terephthalate (T) copolymer resin include 1) [-Alk-F-Alk-T-] as a repeating unit m (particularly preferably 500 to 1000); Alternating copolymer [Chemical formula 4 above], 2) Random copolymer in which the arrangement of [F] and [T] is irregular in the alternating copolymer (not shown in [Chemical formula 4] because it is random), 3) A block copolymer containing [-Alk-T-] m1 (particularly preferably m1 is 125 to 250) polymer units and [-Alk-F-] m2 (particularly preferably m2 is 375 to 750) polymer units. Chemical formula 4 below] can be exemplified, and the following specific examples also have any of the embodiments 1) to 3). Polyethylene/furanoate/terephthalate copolymer fiber is specifically a fiber melt-spun from PE/F/T resin obtained by polycondensation of monoethylene glycol, terephthalic acid, and 2,5-furandicarboxylic acid. Polypropylene/furanoate/terephthalate copolymer fiber is specifically a fiber melt-spun from PP/F/T resin obtained by polycondensation of monopropylene glycol, terephthalic acid, and 2,5-furandicarboxylic acid. Polybutylene/furanoate/terephthalate copolymer fiber is specifically a fiber melt-spun from PB/F/T resin obtained by polycondensation of monobutylene glycol, terephthalic acid, and 2,5-furandicarboxylic acid. Polytrimethylene/furanoate/terephthalate copolymer fibers were specifically melt spun from PtM/F/T resin obtained by polycondensation of trimethylene glycol, terephthalic acid, and 2,5-furandicarboxylic acid. It is a fiber. In particular, polyethylene/furanoate/terephthalate copolymer fibers are preferred because they can easily produce high biomass. Monoethylene glycol and 2,5-furandicarboxylic acid, which can provide a high biomass degree, are the same as described in paragraph [0021]. In these copolymer fibers, the terephthalic acid component is also preferably biomass terephthalic acid derived from plants. Furthermore, 1 to 99% by mass of the terephthalic acid component can be replaced with isophthalic acid or phthalic acid. (*The "/" exists to clarify the copolymerized components, and all copolymers are treated the same way.)

Weaving and knitting of the fabric used for the base material of the industrial composite sheet of the present invention (warp thread/weft thread, warp thread/upper right 30-60° bias thread/upper left 30-60° bias thread, warp thread/weft thread/ The yarns used for the upper right 30~60° bias yarn/upper left 30~60° bias yarn) are: 1) Woven fabric for tarpaulin with a porosity of about 6~25% (plain woven fabric, basket woven fabric, satin woven fabric, It is a long fiber multifilament yarn that makes up twill fabric, raschel fabric, etc., and its fineness is about 250 to 2000 denier (278 to 2222 dtex), and the number of filaments for 278 dtex is 100 to 200, and the number of filaments for 1111 dtex is 400. ~800 yarns, and may be untwisted (elliptical or flat in cross section) or twisted yarns. 2) Short fiber spun multifilament yarn that constitutes canvas fabric (plain weave, diagonal weave, satin weave, twill weave, etc.) with a porosity of about 0 to 10%, and its fineness is cotton count 10. The range of number (591 dtex) to number 60 (97 dtex), especially number 10 (591 dtex), number 14 (422 dtex), number 16 (370 dtex), number 20 (295 dtex), number 24 (246 dtex), number 30 (197 dtex), etc. In addition to these single yarns, double-twisted yarns (single-twisted yarns), yarns twisted together with two or more single yarns (ply-twisted yarns), bulky processed yarns (Taslan processed yarns, woolly processed yarns, etc.), covering yarns, etc. Yarn (core-sheath composite yarn in which short fibers of the same or different types are wound around the outer periphery of a multifilament yarn) can also be used. 3) A long-fiber multifilament yarn constituting a coarse woven fabric (plain woven fabric, mosa woven fabric, stacked net, etc.) for mesh sheets with a porosity of about 10 to 70%, and its fineness is the same as in 1). In particular, it may be a long fiber multifilament yarn (coated yarn) whose entire yarn is coated with a resin.

