JP2023018433A - Industrial material film and industrial composite sheet - Google Patents

Abstract

To provide a regenerative recycling industrial material film which is made of a soft vinyl chloride resin including at least a specific plasticizer, and a regenerative recycling industrial composite sheet such as a tarpaulin, a canvas and a mesh sheet which is made of a soft vinyl chloride resin layer including at least a specific fabric and a specific plasticizer.SOLUTION: An industrial material film is provided which is composed of a composition containing at least a vinyl chloride-based resin and a polyglyceryl fatty acid ester compound, and as necessary, further containing a furandicarboxylic acid dialkyl ester compound. An industrial composite sheet is provided having a fabric as a base material, and having a soft vinyl chloride resin layer which is composed of a composition containing at least a vinyl chloride-based resin and a polyglyceryl fatty acid ester compound, and as necessary, further containing a furandicarboxylic acid fatty acid ester compound formed on one or more surfaces of the fabric.SELECTED DRAWING: None

Description

The present invention relates to vinyl greenhouses for agriculture and gardening, simple clean booths for medical use, simple clean booths for industrial use, partitions for public facilities, covering protective materials for automobiles and railway vehicles, covering protective materials for floors and walls, and waterproofing for roofs and ceilings. Industrial material films used for coating materials, large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, visual façades, Tarpaulins used for flexible containers, lifting type sheet shutters, floor sheets, partition sheets, etc., canvas used for truck hoods, open-air waterproof sheets, house tents, etc., architectural curing mesh sheets, wind and snow nets, anti-glare nets, sun-exposed facades The present invention relates to an industrial composite sheet such as a mesh sheet used for, for example. More specifically, it relates to a recycled and recyclable industrial material film made of a soft vinyl chloride resin containing at least a plasticizer synthesized from a plant-derived substance, and a polyalkylene furanoate fiber thread or an alkylene furanoate-containing copolymer fiber thread. Recycled and recycled industrial composite sheets such as tarpaulins, canvases, and mesh sheets based on fabrics made of fabrics with The present invention relates to a recycling-type industrial composite sheet comprising a resin layer. In the present specification, biomass-derived means derived from animals and plants, and recycling type mainly means carbon-neutral.

Large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, façade sheets, flexible containers, elevating sheet shutters, floor sheets, Industries such as tarpaulin used for partition sheets, canvas used for truck hoods, open-air waterproof sheets, roof tents, etc., mesh sheets used for architectural protection mesh sheets, wind and snow nets, anti-glare nets, facade meshes, etc. As the base material of the composite sheet for industrial use, a fabric is used, the weaving element of which is a polyester fiber thread spun from polyethylene terephthalate (hereinafter referred to as PET resin). In particular, a tarpaulin is obtained by laminating thermoplastic resin composition films on both sides of a fabric (woven fabric) having a porosity of about 6 to 25%, and a liquid thermoplastic resin composition on both sides of the fabric having a porosity of about 0 to 10%. is impregnated and coated to form a film, which is a canvas, and a liquid thermoplastic resin composition is impregnated and coated on the entire surface of a coarse fabric having a porosity of about 15 to 70%, and the coated product is formed into a film. A thing is a mesh sheet. Converting the PET resin fabric synthesized using a petroleum-based material used as the base material of these industrial composite sheets to a PET resin fabric synthesized using a plant as a starting material is a low-cost method that does not increase the amount of carbon dioxide. It is one of the proposals for a low-carbon society with an environmental impact.

On the other hand, in recent years, a recycling business that uses waste PET bottles as raw materials to produce fibers (carpets, clothes), sheets, molded products (stationery, sundries, containers), etc. has become established, but the quality of the collected PET bottles varies greatly. The quality and physical properties of the recycled products were inferior. In recent years, however, the recycling awareness of recycling PET bottles for beverages immediately has become widely established, and it has become possible to stably obtain high-quality recovered PET bottles with little quality deterioration, which was not possible before. , "bottle-to-bottle" horizontal recycling that recycles into new PET bottles for beverages has been realized. The background to this is the predicted depletion of petroleum, which is the raw material for plastics, the global warming of carbon dioxide generated by the incineration of plastics (abnormal weather, wind and flood damage, rising water levels, ecosystem abnormalities, etc.), and the ocean caused by degraded plastics (microplastic particles). Problems such as pollution and damage to organisms have become urgent, and various efforts are being made not only to reduce plastic waste, but also to substitute natural products and depolymerize waste plastics to make fuel. Recently, there has been advocated conservation of the global environment by replacing plastics with low-environmental-load products, and in particular, replacement of PET resins, which are widely used worldwide, with PET resins synthesized from plant-derived substances is under study. This plant-derived PET resin is synthesized from Biomass ethylene glycol and Biomass terephthalic acid. Biomass ethylene glycol is a diol obtained by dehydrating bioethanol from fermentation of sugar cane molasses, for example, to ethylene, oxidizing it to ethylene oxide, and hydrolyzing it. Isobutylene is obtained by dehydrating isobutanol by fermentation, and paraxylene obtained by dimerization and cyclization by radical reaction is converted to terephthalic acid. However, the production process of Biomass terephthalic acid becomes complex with multiple steps, and the energy involved in the entire process increases, so 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 attached to chemical substance nouns is referred to as Biomass to avoid misunderstanding due to consecutive katakana notation. , and the following paragraphs as well)

On the other hand, attention is being paid to polyalkylene furanoate resins as an alternative to PET resins. In particular, polyethylene furanoate resin (hereafter 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 a biomass diol obtained by dehydrating Biomass ethanol obtained by fermenting sugar cane molasses to obtain Biomass ethylene, oxidizing this to obtain Biomass ethylene oxide, and further hydrolyzing Biomass diol. Biomass 2,5-furandicarboxylic acid is synthesized by dehydration of fructose (formation of oxygen-containing five-membered ring structure) and oxidation, so a biomass degree of 100% is possible. Specifically, PEF resin is used in a multi-layer container having a gas barrier layer, and Patent Document 1 discloses an invention of a gas-barrier multi-layer container in which the PEF resin is a PEF resin obtained from Biomass polyethylene glycol and Biomass furandicarboxylic acid. there is In addition, Patent Document 2 discloses an invention of a lightweight and high-strength container (resin molded product) containing a terephthalate-based polyester resin and a PEF resin, wherein the proportion of the PEF resin is 2 to 25% by mass. It is The multi-layered polyester resin container of Patent Document 1 and the resin container made of the 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 reusability, but they are resources with high reuse potential. Horizontal recycling is difficult because of the structure and resin blend.

Therefore, if a plant-derived biomass resin that is easier to synthesize and has performance equal to or higher than that of petroleum-derived PET resin is developed, it will be possible to obtain a recycled biomass fabric using fibers spun from the plant-derived resin. At the same time, high biomass is being promoted for constituent materials such as a thermoplastic resin composition film that coats biomass fabric and a thermoplastic resin composition film that impregnates and coats biomass fabric, especially in soft vinyl chloride resin compositions. , its main component vinyl chloride resin, and plasticizer, if it is possible to rationally de-dependence on petroleum in the synthesis process, a more recyclable industrial composite sheet will become a reality. Furthermore, the thermoplastic resin composition film constituting the industrial composite sheet can also be widely used as a recycling-type industrial material film by itself. Moreover, by switching to such recycling-type industrial material films and industrial composite sheets, even if they are incinerated, the carbon dioxide generated is carbon-neutral (bio-resins derived from carbon dioxide absorbed by plants can be recycled again). As a campaign that can contribute to the conservation of the global environment, it is desired to develop and put it into practical use as soon as possible.

