JP2018138704A - Filament nonwoven fabric and membrane base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filament nonwoven fabric which can exert dimension stability and durability performance in applications of a separation membrane base material as it comprises an environmental load reduction type material and has high strength and is excellent in abrasion characteristics.SOLUTION: The filament nonwoven fabric comprises a polyester as a main component, and a part of the polyester contains a component derived from 1,2-propane diol in an amount of 1-500 ppm. In particular, the filament nonwoven fabric is composed of core-sheath type conjugate fibers. It is preferable that the sheath component contains the component derived from 1,2-propane diol. The filament nonwoven fabric is composed of filaments comprising the core-sheath type conjugate fibers. The membrane separation support is a filament nonwoven fabric laminate formed by laminating 2 to 5 layers of the filament nonwoven fabric and includes the laminate as a base material.EFFECT: The nonwoven fabric comprising the filaments has enhanced adhesion properties among fibers by a crystallinity inhibitory effect and the nonwoven fabric has more improved abrasion resistance and strength. Thus, even a separation membrane support to which a high pressure is applied can maintain dimension stability and durability.SELECTED DRAWING: None

Description

  The present invention relates to a long-fiber nonwoven fabric preferably made of a biomass material-derived polyester raw material and a membrane substrate made using the same.

  Polyethylene terephthalate, which is a polyester raw material, is produced from terephthalic acid or an ester-forming derivative thereof and ethylene glycol. All of these raw materials are usually obtained from fossil resources. Petroleum, a fossil resource, is an important raw material for the chemical industry, but there are concerns about depletion in the future, and since a large amount of carbon dioxide is emitted during the manufacturing process and incineration, global warming, etc. Is inviting problems. Under such circumstances, much attention has been paid to recycled raw materials and materials with low environmental impact.

  Among them, the biomass resources are plants converted from water and carbon dioxide as raw materials by photosynthesis, and such biomass resources include starch, carbohydrates, cellulose, and lignin. Biomass resources use carbon dioxide as a raw material in the production process. Therefore, even if materials using biomass resources are incinerated after use and decomposed into carbon dioxide and water, new carbon dioxide is emitted. It is a carbon-neutral renewable resource because it may be taken back into the plant in some cases. If these biomass resources can be used as an alternative to petroleum resources, the reduction of fossil resources will be suppressed, and the amount of carbon dioxide emissions will also be suppressed.

  Against this background, attempts have been made to use polyethylene terephthalate synthesized from renewable biomass resources even in the world's most used polyester, and studies are also being conducted in the field of nonwoven fabrics.

  For example, interior materials for automobiles using a short fiber nonwoven fabric made of a core-sheath type composite fiber having a core made of polyethylene terephthalate derived from biomass resources and a sheath part made of a heat-sealing component, or derived from biomass resources. The polyethylene terephthalate contains a component derived from 1,2-propanediol, so that a proposal for an artificial leather substrate (see Patent Document 2) made of a short fiber nonwoven fabric excellent in wear resistance has been made.

JP 2013-11028 A WO2014 / 034780

  However, the non-woven fabric composed of the above short fibers is not a non-woven fabric having abrasion resistance and mechanical strength that can sufficiently withstand use in industrial applications.

  Accordingly, an object of the present invention is to provide a high-strength, long-fiber nonwoven fabric excellent in wear characteristics by using polyester synthesized from renewable biomass resources and suppressing generation of yarn breakage and base stain during spinning. is there.

  Another object of the present invention is to provide a membrane substrate such as a reverse osmosis membrane comprising the long-fiber nonwoven fabric of the present invention, having excellent productivity and suppressing curling after membrane formation.

  The present invention is to solve the above-mentioned problems, and the long-fiber nonwoven fabric of the present invention is a long-fiber nonwoven fabric made of a thermoplastic resin mainly composed of polyester, and at least a part of the polyester. A long-fiber non-woven fabric containing 1 to 500 ppm of a component derived from 1,2-propanediol.

  According to a preferred embodiment of the long fiber nonwoven fabric of the present invention, the polyester containing 1 to 500 ppm of the 1,2-propanediol-derived component forms at least a part of the surface of the filament constituting the long fiber nonwoven fabric. It is done.

  According to a preferred aspect of the long-fiber nonwoven fabric of the present invention, the filament constituting the long-fiber nonwoven fabric is composed of a core-sheath type composite fiber.