In the industrial composite sheet of the present invention, 1) it is a woven fabric (plain fabric, diagonal fabric, satin fabric, twill fabric, raschel fabric, etc.) with about 6 to 25% voids, woven with long fiber multifilament yarn; A tarpaulin whose base material is a woven fabric with a basis weight of 100 to 500 g/m ² is prepared by calender rolling or T-die extrusion molding a soft vinyl chloride resin composition on both sides of the base material to a thickness of 0.1 g/m2. A film that can be obtained by hot-pressure laminating films or sheets with a thickness of ~1 mm, and is placed on the front and back sides of a woven fabric with voids (voids created by entangling the axes) having a porosity of 6 to 25%. Or, by melting and integrating the sheets, the soft vinyl chloride resin layers on the front and back sides firmly adhere to the woven fabric. If the tarpaulin has a thickness of 0.4 to 1.5 mm and a mass of 500 to 2000 g/m, it can be used as a membrane roof for large tent structures (indoor sports facilities, pavilions, event halls), circus tents, tent warehouses, and architectural spaces. Suitable for raw material for membrane structures such as membrane ceilings (membrane ceilings), and raw material for flexible containers. 2) Canvas fabric (plain weave, diagonal weave, satin weave, twill weave, etc.) with a porosity of about 0 to 10%, and a fabric weight of 100 to 100%, which is woven with short fiber spun multifilament yarn. A canvas based on a 500 g/ ^m2 spun fabric is prepared by dip coating or coating a liquid material of a soft vinyl chloride resin composition on both sides of the base material, and drying the coated material. It can be obtained as a film with a thickness of 0.05 to 0.3 mm, and it is preferable that a part of the coated material is impregnated into a spun fabric. Canvas with a thickness of 0.4 to 1.0 mm and a mass of 400 to 1,500 g/m are suitable as raw material for truck hoods, tent warehouses, etc. In addition, 3) and coarse woven fabrics for mesh sheets (plain woven fabrics, mosa woven fabrics, stacked nets, etc.) with a porosity of about 10 to 70%, with a basis weight of 30 to 200 g/knitted with long fiber multifilament yarns. A mesh sheet based on a ^coarse woven fabric with a size of 0.05 to 0.3 mm is obtained by dip-coating a liquid material of a soft vinyl chloride resin composition over the entire base material and drying the coated material. It is preferable that a part of the coating material is impregnated into a coarse fabric. Moreover, it is a mesh sheet obtained by weaving and knitting a long fiber multifilament yarn (coated yarn) whose entire yarn is coated with a liquid material of a soft vinyl chloride resin composition. A mesh sheet with a thickness of 0.4 to 1.0 mm and a mass of 200 to 1000 g/m is suitable for raw materials such as architectural curing mesh sheets, wind and snow nets, anti-glare nets, and facade meshes.

On one or more surfaces of the industrial material film and industrial composite sheet of the present invention, acrylic resin, urethane resin, acrylic/silicon copolymer resin, fluorine copolymer resin, acrylic resin and fluorine copolymer resin, etc. An antifouling layer may be formed of a coating film of a blend of polymer resins, a urethane/silicon graft copolymer resin, a urethane/fluorine graft copolymer resin, or a fluororesin layer. /Aminoethylated acrylic resin epoxy cured product adhesive layer, fluororesin layer/Acrylic resin adhesive layer, fluororesin layer/Acrylic resin layer/Aminoethylated acrylic resin epoxy cured product adhesive layer, and fluororesin layer/ A fluororesin film such as an acrylic resin layer/vinyl chloride resin adhesive layer can be laminated as an antifouling layer. By applying these antifouling layers to membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) of architectural spaces, and monuments, we have dramatically improved their durability when used outdoors. let Furthermore, on the surface of these antifouling layers, there is an antistatic layer in which nanoparticles made from an inorganic colloid material with a primary particle diameter of 3 nm to 150 nm are supported on a binder component containing a hydrolyzed condensate of a silane coupling agent. An antifouling layer may be provided. Inorganic colloidal substances include 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 oxides. Metal oxides such as (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol.