JP 2018-199258 A JP 2018-104070 A

The present invention provides a recyclable industrial material film made of a soft vinyl chloride resin containing at least a specific plasticizer, and a tarpaulin comprising a specific cloth and a soft vinyl chloride resin layer containing at least a specific plasticizer, An object of the present invention is to provide recycle-type 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 in the cycle of returning to and being absorbed by plants again), and can contribute to the realization of a low environmental impact and low carbon society that can suppress the increase in the amount of carbon dioxide in the global environment. In the present invention, the recycling type mainly means carbon neutral.

As a result of repeated studies in consideration of such points, the present invention has found that 1) an industrial material film made of a composition containing at least a vinyl chloride resin and a specific polyglycerol fatty acid ester compound, and 2) a specific fabric as a base material As 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 polyglycerol fatty acid ester compound is formed on one or more surfaces of a specific fabric is carbon neutral The present invention has been completed by discovering that it can be a recycled and circulated product by conforming to the above.

＊式中Ｒはアルキル基

That is, the industrial material film of the present invention is preferably composed of a composition containing at least one of a vinyl chloride resin and a polyglycerin fatty acid ester compound [Formula 1], and the composition is a dialkyl furandicarboxylate The compound [Formula 2] can be further included. Polyglycerin fatty acid ester compound [Formula 1] is a plasticizer synthesized by reaction (esterification) of glycerin and fatty acid. Those synthesized from plant-derived substances are preferred. Furandicarboxylic acid dialkyl ester compound [Formula 2] is a plasticizer synthesized by reaction (esterification) of furandicarboxylic acid and alcohol, especially those synthesized from plant-derived substances with furandicarboxylic acid and alcohol. preferable. Vinyl chloride-based resins are obtained by radical polymerization of vinyl chloride-based monomers, and vinyl chloride-based monomers synthesized from plant-derived substances are particularly preferred. [Chemical 1] and vinyl chloride-based resin, or [Chemical 1], [Chemical 2] and vinyl chloride-based resin are most preferably synthesized from plant-derived substances, but at least [Chemical 1] is It is preferably a compound synthesized from a plant-derived substance, and [Chemical 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 structure are incinerated, the carbon dioxide generated from it is carbon neutral (a biomass film derived from carbon dioxide absorbed by plants returns to nature, Theoretically, it can be a recycle-type industrial material film.

*In the formula, R is an alkyl group

＊式中Ｒはアルキル基

In the industrial composite sheet of the present invention, a fabric is used as a base material, and a soft vinyl chloride resin layer made of a composition containing at least one of a vinyl chloride resin and a polyglycerin fatty acid ester compound [Formula 1] is It is preferably formed on one or more surfaces of the fabric, and the composition may further contain a furandicarboxylic acid dialkyl ester compound [Formula 2]. Polyglycerin fatty acid ester compound [Formula 1] is a plasticizer synthesized by reaction (esterification) of glycerin and fatty acid. Those synthesized from plant-derived substances are preferred. Furandicarboxylic acid dialkyl ester compound [Formula 2] is a plasticizer synthesized by reaction (esterification) of furandicarboxylic acid and alcohol, especially those synthesized from plant-derived substances with furandicarboxylic acid and alcohol. preferable. Vinyl chloride-based resins are obtained by radical polymerization of vinyl chloride-based monomers, and vinyl chloride-based monomers synthesized from plant-derived substances are particularly preferable. [Chemical 1] and vinyl chloride-based resin, or [Chemical 1], [Chemical 2] and vinyl chloride-based resin are most preferably synthesized from plant-derived substances, but at least [Chemical 1] is It is preferably a compound synthesized from a plant-derived substance, and [Chemical 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 structure are incinerated, the carbon dioxide generated is carbon neutral (a biomass film derived from carbon dioxide absorbed by plants returns to nature and can be theoretically recycled and recycled for industrial use.

*In the formula, R is an alkyl group

In the composite sheet for industrial use of the present invention, the cloth contains multifilament yarns made of polyalkylene furanoate [Chem. 3] fibers or alkylene/furanoate/terephthalate copolymer [Chem. 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 alkylene /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 preferably one or more selected from united fibers. The polyalkylene furanoate [Chemical Formula 3] is obtained by polycondensation of alkylene glycol and furandicarboxylic acid, and it is particularly preferred that the alkylene glycol and furandicarboxylic acid are synthesized from plant-derived substances. Alkylene/furanoate/terephthalate copolymer [Formula 4] is an alternating or random copolymer or block copolymer obtained by polycondensation of alkylene glycol with furandicarboxylic acid and terephthalic acid. Carboxylic acids and terephthalic acids synthesized from plant-derived substances are most preferred. At least alkylene glycol and furandicarboxylic acid are preferably 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 structure are incinerated, the carbon dioxide generated is carbon neutral (a biomass film derived from carbon dioxide absorbed by plants returns to nature, In theory, it can be a recycling-type industrial composite sheet by fulfilling the requirement that it is counted in the cycle in which it is reabsorbed by plants.

In the industrial composite sheet of the present invention, the weaving and knitting elements of the fabric are warp/weft, warp/upper right 30 to 60° bias yarn/upper left 30 to 60° bias yarn, warp/weft/ It is preferably one type selected from upper right 30 to 60° bias yarn/upper left 30 to 60° bias yarn. Here, "warp/weft" is a biaxial fabric, "warp/upper right 30 to 60° bias yarn/upper left 30 to 60° bias yarn" is triaxial fabric, and "warp/weft/upper right 30" ~60° Bias Yarn/Upper Left 30-60° Bias Yarn” refers to a tetraaxial fabric. In particular, by using triaxial woven fabrics and tetraaxial woven fabrics as base materials, the resulting industrial composite sheets are extremely excellent in dimensional stability, breaking strength, penetration resistance, and tear resistance. 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 shattered objects at blast construction sites, and equipment for receiving falling objects 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). It is counted in the recycling cycle in which plants absorb it again), and it can contribute to the realization of a low-environmental-load and low-carbon society that can curb the increase in carbon dioxide emissions. Widely used for greenhouses for horticulture, simple clean booths for medical use, simple clean booths for industrial use, partitions for public facilities, covering protective materials for automobiles and railway vehicles, covering protective materials for floors and walls, waterproof covering materials for roofs and ceilings, etc. Industrial composite sheets are also expected to be used in large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, and visual façades. , flexible containers, liftable sheet shutters, floor sheets, tarpaulins used for partition sheets, etc., and canvas used for truck hoods, open-air waterproof sheets, house tents, etc., architectural curing mesh sheets, wind and snow nets, anti-glare nets, and sunscreens. It is expected to be widely used for mesh sheets used in facades and the like.

A) The industrial material film of the present invention is an embodiment (Aa) comprising a composition containing at least a vinyl chloride resin and a polyglycerin fatty acid ester compound, and this composition further contains a furandicarboxylic acid dialkyl ester compound. It is the aspect (Ab) containing. In addition, in the recycled recycling type B) industrial composite sheet of the present invention, a fabric is used as a base material, and a soft vinyl chloride resin layer made of a composition containing at least a vinyl chloride resin and a polyglycerol fatty acid ester compound is formed on the fabric. It is an embodiment (Ba) formed on one or more surfaces, and it is an embodiment (Bb) in which the composition further comprises a furandicarboxylic acid dialkyl ester compound, and the fabric is a polyalkylene furanoate fiber or an alkylene/furanoate/ It is an embodiment (Bc) in which a multifilament yarn made of a terephthalate copolymer fiber is included in the weaving and knitting elements, and the weaving and knitting elements of the fabric are warp/weft, warp/upper right 30 to 60° bias yarn/ This is an embodiment (Bd) which is one type selected from upper left 30 to 60° bias yarn, warp/weft/upper right 30 to 60° bias yarn/upper left 30 to 60° bias yarn.