  The long fiber nonwoven fabric laminate of the present invention is a long fiber nonwoven fabric laminate in which 2 to 5 layers of the above-mentioned long fiber nonwoven fabric are laminated.

  The membrane substrate of the present invention is a membrane substrate comprising the above-mentioned long fiber nonwoven fabric or long fiber nonwoven fabric laminate.

  The separation membrane support of the present invention is a separation membrane support comprising the above-mentioned membrane substrate.

  The bonding base material of this invention is a bonding base material which consists of said long fiber nonwoven fabric or a long fiber nonwoven fabric laminated body.

  According to the present invention, it is a long-fiber nonwoven fabric made of a thermoplastic resin mainly composed of polyester, and contains 1 to 500 ppm of 1,2-propanediol-derived component in the polyester. A long fiber nonwoven fabric excellent in wear and strength can be obtained. Moreover, by using the long-fiber nonwoven fabric of the present invention, a membrane substrate suitable for a reverse osmosis membrane or the like having excellent adhesion between long-fiber nonwoven fabrics and suppressing curling after film formation can be obtained.

  The long-fiber non-woven fabric of the present invention is a long-fiber non-woven fabric made of a thermoplastic resin containing polyester as a main component, and at least a part of the polyester contains 1 to 500 ppm of 1,2-propanediol-derived component. It is a long-fiber nonwoven fabric.

  It is important that the long fiber nonwoven fabric of the present invention is made of a thermoplastic resin mainly composed of polyester. Short fiber nonwoven fabrics are short in fiber length and have few fiber intersections, so they are easily fluffed and inferior in wear resistance and strength. On the other hand, since the long fiber nonwoven fabric is composed of filaments, the fibers are continuously entangled and the fibers are bonded to each other, and the wear resistance and mechanical strength are excellent. Further, the long fiber nonwoven fabric does not require the use of an adhesive such as a binder, can be continuously produced, and is excellent in productivity.

  The main component in the present invention means that the component is contained in an amount of 85% by mass or more and includes only the component.

  The filament constituting the long-fiber nonwoven fabric of the present invention is made of polyester, and it is important that at least a part thereof contains 500 ppm or less of a component containing 1,2-propanediol in the polyester. Preferably it is 400 ppm or less. By doing so, sufficient heat resistance can be obtained without excessively including 1,2-propanediol in the main chain of the polyester.

  In the present invention, it is important that the component derived from 1,2-propanediol in the polyester is 3 ppm or more, more preferably 5 ppm or more. By doing in this way, a 1, 2- propanediol component reacts preferentially with a catalyst at the time of superposition | polymerization, and it can suppress a thermal decomposition reaction.

  In the present invention, the 1,2-propanediol-derived component is the total amount of 1,2-propanediol detected when the polyester is decomposed and analyzed, and is copolymerized in the polymer chain. 1,2-propanediol having a structure derived from 2-propanediol, and the total amount of 1,2-propanediol mixed between polymers. That is, this 1,2-propanediol may be partially copolymerized in the polyester main chain, and it is allowed to be contained as a single substance without being copolymerized.

  Examples of the dicarboxylic acid and / or ester-forming derivative thereof used in the present invention include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (for example, 2,6-naphthalenedicarboxylic acid), and diphenyldicarboxylic acid (for example, diphenyl-4). , 4′-dicarboxylic acid), oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic carboxylic acids, cyclohexane Alicyclic dicarboxylic acid such as dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-sulfoisophthalic acid salt (5-sulfoisophthalic acid lithium salt, 5-sulfoisophthalic acid potassium salt, 5-sulfoisophthalic acid sodium salt, etc.) Aromatic dicarboxylic acids and their Such as ester forming derivatives thereof.

  The ester-forming derivative referred to in the present invention means lower alkyl esters, acid anhydrides and acyl chlorides of these dicarboxylic acids, and for example, methyl esters, ethyl esters and hydroxyethyl esters are preferably used.

  A more preferred embodiment of the dicarboxylic acid and / or ester-forming derivative thereof used in the present invention is terephthalic acid, isophthalic acid and / or dimethyl ester thereof.