The industrial material film and industrial composite sheet of the present invention can be joined and sewn by thermal fusion such as high-frequency welder fusion, hot plate fusion, hot air fusion, and ultrasonic fusion, and by machine sewing. is applicable. In particular, in the high-frequency fusion method, the soft vinyl chloride resin layers on the front and back sides are remelted by heat-generating press using a weld bar, and by reheating the fabric (base material), the adhesion effect with the fabric (yarn) is increased. Improves the creep property (preventing thread pull-out fracture) at the lap joint of the membrane structure. In particular, by using threads made of polyalkylene furanoate fibers as a constituent element of the fabric, thread removal failure does not occur at the lap joint between industrial composite sheets, and the joint strength and durability of the joint are increased. It should have excellent creep properties. The main reason for this effect is that the melting point of polyalkylene furanoate resin (fiber raw material) is 210 to 230 °C, which is 20 to 60 °C lower than the melting point of polyethylene terephthalate resin (PET fiber raw material), 250 to 270 °C. It is considered that by approaching the melting point of the resin layer of 200° C. or lower, the adhesion between the fabric and the soft vinyl chloride resin layer during manufacturing and lap bonding was effectively improved. In addition, the main reason why the strength performance and tear resistance of the industrial composite sheet body were sufficiently developed was that the strength (E-modulus) of PET resin (fiber raw material) was 2.1 to 2.2 GPa, whereas the The strength of the alkylene furanoate resin (fiber raw material) is 3.1 to 3.3 GPa, which is considered to be a good result due to the approximately 50% higher value. The main reason for the flexibility of the industrial wind sheet is that the crystallization speed when melt-spinning fibers from PET resin and stretching and cooling them is about 2 to 3 minutes, whereas the polyalkylene furano sheet In the case of ate resin (fiber raw material), it is considered that the good results are due to the crystallization being about 10 times slower, at about 20 to 30 minutes. It is also considered that similar effects due to differences in melting point, strength, and crystallization rate are fully expressed in alkylene/furanoate/terephthalate copolymer fibers.

Examples The present invention will be further explained with reference to the following examples and comparative examples, but the present invention is not limited to the scope of these examples.
Biomass degree (proof of biomass origin)
The concentration of carbon isotope " ¹⁴ C" contained in all carbon atoms constituting the polymer (detection ratio of " ¹⁴ C" and " ¹² C" in the polymer) is determined using an accelerator mass spectrometer, and " ¹⁴ The bioconversion rate is proven by the detection ratio of "C".
The amount of carbon isotope `` <sup>14C</sup> '' in the atmosphere is almost constant due to the equilibrium between `` ^14C '' production by cosmic rays and radioactive decay (half-life approximately ^5,730 years). It is accumulated in plants through photosynthesis and then distributed among animals in the food chain, so the concentration of ^14C (detection ratio of ^14C and ^12C ) in all living things on earth is almost constant. On the other hand, since petroleum is a biological material that is 100 to 200 million years old, the concentration of ¹⁴ C in petroleum has long passed its half-life and is considered virtually zero, making it difficult to produce biomass-derived products. contains a certain concentration of ^14C , and petroleum-derived products do not contain ^14C . Therefore, measuring the " ¹⁴ C" concentration (detection ratio of " ¹⁴ C" and " ¹² C") can prove that it is a biomass-derived product.