The industrial material film of the present invention is a soft vinyl chloride resin (plasticizer-containing) composition, and is mainly composed of 100 parts by mass of straight vinyl chloride resin (fine particles) obtained by suspension polymerization and 30 to 100 parts by mass of a plasticizer. As stabilizers for vinyl chloride resins, calcium-zinc composite stabilizers, barium-zinc composite stabilizers, organic tin laurate stabilizers, organic tin mercaptite stabilizers, epoxy stabilizers, and the like can be optionally used. Pigments, flame retardants, fillers, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, cross-linking agents and the like can be optionally used as necessary. Preferably, the soft vinyl chloride resin composition is calender rolled or T-die extruded to a thickness of 0.1 to 1 mm. The main plasticizer in such a resin composition is one or more polyglycerol fatty acid ester compounds [Chemical 1], and the plasticizer that can be additionally included in this composition is a furandicarboxylic acid dialkyl ester compound [Chemical 2]. Similarly, the recycled recycling type industrial material sheet of the present invention includes: 1) a tarpaulin formed by laminating a soft vinyl chloride resin film on one or more sides of a cloth substrate; 3) A mesh sheet formed by forming a soft vinyl chloride resin-impregnated coating layer on both sides of a coarse fabric as a base material, and a soft chloride resin for tarpaulins. The vinyl resin film is the same as the above-mentioned film, and the soft vinyl chloride resin-impregnated coating layer for the canvas and mesh sheet is a paste of 100 parts by mass of vinyl chloride resin (fine particles) obtained by emulsion polymerization, and 30 to 100 parts by mass of a plasticizer. As stabilizers for vinyl chloride resins, calcium-zinc composite stabilizers, barium-zinc composite stabilizers, organic tin laurate stabilizers, organic tin mercaptite stabilizers, epoxy stabilizers, and the like can be optionally used. Pigments, flame retardants, fillers, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, cross-linking agents and the like can be optionally used as necessary. A film obtained by coating the paste on a cloth or by dipping the cloth in a liquid bath of the paste and gelling it by heat treatment is preferred. The main plasticizer in such a resin composition is one or more polyglycerol fatty acid ester compounds [Chemical 1], and the plasticizer that can be additionally included in this composition is a furandicarboxylic acid dialkyl ester compound [Chemical 2].

＊式中Ｒはアルキル基 Polyglycerin fatty acid ester compound [Chemical 1] is an esterification of polyglycerin and fatty acid, and includes polyglycerin fatty acid monoester compound [Chemical 1 upper], polyglycerin fatty acid diester compound [Chemical 1 middle], and polyglycerin fatty acid triester. compound [Chem. 1 below], and mixtures thereof. Polyglycerin is a multimer (polymer) obtained by dehydration condensation of glycerin as a monomer. In particular, glycerin is obtained by hydrolyzing triacylglycerol contained in the oils and fats of living organisms (animals, fish, insects, etc.), and by-products ( Non-petroleum-derived biomass glycerin is preferred, such as glycerin), a by-product (glycerin) in the production of fatty acid methyl ester by transesterification of fats and oils with methanol, and biomass glycerin obtained by converting biomass propylene into epichlorohydrin and hydrolyzing it. Further, the fatty acid is preferably a saturated or unsaturated fatty acid having 2 to 10 carbon atoms, and these may be linear or branched. Specifically, acetic acid, propionic acid, butyric acid, caproic acid (hexanoic acid), capryl 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., but in terms of non-petroleum origin, linoleic acid, linolenic acid contained in safflower oil, corn oil, soybean oil, olive oil, coconut oil, palm oil, etc. Acids such as oleic acid, lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), and palmitic acid (hexadecanoic acid) are preferred. Polyglycerin fatty acid ester compounds [Chemical 1] 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, polyglycerol/laurate mono (or di or tri) ester, polyglycerol/palmitate mono (or di or tri) ester, and the like. (* "/" is used to avoid visual confusion due to the continuation of katakana nouns of chemical substances. All polyglycerin fatty acid ester compounds are treated in the same way.) A polyglycerol fatty acid ester compound [Formula 1] obtained by esterifying the derived fatty acid can be a recyclable biomass compound. The amount of the furandicarboxylic acid dialkyl ester compound [Formula 2] is 1 to 50% by mass based on the amount of the polyglycerol fatty acid ester compound [Formula 1]. The greater the amount of the compound [Formula 2] used in combination, the better the filler dispersion and filling effect for the soft vinyl chloride resin film and the soft vinyl chloride resin-impregnated coating layer. To have an excellent deterrent effect and to reduce the stickiness of the surface of an article due to the plasticizer, thereby reducing the adhesion of soot and dust, thereby exhibiting the effect of preventing contamination and maintaining the texture for a long period of time due to the effect of suppressing volatilization of the plasticizer. becomes possible.

*In the formula, R is an alkyl group

Furandicarboxylic acid dialkyl ester compound [Formula 2] is a plasticizer synthesized by reaction (esterification) of furandicarboxylic acid and alcohol with n = 4 to 20, especially 2,5-furandicarboxylic acid and C4 ~ Preferred are 2,5-furandicarboxylic acid dialkyl ester compounds synthesized by reaction (esterification) of C12 (which may be C13-C20) with an alcohol. 2,5-Furandicarboxylic acid is a recyclable biomass compound synthesized, for example, by dehydration (production of oxygen-containing five-membered ring structure) and oxidation of fructose (fructose). Regenerative circulation means that the carbon dioxide emitted by the combustion of biomass products is absorbed by plants, and the sugars produced by the plants are converted into biomass compounds to synthesize biomass compounds (in this paragraph, the plasticizer of [Chemical 2]). means a cycle to The carboxylic acid of furandicarboxylic acid can be coordinated at the 2,3-position, 2,4-position, and 3,4-position other than the 2,5-position, but 2,5-furandicarboxylic acid is a biomass compound. Synthesis is the simplest. Specific examples of [Chemical Formula 2] include dibutyl 2,5-furandicarboxylate (MW268) and diisobutyl 2,5-furandicarboxylate (MW268) obtained by reacting 2,5-furandicarboxylic acid with a C4 alcohol. Dipentyl 2,5-furandicarboxylate (MW 296) by reaction with C5 alcohols, Dihexyl 2,5-furandicarboxylate (MW 324) by reaction with C6 alcohols, and 2,5-dipentyl furandicarboxylate (MW 324) by reaction with C7 alcohols. Diheptyl furandicarboxylate (MW 352), di(2-ethylhexyl) 2,5-furandicarboxylate (MW 380) similarly by reaction with C8 alcohols, dinonyl 2,5-furandicarboxylate (MW 380) similarly by reaction with C9 alcohols MW408) and diisononyl 2,5-furandicarboxylate (MW408), likewise didecyl 2,5-furandicarboxylate (MW436) and diisodecyl 2,5-furandicarboxylate (MW436) by reaction with a C10 alcohol, likewise Diundecyl 2,5-furandicarboxylate (MW464) by reaction with C11 alcohol, dilauryl 2,5-furandicarboxylate (MW492) by reaction with C12 alcohol, and the like can be used in combination. The C4-C12 alcohols used in the synthesis are also preferably plant-derived compounds, 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 2] thus obtained have a biomass content of 100% and can be recycled.