  As terephthalic acid and isophthalic acid and / or dimethyl ester thereof, terephthalic acid and isophthalic acid and / or dimethyl ester derived from biomass resources are preferably used. As a method for obtaining terephthalic acid and isophthalic acid derived from biomass resources, for example, p-cymene is synthesized from cineole obtained from a plant of the genus Eucalyptus (see Journal of Chemical Society of Japan, (2), P217-219; 1986), and thereafter. And p-methylbenzoic acid (see Organic Synthesis, 27; 1947) to obtain terephthalic acid. Still another method includes a method of obtaining terephthalic acid from furandicarboxylic acid and ethylene by Diels-Alder reaction (see WO2009-0664515). The biomass resources-derived terephthalic acid and isophthalic acid obtained in this manner are further allowed to be converted into ester-forming derivatives and used.

  Examples of the diol used in the present invention include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, diethylene glycol, 2- Examples thereof include diol components such as methyl-1,3-propanediol, polyoxyalkylene glycol having a molecular weight of 500 to 20000 (polyethylene glycol, etc.), and bisphenol A-ethylene oxide adduct, among which ethylene glycol is preferably used. Furthermore, as ethylene glycol, ethylene glycol derived from biomass resources often contains 1,2-propanediol, so it is more preferable to use ethylene glycol derived from biomass resources whose content has been adjusted by purification. This is a preferred embodiment.

  As a copolymerization component of polyester constituting the filament of the long-fiber nonwoven fabric of the present invention, structural units derived from the following components can be contained. For example, aliphatic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid, 5-sulfoisophthalic acid salt (5-sulfoisophthalic acid lithium salt, and 5-sulfoisophthalic acid potassium salt, A structural unit derived from an aromatic dicarboxylic acid such as 5-sulfoisophthalic acid sodium salt) can be contained as a copolymerization component.

Among them, 5-sulfoisophthalic acid lithium salt, 5-sulfoisophthalic acid potassium salt,
More preferred are 5-sulfoisophthalic acid salts such as 5-sulfoisophthalic acid sodium salt and ester-forming derivatives thereof, and polyoxyalkylene glycols having a molecular weight of 500 to 20000. As the polyoxyalkylene glycol, polyethylene glycol is preferable, and polyethylene glycol having a molecular weight of 500 to 10,000 is particularly preferably used.

  The 5-sulfoisophthalate is preferably copolymerized in an amount of 0.1 to 10 mol% based on the total dicarboxylic acid component constituting the polyester, and the polyoxyalkylene glycol having a molecular weight of 500 to 30,000 is obtained as a polyester. It is preferable that 0.1-10.0 mass% is copolymerized on the basis of the mass of this. By including this copolymer component, it is possible to further suppress a decrease in viscosity during melt molding.

  These copolymer components may be used alone, but when two or more types are copolymerized, the degree of improvement in heat resistance becomes more remarkable. The polyester containing the copolymer component is preferably used as, for example, a sheath component of the core-sheath composite fiber, but when forming the sheath component, by including a component derived from 1,2-propanediol, The fibers can be more suitably used because the fibers are more thermally fused and the wear resistance and strength are improved due to the crystallinity-inhibiting effect.

  Examples of a method for obtaining biomass-derived ethylene glycol include a method for obtaining biomass resources such as corn, sugarcane, and wheat or crop stalks. These biomass resources are first converted to starch, then starch is converted to glucose with water and enzymes, followed by hydrogenation to sorbitol, and sorbitol continues to be a catalyst at a constant temperature and pressure. Below, there is a method in which a mixture of various glycols is obtained by hydrogenation reaction and purified to obtain ethylene glycol.

In the present invention, the proportion of carbon derived from biomass resources is also referred to as a biogenic rate. When a raw material derived from a biomass resource is used, the biodegradation rate of the obtained polyester can be determined by measuring the ¹⁴ C concentration (pMC).

The concentration of radioactive carbon ¹⁴ C can be measured by the following radioactive carbon concentration measurement method. The radiocarbon concentration measurement method uses an accelerator mass spectrometer (AMS: Accelerator Mass Spectrometry) to calculate the carbon isotope ( ¹² C, ¹³ C, ¹⁴ C) contained in the sample to be analyzed by using the atomic weight difference. It is a method of physically separating and measuring the abundance of each isotope atom. The carbon atom is usually ¹² C, and the isotope ¹³ C is present in about 1.1%. ¹⁴ C is called a radioisotope and its half-life regularly decreases at about 5370 years. It takes 26,000 years for all of these to collapse.