[Example 1]
<Tarpaulin made of fabric (1)>
1000 d of polyethylene phenolate (PEF) fibers made by melt-spinning 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) (1111dtex) multifilament yarn (192 filaments), S twist 200T/m as warp group and weft group, setting density of 19 warps/inch x 20 wefts/inch, mass 190g/ A fabric (1) with a size of 1.2 m ² and a porosity of 10% is used.
*Polyethylene phenolate (PEF) fibers are melt-spun from polyethylene phenolate (PEF) resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and all polymerized monomers are derived from biomass. Monoethylene glycol is a compound obtained by dehydrating biomass ethanol from fermentation of sugarcane sludge to produce biomass ethylene, oxidizing this to biomass ethylene oxide, and further hydrolyzing it, and 2,5- Furandicarboxylic acid is a plant-derived compound synthesized by dehydrating fructose (creating an oxygen-containing five-membered ring structure) and oxidizing it, and the resulting polyethylene phenolate (PEF) fiber has a biomass content of 100%. The fabric (1) having yarn as a weaving/knitting element also has a biomass degree of 100%.
<Manufacture of tarpaulin>
A film with a thickness of 0.16 mm was formed on both sides of the fabric (1) by calender molding at 165°C to 180°C from a soft vinyl chloride resin compound of the following [Formulation 1], and a film was rolled at 170°C using a laminator. If they are laminated in a softened state, an industrial composite sheet (1) in the form of a tarpaulin with a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass content of this industrial composite sheet (1) is theoretically approximately 100% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*The molded film of [Formulation 1] with a thickness of 0.16 mm can be used separately as an industrial material film of the present invention.
[Formulation 1] Soft vinyl chloride resin compound composition Vinyl chloride resin obtained by suspension polymerization (degree of polymerization 1300) 100 parts by mass *Biomass ethylene obtained by dehydrating Biomass ethanol produced by fermentation of sugarcane sludge sugar is chlorinated. Biomass polymer produced by radical polymerization of vinyl chloride monomer Diisononyl 2,5-furandicarboxylate (plasticizer) 60 parts by mass *Synthesized by the reaction (esterification) of 2,5-furandicarboxylic acid and isononyl alcohol, , 5-furandicarboxylic acid is derived from plants and is synthesized by dehydrating fructose (creating an oxygen-containing 5-membered ring structure) and oxidizing it, and isononyl alcohol is produced via Biomass alcohol by fermenting sugarcane sludge sugar. Compounds with 100% biomass content Epoxidized soybean oil (partial biomass plasticizer) 10 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Rutile titanium dioxide (white pigment) 5 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass

[Example 2]
<Canvas made from fabric (2)>
Polyethylene phenolate (PEF) short fiber spun by melt-spinning 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) Plain weave spun cloth made of yarn (S twist 600T/m), warp 20 count twin yarn (590 dtex) 46 pieces/inch x weft 20 count twin yarn (590 dtex) 42 pieces/inch: porosity 5%: mass 228 g/ ^m2 is used for the fabric (2).
*Polyethylene phenolate (PEF) fibers are made by cutting long fibers into 4-10 cm long fibers that are melt-spun from polyethylene phenolate (PEF) resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid. In the staple-spun yarn, all polymerized monomers are biomass-derived compounds, and monoethylene glycol is produced by dehydrating biomass ethanol from fermentation of sugarcane sludge to produce biomass ethylene, which is then oxidized to produce biomass ethylene oxide. 2,5-Furandicarboxylic acid is a biomass-derived compound synthesized by dehydrating fructose (creating an oxygen-containing five-membered ring structure) and oxidizing it, and the resulting polyethylene phenolate. The (PEF) fiber becomes a spun yarn derived from 100% biomass, and the fabric (2) using this spun yarn as a weaving or knitting element also has a biomass content of 100%.
<Manufacture of canvas>
Fabric (2) is immersed in a liquid bath filled with the soft vinyl chloride resin paste sol composition of [Formulation 2] below, and the fabric (2) is dip-impregnated with the paste sol composition of [Formulation 2]. At the same time as fabric (2) is pulled up, it is compressed with a rubber roll and then heated in a hot air oven at 180°C for 3 minutes to complete the gelation of the paste-sol composition of [Formulation 2], and the fabric (2) is impregnated with soft vinyl chloride resin. An industrial composite sheet (2) in the form of a canvas having a thickness of 0.47 mm and a mass of 560 g/m ² with soft vinyl chloride resin layers formed on both sides of the fabric (2) is obtained. The biomass content of this industrial composite sheet (2) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, ultraviolet absorbers, and curing agents).
[Formulation 2] Soft vinyl chloride resin paste sol composition Vinyl chloride resin obtained by emulsion polymerization (degree of polymerization 1700) 100 parts by mass * Biomass ethylene obtained by dehydrating biomass ethanol obtained by fermentation of sugarcane sludge sugar with chlorine. Biomass polymer produced by radical polymerization of converted vinyl chloride monomer Diisononyl 2,5-furandicarboxylate (plasticizer) 60 parts by mass *Synthesized by reaction (esterification) of 2,5-furandicarboxylic acid and isononyl alcohol 2,5-furandicarboxylic acid is synthesized from plants by dehydrating fructose (creating an oxygen-containing five-membered ring structure) and oxidizing it, and isononyl alcohol is synthesized from biomass by fermenting sugarcane sludge sugar. Compounds with 100% biomass via alcohol Epoxidized soybean oil (partial biomass plasticizer) 10 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Rutile titanium oxide (white pigment) 5 parts by mass Cyanine green (green pigment) 5 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass Isocyanurate-modified triisocyanate (curing agent) 5 parts by mass