The vinyl chloride resin used for the industrial material film and the 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, vinyl chloride/vinyl acetate copolymers, vinyl chloride/acrylic graft polymers, and other copolymers containing more than 60% by mass of vinyl chloride components. Vinyl chloride monomer is produced by reacting ethylene obtained by thermally decomposing naphtha with chlorine obtained by electrolyzing salt to obtain ethylene dichloride. Ethylene obtained by thermally decomposing and hydrogen chloride produced as a by-product of the direct chlorination method are reacted in the presence of oxygen to obtain ethylene dichloride, and this ethylene dichloride is dehydrated and thermally decomposed to obtain oxychlorination. is general purpose. However, the vinyl chloride-based resin used in the present invention is preferably a biomass vinyl chloride-based resin polymerized using a vinyl chloride monomer derived from biomass ethylene obtained by dehydrating biomass ethanol obtained by fermentation of sugarcane molasses. As a plasticizer for this biomass vinyl chloride resin, a Biomass furandicarboxylic acid dialkyl ester compound [Formula 1] is used, and if necessary, a Biomass polyglycerol fatty acid ester compound [Formula 2] is used as a plasticizer. The resulting industrial material film and industrial composite sheet can be a carbon-neutral biomass industrial material film and industrial composite sheet. If the degree of biomass is arbitrary, epoxidized soybean oil, epoxidized linseed oil, phthalate, isophthalate, terephthalate, cyclohexanedicarboxylate, cyclohexene dicarboxylate, adipic acid , sebacic acid-based, chlorinated paraffin-based, polyester-based, ethylene/vinyl acetate/carbon monoxide terpolymer resin, ethylene/(meth)acrylate/carbon monoxide terpolymer resin, etc. may be used together 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 most suitable as a combined plasticizer in the present invention because the soybean oil and linseed oil portions of the chemical structure are derived from biomass.

The fabric used for the base material of the composite sheet for industrial use of the present invention is a woven or knitted element comprising multifilament yarns comprising at least polyalkylene furanoate [Chemical 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical 4] fibers. 1) Woven fabric for tarpaulins (plain weave, basket weave, satin weave, twill weave, raschel weave, etc.) with a porosity of about 6 to 25%, and a basis weight woven and knitted with long-fiber multifilament yarns 100-500 g/m ² woven fabric, 2) fabric for canvas (plain weave, basket weave, satin weave, twill weave, etc.) with a porosity of about 0-10%, and short fiber spun (spun) multifilament yarn A spun fabric with a basis weight of 100 to 500 g / m ² woven and knitted in rows, 3) and a coarse fabric for mesh sheets with a porosity of about 10 to 70% (plain weave, patterned fabric, stacked net, etc.), Coarse fabric with a basis weight of 30 to 200 g/m ² woven and knitted with long multifilament yarns, and long fiber multifilament yarns (coated yarn) coated with resin, with a basis weight of 25 to 350 g / m ^Two woven meshes and stacked meshes can be exemplified. The void ratio 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 of gaps generated by entanglement and crossing of axial threads such as bias threads, and can be obtained by subtracting from 100 the area of the yarn occupied in the unit area of the fabric as a percentage. Specifically, it is possible to calculate the average value of the yarn width, and calculate the value converted from the void ratio per inch square meter from the relationship between 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, with the exception of polyester (polyethylene Terephthalate: PET, polybutylene terephthalate: PBT, polynaphthalene terephthalate: PNF) fiber, polyethylene fiber, polypropylene fiber, nylon fiber, vinylon fiber, one or more types of multifilament yarn (long fiber, short fiber spun yarn ) can be mixed, and the mixing ratio of these yarns is preferably 50% by mass or less from the viewpoint of the degree of biomass. Mixed yarns are regularly arranged or randomly arranged at an arbitrary spacing (n alternating, n alternating, n straddling: n is an integer) to form a lattice pattern or a geometric pattern in appearance. may be The weaving elements of the fabric by the above yarns are warp/weft, warp/upper right 30-60° bias yarn/upper left 30-60° bias yarn, warp/weft/upper right 30-60° It is one type selected from bias yarn/upper left 30-60° bias yarn. Here, "warp/weft" is a biaxial fabric, "warp/upper right 30 to 60° bias yarn/upper left 30 to 60° bias yarn" is triaxial fabric, and "warp/weft/upper right 30" ~60° Bias Yarn/Upper Left 30-60° Bias Yarn” refers to a tetraaxial fabric. (* In the description of the weaving elements of fabric, "/" means a combination of yarn directions, that is, and. The same applies to all weaving elements of fabric.) Especially triaxial and tetraaxial fabrics are used as base materials As a result, the resulting industrial composite sheet is extremely excellent in dimensional stability, breaking strength, penetration resistance, and tear resistance. It can also be used for special purposes such as a protective cover, to avoid crushed and scattered objects at blast construction sites, and as equipment for receiving falling objects at work sites. The tarpaulin is a woven fabric with a porosity of about 6 to 25% and a thermoplastic resin composition film is laminated on both sides, and the canvas is 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 formed by impregnating and coating a liquid thermoplastic resin composition on the entire surface of a coarse fabric having a porosity of about 10 to 70%. is a film-formed embodiment.

これらのポリアルキレンフラノエート繊維は、密度１．４１～１．４５ｇ/ｃｍ³、融点２１０～２３０℃、強度（Ｅ-modulus）３．１～３．３ＧＰａ、の少なくとも１項を満たすポリアルキレンフラノエート樹脂から溶融紡糸された繊維が特に好ましい。ポリエチレンフラノエート繊維は具体的に、モノエチレングリコールと２，５－フランジカルボン酸との重縮合によって得られるＰＥＦ樹脂から溶融紡糸された繊維で、ポリプロピレンフラノエート繊維は具体的に、モノプロピレングリコールと２，５－フランジカルボン酸との重縮合によって得られるＰＰＦ樹脂から溶融紡糸された繊維で、ポリエチレンフラノエート繊維は具体的に、モノブチレングリコールと２，５－フランジカルボン酸との重縮合によって得られるＰＢＦ樹脂から溶融紡糸された繊維で、ポリトリメチレンフラノエート繊維は具体的に、トリメチレングリコールと２，５－フランジカルボン酸との重縮合によって得られるＰｔＭＦ樹脂から溶融紡糸された繊維である。特にポリエチレンフラノエート繊維は１００％バイオマス化が容易で好ましく、バイオマス度１００％を達成するモノエチレングリコールは例えば、サトウキビの廃蜜糖の発酵によるBiomassエタノールを脱水してエチレンとし、これを酸化してエチレンオキサイドとし、さらに加水分解した植物由来のジオールで、これらは再生持続可能である。また２，５－フランジカルボン酸は例えば、フルクトース（果糖）の脱水（含酸素５員環構造の生成）、酸化により合成した植物由来の化合物が好ましく、これらは再生持続可能である。上記ポリアルキレンフラノエート繊維全般において、原料となるフランジカルボン酸のカルボン酸の配位は２，５位以外、２，３位、２，４位、３，４位の態様も可能であるが、植物由来化合物として２，５－フランジカルボン酸が最も合成が容易である。再生持続可能とは、バイオマス製品の燃焼により排出された二酸化炭素が、植物に吸収され、植物の生産する糖をバイオマスモノマーに転化し、これによりバイオマス製品を合成するサイクルを意味する。 The fabric used for the base material of the composite sheet for industrial use of the present invention is a woven or knitted element comprising multifilament yarns comprising at least polyalkylene furanoate [Chemical 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical 4] fibers. Specifically, 1) the polyalkylene furanoate fiber is one or more selected from polyethylene furanoate fiber, polypropylene furanoate fiber, polybutylene furanoate fiber, and polytrimethylene furanoate fiber. . "-(CH ₂ ) _n -" in [Chemical 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 preferred polymerization degree m is 500 to 1000

These polyalkylene furanoate fibers have a density of 1.41 to 1.45 g/cm ³ , a melting point of 210 to 230° C., and a strength (E-modulus) of 3.1 to 3.3 GPa. Fibers melt-spun from ate resins are particularly preferred. Polyethylene furanoate fibers are specifically fibers melt-spun from PEF resins obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and polypropylene furanoate fibers are specifically fibers made from monopropylene glycol and Fibers melt-spun from PPF resins obtained by polycondensation with 2,5-furandicarboxylic acid, polyethylene furanoate fibers are specifically obtained by polycondensation with monobutylene glycol and 2,5-furandicarboxylic acid. Polytrimethylene furanoate fibers are specifically melt-spun fibers from PtMF resin obtained by polycondensation of trimethylene glycol and 2,5-furandicarboxylic acid. . In particular, polyethylene furanoate fiber is preferable because it is easy to convert to 100% biomass, and monoethylene glycol, which achieves a biomass degree of 100%, is obtained by dehydrating biomass ethanol obtained by fermentation of sugar cane molasses to ethylene, which is then oxidized. As ethylene oxide and hydrolyzed plant-derived diols, these are renewable and sustainable. Further, 2,5-furandicarboxylic acid is preferably a plant-derived compound synthesized by dehydration of fructose (formation of oxygen-containing five-membered ring structure) and oxidation, and these are regeneratively sustainable. In the polyalkylene furanoate fiber in general, the coordination of the carboxylic acid of the raw furandicarboxylic acid may be 2,3-position, 2,4-position, or 3,4-position other than 2,5-position. 2,5-Furandicarboxylic acid is the easiest plant-derived compound to synthesize. Renewable sustainability means a cycle in which carbon dioxide emitted by combustion of biomass products is absorbed by plants and the sugars produced by the plants are converted into biomass monomers, thereby synthesizing biomass products.