[Example 3]
<Mesh sheet made of fabric (3)>
Made of polyethylene phenolate (PEF) fibers made by melt-spinning 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). The yarn density was ``750d (833dtex), number of filaments: 147, S twist: 200T/m: /3 strands'' was used as the warp and warp threads, and the weft threads were woven with 8 warp threads/inch and 9 weft threads/inch. , a coarse fabric (3) having a mass of 195 g/m ² and a porosity of 15% is used.
*Polyethylene phenolate (PEF) fibers are melt-spun from polyethylene phenolate (PEF) resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and all polymerized monomers are derived from biomass. Monoethylene glycol is a compound obtained by dehydrating Biomass ethanol produced by fermentation of sugarcane sludge to produce Biomass ethylene, oxidizing this to Biomass ethylene oxide, and further hydrolyzing it, and 2,5-furandicarboxylic acid. is a biomass-derived compound synthesized by dehydrating fructose (creating an oxygen-containing five-membered ring structure) and oxidizing it. The resulting polyethylene phenolate (PEF) fiber has a biomass content of 100%, and this fiber thread is woven. The coarse fabric (3) used as a knitting element also has a biomass degree of 100%.
<Manufacture of mesh sheets>
The fabric (3) is immersed in a liquid bath filled with the above-mentioned soft vinyl chloride resin paste sol composition of [Formulation 2], and the fabric (3) is dip-impregnated with the paste sol composition of [Formulation 2], When the fabric (3) is pulled up and simultaneously compressed with a rubber roll and heated in a hot air oven at 180°C for 3 minutes to complete the gelation of the paste-sol composition of [Formulation 2], the soft vinyl chloride resin is formed on the fabric (3). An industrial composite sheet (3) in the form of a mesh sheet with a thickness of 0.42 mm, a mass of 465 g/m ² and a porosity of 13% is obtained, which is impregnated and has a soft vinyl chloride resin layer formed on the entire surface of the fabric (3). . The biomass content of this industrial composite sheet (3) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, ultraviolet absorbers, and curing agents).

[Example 4]
Same as Example 1 except that diisononyl 2,5-furandicarboxylate: Mw408 in [Formulation 1] of Example 1 was completely replaced with diisodecyl 2,5-furandicarboxylate: Mw436 to form [Formulation 3]. In this way, an industrial 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 content of this industrial composite sheet (4) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*The molded film of [Formulation 3] with a thickness of 0.16 mm can be used separately as an industrial material film of the present invention.

[Example 5]
The procedure was carried out except that 30 parts by mass of 60 parts by mass of diisononyl 2,5-furandicarboxylate in [Formulation 1] of Example 1 was replaced with 30 parts by mass of polyglycerin/oleic acid monoester to form [Formulation 4]. If the procedure is the same as in Example 1, an industrial composite sheet (5) in the form of a tarpaulin with a thickness of 0.75 mm and a mass of 915 g/m ² will be obtained. The biomass content of this industrial composite sheet (5) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*Polyglycerin/oleic acid monoester is a 100% biomass monoester made by esterifying polyglycerin and oleic acid. Oleic acid (CH ₃ (CH ₂ ) ₇ CH=CH(CH ₂ ) ₇ COOH) is a biomass-derived glycerin dimer (average degree of polymerization n=2) obtained by isolation and dehydration condensation. Uses plant-derived products refined from olive oil.
*The molded film of [Formulation 4] with a thickness of 0.16 mm can be used separately as an industrial material film of the present invention.

[Example 6]
Example 1 except that 30 parts by mass of 60 parts by mass of diisononyl 2,5-furandicarboxylate in [Formulation 1] of Example 1 was replaced with 30 parts by mass of polyglycerin/linoleic acid diester to form [Blend 5]. 1, a tarpaulin-like industrial composite sheet (6) having a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass content of this industrial composite sheet (6) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*Polyglycerin/linoleic acid diester is a 100% biomass diester obtained by esterifying polyglycerin and linoleic acid. Polyglycerin is obtained by isolating glycerin, which is a by-product during the production of fatty acid methyl ester through the transesterification reaction of fats and oils and methanol. , is a biomass-derived glycerin dimer (average degree of polymerization n=2) obtained by dehydration condensation of linoleic acid (CH ₃ (CH ₂ ) ₄ (CH=CHCH ₂ ) ₂ (CH ₂ ) ₆ COOH). uses a plant-derived product refined from safflower oil.
*The molded film of [Formulation 5] with a thickness of 0.16 mm can be used separately as an industrial material film of the present invention.

[Example 7]
The procedure was carried out except that 30 parts by mass of 60 parts by mass of diisononyl 2,5-furandicarboxylate in [Formulation 1] of Example 1 was replaced with 30 parts by mass of polyglycerin/myristate triester to form [Formulation 6]. If the procedure is the same as in Example 1, an industrial composite sheet (7) in the form of a tarpaulin with a thickness of 0.75 mm and a mass of 915 g/m ² will be obtained. The biomass content of this industrial composite sheet (7) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*Polyglycerin/myristic acid triester is a 100% biomass triester made by esterifying polyglycerin and myristic acid. Myristic acid (CH ₃ (CH ₂ ) ₁₂ COOH) is a biomass-derived glycerin dimer (average degree of polymerization n = 2) obtained by dehydration condensation. Use the one.
*The molded film of [Formulation 6] with a thickness of 0.16 mm can be used separately as an industrial material film of the present invention.

[Example 8]
If the procedure is the same as in Example 1 except that the fabric (1) in Example 1 is replaced with fabric (4), an industrial composite sheet (8) in the form of a tarpaulin with a thickness of 0.75 mm and a mass of 908 g/m ² is obtained. The biomass content of this industrial composite sheet (8) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (4)>
Polyethylene/phenolate made by melt-spinning polyethylene/phenolate/terephthalate alternating copolymer resin (density 1.40 g/cm ³ , melting point 230-240°C, glass transition temperature Tg 82°C, strength: E-modulus 2.6-2.7 GPa) /1000d (1111dtex) multifilament yarn (192 filaments) made of terephthalate (PE/F/T) fiber, S twist 200T/m as warp group and weft group, 19 warps/inch x 20 wefts A fabric (4) with a mass of 180 g/m ² and a porosity of 10% is used, with a driving density of books/inch. The fabric (4) has a biomass degree of 100% due to the following monomer composition.
*Polyethylene/phenolate/terephthalate (PE/F/T) fiber is a copolymer obtained by polycondensation of 50 mol% monoethylene glycol, 25 mol% 2,5-furandicarboxylic acid, and 25 mol% terephthalic acid. It is melt-spun from a composite (PE/F/T) resin, and monoethylene glycol is produced by dehydrating bioethanol from fermentation of sugarcane sludge to produce ethylene, oxidizing this to ethylene oxide, and then adding water. 2,5-furandicarboxylic acid, a decomposed biomass-derived monomer, is a plant-derived monomer synthesized by dehydrating fructose (creating an oxygen-containing five-membered ring structure) and oxidizing it, and terephthalic acid is a plant-derived monomer synthesized by fermentation of corn sugar. It is a plant-derived monomer that is obtained by dehydrating isobutanol to produce isobutylene, and converting paraxylene obtained by dimerization and cyclization through radical reactions into terephthalic acid.

[Example 9]
If the procedure is the same as in Example 1 except that the fabric (1) in Example 1 is replaced with fabric (5), an industrial composite sheet (9) in the form of a tarpaulin with a thickness of 0.77 mm and a mass of 913 g/m ² is obtained. The biomass content of this industrial composite sheet (9) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (5) Triaxial plain woven fabric>
A 1000 d (1111 dtex) multifilament yarn (192 filaments, S twist 200 T/m) made of polyethylene phenolate (PEF) fibers melt-spun from the Biomass polyethylene phenolate resin used in Example 1 was used in the warp group and the upper left bias yarn group. /Used in the upper right bias thread group, the warp group has a weave structure of 13 threads per inch, and the upper left bias thread group/upper right bias thread group each have a weave structure of 13 threads per inch, mass 188 g/m ² , porosity ( A triaxial plain woven fabric with a total cutout area of 10% is used for the fabric (5). The biomass degree of this fabric (5) is 100%.