これらのアルキレン／フラノエート／テレフタレート共重合体繊維は、密度１．３８～１．４２ｇ/ｃｍ³、融点２２０～２５０℃、強度（Ｅ-modulus）２．５～３．０ＧＰａ、の少なくとも１項を満たすアルキレン／フラノエート／テレフタレート共重合体樹脂から溶融紡糸された繊維が特に好ましい。このアルキレン（Alk）／フラノエート（Ｆ）／テレフタレート（Ｔ）共重合体樹脂の態様は、１）〔－Alk－Ｆ－Alk－Ｔ－〕を繰り返し単位ｍ（特に好ましくは５００～１０００）とする交互共重合体〔化４上〕、２）交互共重合体において〔Ｆ〕と〔Ｔ〕の配置が不規則なランダム共重合体（ランダムなので〔化４〕に図示してない）、３）〔－Alk－Ｔ－〕ｍ１（特に好ましくはｍ１が１２５～２５０）重合体単位と〔－Alk－Ｆ－〕ｍ２（特に好ましくはｍ２が３７５～７５０）重合体単位を含むブロック共重合体〔化４下〕が例示でき、下記具体例においても同様１）～３）の態様の何れかである。ポリエチレン／フラノエート／テレフタレート共重合体繊維は具体的に、モノエチレングリコールとテレフタル酸、及び２，５－フランジカルボン酸との重縮合によって得られるＰＥ/Ｆ/Ｔ樹脂から溶融紡糸された繊維で、ポリプロピレン／フラノエート／テレフタレート共重合体繊維は具体的に、モノプロピレングリコールとテレフタル酸、及び２，５－フランジカルボン酸との重縮合によって得られるＰＰ/Ｆ/Ｔ樹脂から溶融紡糸された繊維で、ポリブチレン／フラノエート／テレフタレート共重合体繊維は具体的に、モノブチレングリコールとテレフタル酸、及び２，５－フランジカルボン酸との重縮合によって得られるＰＢ/Ｆ/Ｔ樹脂から溶融紡糸された繊維で、ポリトリメチレン／フラノエート／テレフタレート共重合体繊維は具体的に、トリメチレングリコールと、テレフタル酸、及び２，５－フランジカルボン酸との重縮合によって得られるＰｔＭ/Ｆ/Ｔ樹脂から溶融紡糸された繊維である。特にポリエチレン／フラノエート／テレフタレート共重合体繊維では高バイオマス化が容易で好ましい。高バイオマス度となり得るモノエチレングリコール、及び２，５－フランジカルボン酸は段落〔００２１〕に記載と同一である。これらの共重合体繊維において、テレフタル酸成分も植物由来のBiomassテレフタル酸であることが好ましい。またテレフタル酸成分の１～９９質量％をイソフタル酸、またはフタル酸に置換することもできる。（※「／」は共重合成分を明確にするための存在で、共重合体において全て同様の扱いとする） The alkylene/furanoate/terephthalate copolymer [Chem. 4] fiber includes polyethylene/furanoate/terephthalate copolymer fiber, polypropylene/furanoate/terephthalate copolymer fiber, polybutylene/furanoate/terephthalate copolymer fiber, and polytriphthalate. One or more selected from methylene/furanoate/terephthalate copolymer fibers can be exemplified. "-(CH ₂ ) _n -" in [Chemical 2] 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 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 solid alkylene/furanoate/terephthalate copolymer resins. Aspects of this alkylene (Alk)/furanoate (F)/terephthalate (T) copolymer resin are as follows: 1) [-Alk-F-Alk-T-] is a repeating unit m (particularly preferably 500 to 1000) Alternating copolymer [Formula 4 above], 2) Random copolymer in which the arrangement of [F] and [T] is irregular in the alternating copolymer (because it is random, it is not shown in [Formula 4]), 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 are also any of the embodiments 1) to 3). Polyethylene/furanoate/terephthalate copolymer fibers are specifically fibers melt-spun from PE/F/T resin obtained by polycondensation of monoethylene glycol with terephthalic acid and 2,5-furandicarboxylic acid, Polypropylene/furanoate/terephthalate copolymer fibers are specifically fibers melt-spun from PP/F/T resin obtained by polycondensation of monopropylene glycol with terephthalic acid and 2,5-furandicarboxylic acid, Polybutylene/furanoate/terephthalate copolymer fibers are specifically fibers melt-spun from PB/F/T resins obtained by polycondensation of monobutylene glycol with 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. Fiber. In particular, polyethylene/furanoate/terephthalate copolymer fibers are preferable because high biomass can be easily obtained. Monoethylene glycol and 2,5-furandicarboxylic acid that can have a high degree of biomass 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. Also, 1 to 99% by mass of the terephthalic acid component can be replaced with isophthalic acid or phthalic acid. (* "/" exists to clarify the copolymerization component, and all copolymers are treated in the same way.)

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

In the industrial composite sheet of the present invention, 1) a woven fabric (plain weave, basket weave, satin weave, twill weave, raschel weave, etc.) with a void space of about 6 to 25%, which is woven and knitted with long-fiber multifilament yarns. A tarpaulin based on a woven fabric with a basis weight of 100 to 500 g / m ² is a thickness of 0.1 obtained by calendar rolling molding or T-die extrusion molding from a soft vinyl chloride resin composition on both sides of this base material. A film that can be obtained by thermally laminating a film or sheet of ~1 mm, and is arranged on the front and back of a woven fabric with a void portion (a void caused by entangling of axial threads) having a porosity of 6 to 25% interposed. Alternatively, the soft vinyl chloride resin layers on the front and back sides are strongly bonded to the woven fabric by melting and integrating the sheets. If the thickness of the tarpaulin is in the range of 0.4 to 1.5 mm and the mass is in the range of 500 to 2000 g/m, it can be used for large tent structures (indoor sports facilities, pavilions, event halls), circus tents, tent warehouses, and membrane roofs for architectural spaces. (membrane ceiling) and other membrane structures, and flexible containers. 2) Fabric for canvas (plain weave, basket weave, satin weave, twill weave, etc.) with a porosity of about 0 to 10%, with a basis weight of 100 to woven with short fiber spun (spun) multifilament yarns A canvas based on a 500 g/m ² spun fabric is dip-coated or coated with a soft vinyl chloride resin composition liquid on both sides of this base material, and the coated material is dried to 0. It can be obtained by forming a film having a thickness of 0.05 to 0.3 mm, and it is preferable that a part of the coated product is impregnated with the spun fabric. If the canvas has a thickness of 0.4 to 1.0 mm and a mass of 400 to 1500 g/m, it is suitable as a raw material for truck hoods, tent warehouses, and the like. 3) and a mesh sheet with a porosity of about 10 to 70%. A mesh sheet based on a rough fabric of m ² 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 to a thickness of 0.05 to 0.3 mm. It is preferable that a part of the coated material is impregnated in the coarse woven fabric. It is also a mesh sheet obtained by weaving and knitting a long-fiber multifilament yarn (coated yarn) in which the entire yarn is coated with a liquid of a soft vinyl chloride resin composition. If the mesh sheet has a thickness of 0.4 to 1.0 mm and a mass of 200 to 1000 g/m, it is suitable as a raw material for architectural curing mesh sheets, wind and snow nets, anti-glare nets, facade meshes, and the like.