[Example 10]
Assuming the same as in Example 1 except that the fabric (1) in Example 1 was replaced with fabric (6), an industrial composite sheet (10) in the form of a tarpaulin with a thickness of 0.80 mm and a mass of 919 g/m ² is obtained. The biomass content of this industrial composite sheet (10) is theoretically approximately 100% (excluding additives such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (6) Four-axis plain woven fabric>
A 1000 d (1111 dtex) multifilament yarn (192 filaments, S twist 200 T/m) made of polyethylene phenolate (PEF) fibers melt-spun from the Biomass polyethylene phenolate resin used in Example 1 was used as a warp group, a weft group, and upper left bias yarn group/upper right bias yarn group, the warp group and weft group have a weave structure of 10 threads per inch, and the upper left bias thread group/upper right bias thread group each have a weave structure of 10 threads per inch.The mass is A four-axis plain woven fabric with a porosity of 194 g/m ² and a porosity (total of open areas) of 8% is used for the fabric (6). The biomass degree of this fabric (6) is 100%.

[Reference example 1]
The following acrylic resin paint of [Formulation 7] was applied to both sides of the industrial composite sheet (1) with 100% biomass content using a 100-mesh gravure roll and dried by heating in a hot air oven at 120°C for 2 minutes. Then, an acrylic resin coating layer (5 g/m ² /one side) was formed on the front and back sides to obtain intermediate A (1).
[Formulation 7] Acrylic resin paint methacrylic acid alkyl ester/acrylic acid alkyl ester copolymer
100 parts by mass Methyl ethyl ketone (MEK diluent) 250 parts by mass Toluene (diluent) 250 parts by mass Next, a solution of the aminoethylated acrylic resin epoxy composition of [Formulation 8] below was applied to one surface of this intermediate A (1). Intermediate B, which is coated with a 100 mesh gravure roll, heated and dried in a hot air oven at 120°C for 2 minutes, and has an acrylic resin coating layer (5 g/m ² / one side) attached to the surface side in a semi-cured state. (1).
[Formulation 8] Aminoethylated acrylic resin epoxy composition: methacrylic acid alkyl ester/acrylic acid alkyl ester/methacrylic acid copolymer. Polyethyleneimine is grafted onto the carboxyl group of the product.
The amine value whose side chain is represented by the chemical formula -COO(CH ₂ CH ₂ NH) _n H (solid content 1g
0.7 to 1.3 mmol/g of primary amino group-containing acrylic resin
100 parts by mass Epoxy resin (bisphenol A skeleton-containing trifunctional epoxy resin with epoxy equivalent of 260 g/eq) 20 parts by mass Methyl ethyl ketone (MEK diluent) 150 parts by mass Toluene (diluent) 150 parts by mass Next, this intermediate B (1 ) The corona treated side of a polyvinylidene fluoride (PVdF) film with a thickness of 25 μm and 53 g/m ² was placed opposite to the side of the semi-cured aminoethylated acrylic resin epoxy layer, and the film was heated using a laminator at 150°C. By forming an antifouling layer by laminating a fluororesin film that is passed through and heat-pressed, this industrial composite has excellent soot and dust stain prevention properties and rain streak stain prevention properties, and its beautiful appearance can be restored by wiping and cleaning. A sheet (11) is obtained. Theoretically, the biomass content of this industrial composite sheet (11) is approximately 93%.