An acrylic resin, a urethane resin, an acrylic/silicon copolymer resin, a fluorocopolymer resin, an acrylic resin and a fluorocopolymer are added to one or more surfaces of the industrial material film and industrial composite sheet of the present invention. An antifouling layer made of a coating film of polymer resin blend, urethane/silicon graft copolymer resin, urethane/fluorine graft copolymer resin, or the like may be formed, or a fluororesin layer. /Aminoethylated acrylic resin epoxy cured adhesive layer, fluorine resin layer/acrylic resin adhesive layer, fluorine resin layer/acrylic resin layer/aminoethylated acrylic resin epoxy cured adhesive layer, and fluorine resin layer/ A fluorine resin 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, the durability of outdoor use is dramatically improved. Let Furthermore, on the surface of these antifouling layers, nanoparticles made from an inorganic colloidal substance 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 to prevent static electricity. An antifouling layer may be provided. Inorganic colloidal substances include photocatalytic titanium oxide sols, photocatalytic zinc oxide sols, photocatalytic tin oxide sols, titanium oxide sols, zinc oxide sols, tin oxide sols, silica sols, aluminum oxide sols, zirconium oxide sols, cerium oxide sols, and composite oxides. (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) metal oxides such as sol.

The industrial material film of the present invention and the industrial composite sheet are joined and sewn by thermal fusion such as a high-frequency welder fusion method, hot plate fusion method, hot air fusion method, and ultrasonic fusion method, and machine sewing. is applicable. Especially in the high-frequency fusion method, the soft vinyl chloride resin layers on the front and back are re-melted by the heat-generating press by the weld bar, and the fabric (base material) is reheated to increase the adhesive effect with the fabric (thread). To improve the creep property (restraint against thread pull-out failure) at the lap joint portion of the membrane structure. In particular, by using a yarn made of polyalkylene furanoate fiber as a constituent element of the fabric, it is possible to improve the strength of the joint and the resistance of the joint without causing lap failure at the lap joint between industrial composite sheets. 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 210-230°C, which is 20-60°C lower than the melting point of polyethylene terephthalate resin (PET fiber raw material), which is 250-270°C. It is considered that by approaching the melting point of the resin layer to 200° C. or less, the adhesiveness between the fabric and the soft vinyl chloride resin layer is effectively improved during production and lap bonding. The strength performance and tear resistance of the main body of the composite sheet for industrial use are fully expressed, and the main factor is that the strength (E-modulus) of PET resin (fiber raw material) is 2.1 to 2.2 GPa, whereas the strength of poly 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. In addition, the main factor for the flexibility of the industrial wind sheet body is that the crystallization speed when the fiber is melt-spun from PET resin and stretched and cooled is about 2 to 3 minutes, whereas the polyalkylene furano In the case of ate resin (fiber raw material), it is considered that the crystallization is about 20 to 30 minutes, which is about 10 times slower, resulting in good results. Also in the alkylene/furanoate/terephthalate copolymer fiber, it is considered that similar effects due to the difference in melting point, strength, and crystallization rate are fully exhibited.

EXAMPLES The present invention will be further described with reference to the following examples and comparative examples, but the invention is not limited to the scope of these examples.
Biomass degree (proof of biomass origin)
The carbon isotope " ¹⁴ C" concentration (detection ratio of " ¹⁴ C" and " ¹² C" in the polymer) contained in all carbon atoms constituting the polymer is determined by an accelerator mass spectrometer, and " ¹⁴ The detection ratio of C' proves the bio conversion rate.
The amount of carbon isotope " ¹⁴ C" ⁱⁿ the atmosphere is almost constant due to the equilibrium state of " ¹⁴ C" production by cosmic rays and radioactive decay (half-life of about 5730 years). Accumulated in plants by photosynthesis and distributed in animals in the subsequent food chain, the " ¹⁴ C" concentration (detection ratio of " ¹⁴ C" and " ¹² C") of all organisms 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 exceeded its half-life and is considered to be virtually zero. contains a certain concentration of " ¹⁴ C", petroleum-derived products will not contain " ¹⁴ C". Therefore, the measurement of the " ¹⁴ C" concentration (detection ratio of " ¹⁴ C" and " ¹² C") can prove that the product is a biomass-derived product.