[Comparative example 1]
Example 1 is the same as Example 1 except that [Formulation 1] in Example 1 is changed to [Formulation 9]. Tarpaulin-type industrial composite sheet (12) with a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass content of this industrial composite sheet (12) is theoretically about 23% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers). It is clear that more than half of the carbon dioxide generated during disposal does not meet carbon neutrality, making little contribution to building a low-environmental load and low-carbon society.
[Formulation 9] Soft vinyl chloride resin compound composition Vinyl chloride resin obtained by suspension polymerization (degree of polymerization 1300) 100 parts by mass *Polymer made from petroleum-derived ethylene as a chlorinated vinyl chloride monomer Diisononyl phthalate (plasticizer) 60 parts by mass Parts Epoxidized soybean oil (partial biomass plasticizer) 10 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Rutile titanium dioxide (white) Pigment) 5 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass

[Comparative example 2]
Assuming the same as Example 1 except that fabric (1) in Example 1 was changed to fabric (7) and [Blend 1] was changed to [Blend 9], the thickness was 0.75 mm, the mass was 904 g/ An industrial composite sheet (13) in the form of a tarpaulin of m ² is obtained. The biomass content of this industrial composite sheet (13) is approximately 3% due to 10 parts by mass of epoxidized soybean oil (partial biomass plasticizer). If the biomass content is around 3%, almost all of the carbon dioxide generated during incineration of this industrial composite sheet does not meet carbon neutrality, and it is clear that there is little contribution to creating a low environmental impact and low carbon society. It is.
<Fabric (7)>
1000 d of polyethylene phenolate (PET) fibers made by melt-spinning polyethylene tereftate 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) (1111 dtex) multifilament yarn (192 filaments), S twist 200T/m as warp group and weft group, driving density of 19 warp yarns/inch x 20 weft yarns/inch, mass 179 g/ A fabric (7) with a size of 1.2 m ² and a porosity of 10% is used.
*Polyethylene terephtate resin is synthesized from petroleum-derived ethylene glycol and petroleum-derived terephthalic acid.

According to the industrial material films and sheets of the present invention, most of the carbon dioxide generated during incineration is carbon neutral (raw materials and products derived from carbon dioxide absorbed by plants return to nature as carbon dioxide, In particular, industrial material films are used in agriculture and horticulture because they can contribute to the realization of a low-environmental load and low-carbon society that can suppress the increase in the amount of carbon dioxide emitted. Widely used for plastic greenhouses, medical clean booths, industrial clean booths, partitions for public facilities, protective coverings for automobiles and railway vehicles, protective coverings for floors and walls, waterproof coverings for roofs and ceilings, etc. Industrial composite sheets are expected to be used in large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs for architectural spaces (membrane ceilings), visual facades, Tarpaulins used for flexible containers, elevating sheet shutters, floor sheets, partition sheets, etc.; Canvas used for truck hoods, outdoor waterproof sheets, house tents, etc.; architectural curing mesh sheets, windproof and snowproof nets, anti-glare nets, sunshade facades. It is expected that it will be widely used in mesh sheets used in other applications.

Claims (4)

A soft vinyl chloride resin layer made of a composition containing at least a vinyl chloride resin and a furandicarboxylic acid dialkyl ester compound [Chemical formula 1] is formed on one or more surfaces of the fabric, using a fabric as a base material , An industrial composite sheet characterized in that the fabric contains multifilament yarns made of polyalkylene furanoate [Chemical formula 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical formula 4] fibers in the weaving and knitting elements.
The industrial composite sheet according to claim 1 , wherein the composition further contains one or more polyglycerin fatty acid ester compounds [chemical formula 2].
1) the polyalkylene furanoate fiber is one or more selected from polyethylene furanoate fiber, polypropylene furanoate fiber, polybutylene furanoate fiber, and polytrimethylene furanoate fiber, and 2) the above alkylene/furanoate/ The terephthalate copolymer fibers are polyethylene/furanoate/terephthalate copolymer fibers, polypropylene/furanoate/terephthalate copolymer fibers, polybutylene/furanoate/terephthalate copolymer fibers, and polytrimethylene/furanoate/terephthalate copolymer fibers. The industrial composite sheet according to claim 1, which is one or more selected types. The weaving and knitting elements of the fabric are warp/weft, warp/upper right 30-60° bias yarn/upper left 30-60° bias yarn, warp/weft/upper right 30-60° bias yarn/ The industrial composite sheet according to claim 1 , which is one type selected from upper left 30 to 60° bias yarn.