[Example 1]
<Tarpaulin made of fabric (1)>
1000d of polyethylene phenolate (PEF) fiber obtained 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) (1111 dtex) multifilament yarn (192 filaments), S-twisted 200 T / m as warp group and weft group, with a driving density of 19 warps / inch × 20 wefts / inch, mass 190 g / A fabric (1) with m ² and a porosity of 10% is used.
*Polyethylene phenolate (PEF) fiber is melt-spun from polyethylene phenolate (PEF) resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and all polymerization monomers are derived from biomass. A compound, monoethylene glycol is obtained by dehydrating biomass ethanol obtained by fermentation of sugarcane molasses to obtain biomass ethylene, oxidizing this to biomass ethylene oxide, and further hydrolyzing it, and 2,5- Furandicarboxylic acid is a plant-derived compound synthesized by dehydration of fructose (formation of oxygen-containing five-membered ring structure) and oxidation. The fabric (1) using yarn as a weaving element also has a biomass content of 100%.
<Tarpaulin production>
On both sides of the fabric (1), a film with a thickness of 0.16 mm is formed by calender molding under a heat condition of 165 ° C to 180 ° C from a soft vinyl chloride resin compound of the following [Formulation 1], and a film is applied with a laminator under a hot roll condition of 170 ° C. is laminated in a softened state, a tarpaulin-like industrial composite sheet (1) having a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass degree of this industrial composite sheet (1) is theoretically about 100% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers).
* A molded film having a thickness of 0.16 mm according to [Formulation 1] can be used separately as an industrial material film of the present invention.
[Formulation 1] Soft vinyl chloride resin compound composition Suspension polymerization vinyl chloride resin (degree of polymerization: 1300) 100 parts by mass * Biomass ethylene obtained by dehydrating Biomass ethanol obtained by fermentation of sugarcane waste molasses is chlorinated. Biomass polymer by radical polymerization of vinyl chloride monomer Polyglycerin/oleic acid monoester 60 parts by mass is a biomass-derived glycerin dimer (average degree of polymerization n =
In 2), the oleic acid (CH ₃ (CH ₂ ) ₇ CH=CH(CH ₂ ) ₇ COOH) used is derived from plants refined from olive oil.
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 of fabric (2)>
Polyethylene phenolate (PEF) staple 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) A plain weave spun fabric with a warp count of 20 (590 dtex) 46 threads/inch and a weft count of 20 count (590 dtex) double threads (590 dtex)/inch of yarn (S twist 600 T/m): void ratio 5%: mass 228 g/m ² is used for the fabric (2).
*Polyethylene phenolate (PEF) fibers are melt-spun filaments of polyethylene phenolate (PEF) resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid and cut into 4 to 10 cm lengths. Spun yarn from staples, all polymerized monomers are biomass-derived compounds, monoethylene glycol is biomass ethylene by dehydrating biomass ethanol obtained by fermentation of sugar cane molasses, and biomass ethylene oxide by oxidizing this. , and further hydrolyzed, and 2,5-furandicarboxylic acid is a biomass-derived compound synthesized by dehydration of fructose (production of oxygen-containing five-membered ring structure) and oxidation, polyethylene phenolate obtained The (PEF) fiber is 100% biomass-derived spun yarn, and the fabric (2) using this spun yarn as a weaving and knitting element also has a biomass degree of 100%.
<Manufacturing canvas>
The fabric (2) is immersed in a liquid bath filled with the soft vinyl chloride resin paste sol composition of [Formulation 2] below, and the paste sol composition of [Formulation 2] is dip-impregnated into the fabric (2) to obtain the fabric. (2) is pulled up and at the same time compressed with a rubber roll, followed by heating in a hot air oven at 180°C for 3 minutes to complete the gelation of the paste sol composition of [Formulation 2], impregnating the fabric (2) with the soft vinyl chloride resin. Then, a canvas-like industrial composite sheet (2) having a thickness of 0.47 mm and a mass of 560 g/m ² is obtained, in which soft vinyl chloride resin layers are formed on both sides of the fabric (2). The biomass degree of this industrial composite sheet (2) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, ultraviolet absorbers, and curing agents).
[Composition 2] Soft vinyl chloride resin paste sol composition Vinyl chloride resin obtained by emulsion polymerization (degree of polymerization: 1700) 100 parts by mass Polyglycerin/linoleic acid diester 60 parts by mass *Polyglycerin/linoleic acid diester is a diester with 100% biomass content obtained by esterification of polyglycerin and linoleic acid. , Glycerin, which is a by-product of fatty acid methyl ester formation through the transesterification reaction of fats and oils and methanol, is isolated.
Biomass-derived glycerin dimer obtained by dehydration condensation (average degree of polymerization n = 2)
linoleic acid (CH ₃ (CH ₂ ) ₄ (CH=CHCH ₂ ) ₂ (CH ₂ ) ₆ COOH) is a plant-derived material refined from safflower oil.
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 type 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)>
Polyethylene phenolate (PEF) fibers obtained 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 "750d (833dtex) 147 filaments, S twist 200T / m: / 3 strands" was woven with 8 warps / inch and 9 wefts / inch as weft threads. , a mass of 195 g/m ² and a coarse fabric (3) having a porosity of 15%.
*Polyethylene phenolate (PEF) fiber is melt-spun from polyethylene phenolate (PEF) resin obtained by polycondensation of monoethylene glycol and 2,5-furandicarboxylic acid, and all polymerization monomers are derived from biomass. As a compound, monoethylene glycol is obtained by dehydrating Biomass ethanol obtained by fermenting sugar cane molasses into Biomass ethylene, oxidizing it to form Biomass ethylene oxide, 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 coarse-grained fabric (3) used as the knitting element also has a biomass degree of 100%.
<Manufacturing of mesh sheet>
The fabric (3) is immersed in a liquid bath filled with the soft vinyl chloride resin paste sol composition of [Formulation 2] described above, and the paste sol composition of [Formulation 2] is dip-impregnated into the fabric (3), The cloth (3) is pulled up and at the same time compressed with rubber rolls in a hot air oven at 180° C. for 3 minutes to complete the gelation of the paste sol composition of [Formulation 2]. An industrial composite sheet (3) in the form of a mesh sheet having a thickness of 0.42 mm, a weight of 465 g/m ² and a porosity of 13% is obtained, which is impregnated and a soft vinyl chloride resin layer is formed on the entire surface of the fabric (3). . The biomass degree of this industrial composite sheet (3) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, ultraviolet absorbers, and curing agents).

[Example 4]
In the same manner as in Example 1, except that 60 parts by mass of polyglycerin/oleic acid monoester in [Formulation 1] of Example 1 was entirely replaced with polyglycerol/myristate triester to obtain [Formulation 3], A tarpaulin-like industrial composite sheet (4) with a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass degree of this industrial composite sheet (4) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
*The 0.16 mm-thick film obtained by molding [Formulation 3] can be used separately as an industrial material film of the present invention.
* Polyglycerin/myristic acid triester is a 100% biomass-based triester obtained by esterification of polyglycerin and myristic acid. Polyglycerin is a by-product of fatty acid methyl ester produced by the transesterification reaction between fats and oils and methanol. It is a biomass-derived glycerin dimer (average degree of polymerization n = 2) obtained by isolating and dehydrating it, and myristic acid (CH ₃ (CH ₂ ) ₁₂ COOH) is a plant-derived product refined from coconut oil. Use the one from

[Example 5]
30 parts by mass of 60 parts by mass of polyglycerol/oleic acid monoester in Example 1 [Formulation 1] was replaced with 30 parts by mass of diisononyl 2,5-furandicarboxylate to obtain [Formulation 4]. As in Example 1, a tarpaulin-like industrial composite sheet (5) having a thickness of 0.75 mm and a mass of 915 g/m ² is obtained. The biomass degree of this industrial composite sheet (5) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
* Diisononyl 2,5-furandicarboxylate is synthesized by the reaction (esterification) of 2,5-furandicarboxylic acid and isononyl alcohol. Formation of 5-membered ring structure), derived from plants synthesized by oxidation, isononyl alcohol is a compound with a biomass degree of 100% via biomass alcohol produced by fermentation of sugarcane waste molasses. A 0.16 mm film can be used separately as an industrial material film of the present invention.

[Example 6]
Example 2 except that 30 parts by mass of 60 parts by mass of polyglycerol/linoleic acid diester in [Formulation 2] of Example 2 was replaced with 30 parts by mass of diisodecyl 2,5-furandicarboxylate to obtain [Formulation 5]. If it is the same as 2, a canvas-like industrial composite sheet (6) having a thickness of 0.47 mm and a mass of 560 g/m ² is obtained. The biomass degree of this industrial composite sheet (6) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
* Diisodecyl 2,5-furandicarboxylate is synthesized by the reaction (esterification) of 2,5-furandicarboxylic acid and isodecyl alcohol. 5-membered ring structure), isononyl alcohol is a plant-derived compound synthesized by oxidation, and isononyl alcohol is a compound with a biomass degree of 100% via biomass alcohol produced by fermentation of sugarcane waste molasses.

[Example 7]
30 parts by mass of 60 parts by mass of polyglycerol/myristate triester in [Formulation 3] of Example 4 was replaced with 30 parts by mass of di(2-ethylhexyl) 2,5-furandicarboxylate to obtain [Formulation 6]. A tarpaulin-like industrial composite sheet (7) having a thickness of 0.75 mm and a mass of 915 g/m ² is obtained in the same manner as in Example 4 except that the The biomass degree of this industrial composite sheet (7) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
* 2,5-Furandicarboxylic acid di(2-ethylhexyl) is synthesized by the reaction (esterification) of 2,5-furandicarboxylic acid and (2-ethylhexyl) alcohol, and 2,5-furandicarboxylic acid is fructose. Dehydration of (fructose) (formation of oxygen-containing five-membered ring structure), plant-derived synthesized by oxidation, isononyl alcohol is a compound with a biomass degree of 100% via biomass alcohol by fermentation of sugar cane waste molasses * molding A film having a thickness of 0.16 mm according to [Formulation 6] can be used separately as an industrial material film of the present invention.

[Example 8]
A tarpaulin-type industrial composite sheet (8) having a thickness of 0.75 mm and a mass of 908 g/m ² is the same as in Example 1 except that the fabric (1) of Example 1 is replaced with the fabric (4). is obtained. The biomass degree of this industrial composite sheet (8) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (4)>
Polyethylene/phenolate obtained by melt-spinning a 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 a warp group and a weft group, 19 warps / inch × 20 wefts A fabric (4) with a mass of 180 g/m ² and a porosity of 10% is used, with a stitching density of book/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 coalesced (PE/F/T) resin, and monoethylene glycol is produced by dehydrating bioethanol from the fermentation of sugar cane molasses to ethylene, oxidizing it to ethylene oxide, and then adding water. Decomposed biomass-derived monomers and 2,5-furandicarboxylic acid are plant-derived monomers synthesized by dehydration (formation of oxygen-containing five-membered ring structure) and oxidation of fructose (fructose), and terephthalic acid is the fermentation of corn sugar. It is a plant-derived monomer obtained by dehydrating isobutanol by dehydration to isobutylene, and converting paraxylene obtained by dimerization and cyclization by radical reaction into terephthalic acid.

[Example 9]
A tarpaulin-type industrial composite sheet (9) having a thickness of 0.77 mm and a mass of 913 g/m ² is the same as in Example 1 except that the fabric (1) of Example 1 is replaced with the fabric (5). is obtained. The biomass degree of this industrial composite sheet (9) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (5) triaxial plain weave>
1000 d (1111 dtex) multifilament yarns (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 were used in a warp group and an upper left bias yarn group. /Used for the upper right bias yarn group, the warp yarn group has a weave structure of 13 per inch, and the upper left bias yarn group/upper right bias yarn group has a weave structure of 13 per inch, mass 188 g / m ² , porosity ( A 10% triaxial plain weave is used for the fabric (5). The biomass degree of this fabric (5) is 100%.

[Example 10]
A tarpaulin-type industrial composite sheet (10) having a thickness of 0.80 mm and a mass of 919 g/m ² is the same as in Example 1 except that the fabric (1) of Example 1 is replaced with the fabric (6). is obtained. The biomass degree of this industrial composite sheet (10) is theoretically about 100% (excluding compounding agents such as flame retardants, stabilizers, pigments, and ultraviolet absorbers).
<Fabric (6) Four-axis plain weave>
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 a warp group, a weft group, and 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 per inch, and the upper left bias yarn group/upper right bias yarn group have a weave structure of 10 per inch, respectively. A four-axis plain woven fabric having a weight of 194 g/m ² and a porosity (total void area) of 8% is used for the fabric (6). The biomass degree of this fabric (6) is 100%.

[Reference example 1]
On both sides of the industrial composite sheet (1) having a biomass content of 100% of Example 1, the acrylic resin paint of the following [Formulation 7] is applied with 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) is formed on the front and back to obtain an intermediate A (1).
[Formulation 7] Acrylic resin paint Alkyl methacrylate/Alkyl acrylate 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 the following [Formulation 8] is applied to one surface of this intermediate A (1). Intermediate B is coated with a 100-mesh gravure roll, heated and dried in a hot air oven at 120 ° C. for 2 minutes, and an acrylic resin coating layer (5 g / m ² / one side) is attached on the surface side in a semi-cured state. (1).
[Formulation 8] Aminoethylated acrylic resin epoxy composition Polyethylenimine is grafted to the carboxyl group of the methacrylic acid alkyl ester/acrylic acid alkyl ester/methacrylic acid copolymer,
_Amine value ₍ solid content: ₁ g
Number of mmoles of amine contained in) 0.7 to 1.3 mmol/g primary amino group-containing acrylic resin
100 parts by mass Epoxy resin (trifunctional epoxy resin containing a bisphenol A skeleton with an 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 having a thickness of 25 μm and 53 g/m ² was opposed to the layer side of the semi-cured material of aminoethylated acrylic resin epoxy, and a laminator was applied under hot roll conditions of 150 ° C. Composite for industrial use that has excellent resistance to dust and rain streaks, and can restore its beautiful appearance by wiping it off A sheet (11) is obtained. The degree of biomass of this industrial composite sheet (11) is theoretically about 93%.

[Comparative Example 1]
A tarpaulin-type industrial composite sheet (12) having a thickness of 0.75 mm and a mass of 915 g/m ² was made in the same manner as in Example 1 except that [Formulation 1] in Example 1 was changed to [Formulation 9]. is obtained. The biomass degree of this industrial composite sheet (12) is theoretically about 23% (excluding flame retardants, stabilizers, pigments, and ultraviolet absorbers). It is clear that most of the carbon dioxide generated at the time of disposal does not meet carbon neutrality, making little contribution to the construction of 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 composed of petroleum-derived ethylene as a chlorinated vinyl chloride monomer Diisononyl phthalate (plasticizer) 60 parts by mass Part 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]
If the same as in Example 1 except that the fabric (1) of Example 1 was changed to the fabric (7) and [Formulation 1] was changed to [Formulation 9], the thickness was 0.75 mm and the mass was 904 g/ A tarpaulin-like industrial composite sheet (13) of m ² is obtained. The biomass degree of this industrial composite sheet (13) is about 3% with 10 parts by mass of epoxidized soybean oil (partially biomass plasticizer). At a biomass degree of about 3%, almost all of the carbon dioxide generated during the incineration of this industrial composite sheet does not meet carbon neutrality, and it is clear that it will not contribute to the construction of a low-environmental-impact and low-carbon society. is.
<Fabric (7)>
1000d of polyethylene phenolate (PET) fiber obtained by melt-spinning polyethylene terephthalate resin (density: 1.36 g/cm ³ , melting point: 250 to 270°C, glass transition temperature: Tg: 76°C, strength: E-modulus: 2.1 to 2.2 GPa) (1111 dtex) Multifilament yarn (192 filaments), S-twisted 200 T / m as a warp group and a weft group, with a driving density of 19 warps / inch × 20 wefts / inch, mass 179 g / A fabric (7) with m ² and a porosity of 10% is used.
*Polyethylene terephthalate resin is synthesized from petroleum-derived ethylene glycol and petroleum-derived terephthalic acid.

According to the industrial material film and 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 naturally return as carbon dioxide, It is counted in the regeneration cycle in which plants absorb it again), and it can contribute to the realization of a low-environmental-burden and low-carbon society that can suppress the increase in the amount of carbon dioxide emitted. Plastic greenhouses for medical use, simple clean booths for medical use, simple clean booths for industrial use, partitions for public facilities, covering protective materials for automobiles and railway vehicles, covering protective materials for floors and walls, waterproof covering materials for roofs and ceilings, etc. Industrial composite sheets are expected to be used for large tent structures (sports facilities, pavilions, circuses, planetariums, etc.), tent warehouses, architectural curing (soundproofing) sheets, membrane roofs (membrane ceilings) for architectural spaces, visual façades, Tarpaulins used for flexible containers, lifting type sheet shutters, floor sheets, partition sheets, etc., canvas used for truck hoods, open-air waterproof sheets, house tents, etc., architectural curing mesh sheets, wind and snow nets, anti-glare nets, sun-exposed facades It is expected to be widely used for mesh sheets used in such as.

Claims (7)

An industrial material film made of a composition containing at least one of a vinyl chloride resin and a polyglycerin fatty acid ester compound [Formula 1].

*In the formula, R is an alkyl group 2. The industrial material film according to claim 1, wherein the composition further contains a furandicarboxylic acid dialkyl ester compound [Formula 2].

Using a fabric as a base material, a soft vinyl chloride resin layer made of a composition containing at least one of a vinyl chloride resin and a polyglycerin fatty acid ester compound [Formula 1] is formed on one or more surfaces of the fabric. industrial composite sheet.

*In the formula, R is an alkyl group 4. The industrial composite sheet according to claim 3, wherein the composition further contains a furandicarboxylic acid dialkyl ester compound [Formula 2].

5. The industrial use according to claim 3 or 4, wherein the fabric comprises multifilament yarns made of polyalkylene furanoate [Chemical 3] fibers or alkylene/furanoate/terephthalate copolymer [Chemical 4] fibers in weaving and knitting elements. composite sheet.

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 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. 6. The composite sheet for industrial use according to claim 5, which is one or more selected. The weaving 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/ 6. The composite sheet for industrial use according to claim 5, which is one selected from upper left 30 to 60° bias yarn.