In the Earth's upper atmosphere, cosmic rays continue to be radiated, and although in trace amounts, ¹⁴ C is constantly generated and balanced with radiation decay, and the concentration of ¹⁴ C is almost constant (carbon atoms in the atmosphere). About one trillionth of the total. The ¹⁴ C immediately undergoes an exchange reaction with ¹² C of carbon dioxide, and carbon dioxide containing ¹⁴ C is generated.

Since plants take in carbon dioxide in the atmosphere and grow by photosynthesis, ¹⁴ C is always contained at a constant concentration. In contrast, fossil resources such as oil, coal, and natural gas, which were originally included in ¹⁴ C, have already been destroyed over the years and are hardly included. Therefore, by measuring the concentration of ¹⁴ C, it is possible to determine how much carbon derived from biomass resources is contained and how much carbon derived from fossil resources is contained. At present, it is common practice to use a standard in which the concentration of ¹⁴ C in the circulating carbon in the natural world in the 1950s is 100%, and oxalic acid (supplied by the American Standards and Science and Technology Association NIST) is used as the standard substance. A value expressed as follows is obtained. As a unit of this ratio, pMC (percent modern carbon) is used.
PMC = ( ¹⁴ Csa / ¹⁴ C50) × 100
¹⁴ C50: ⁽¹⁴ C concentration in the circulation of carbon in the natural world of the 1950s) ¹⁴ C concentration of the standard substance
¹⁴ Csa: ¹⁴ C concentration of the measurement sample.

The ¹⁴ C concentration in the atmosphere measured as of 2011 is known to be 105 pMC (percent Modern Carbon), so if it is a substance derived from 100% biomass resources, it will show the same value of about 105 pMC. It is known. On the other hand, since the ¹⁴ C concentration (pMC) of the fossil resource is 0 pMC, the bioification rate can be calculated by assigning 100% to 105 pMC and assigning 0% to 0 pMC. The bioavailability Y (%) of the measured value X (pMC) is obtained from the following equation.
105: 100 = X: Y.

  The polyester used in the present invention preferably has a bioification rate of 10% or more, and is more preferably 15% or more from the viewpoint of reducing environmental burden.

  As the polyester constituting the filament of the long-fiber nonwoven fabric of the present invention, dicarboxylic acid and / or its ester-forming derivative component (hereinafter sometimes abbreviated as dicarboxylic acid component), terephthalic acid and / or dimethyl thereof Polyethylene terephthalate obtained by using ethylene glycol as the ester or diol component is preferred, and the degree of improvement in heat resistance becomes more remarkable when the polyester copolymer mainly contains ethylene terephthalate units. Further, when the long fiber nonwoven fabric of the present invention is used as a membrane substrate, polyethylene terephthalate is preferably used because of excellent durability such as mechanical strength, heat resistance, water resistance and chemical resistance.

  Examples of the long fiber nonwoven fabric of the present invention include a spunbond nonwoven fabric produced by a spunbond method and a meltblown nonwoven fabric produced by a meltblowing method. The long fiber nonwoven fabric is composed of thermoplastic filaments, and is excellent in mechanical strength and dimensional stability. Therefore, a spunbond nonwoven fabric is preferable.

  In the case of the spunbond method as a method for producing a long-fiber nonwoven fabric, a molten thermoplastic polymer is extruded from a nozzle, and is drawn by a high-speed suction gas to be spun and spun, and then the fibers are collected on a moving conveyor. It is made into a fiber web, and further this fiber web is continuously thermocompression bonded and entangled etc. to produce a nonwoven fabric sheet that is integrated, but in order to make the constituent fibers more highly oriented and crystallized, the spinning speed Is preferably 2000 m / min or more, more preferably 3000 m / min or more, and further preferably 3500 m / min or more. When the thermoplastic filament is formed into a composite form such as a core-sheath type, a normal composite method can be employed.

  Moreover, by suppressing excessive orientation crystallization of the fibers, it is possible to obtain thermal adhesiveness that contributes to improving the mechanical strength of the nonwoven fabric sheet. When used as a separation membrane support, The spinning speed is preferably 5500 m / min or less, more preferably 5000 m / min or less, even more preferably 4500 m / min, because even when heated, the long-fiber nonwoven fabric can be prevented from being bent or rounded. Is less than a minute. In the case of the spunbond method, the spinning speed can be controlled by adjusting the suction pressure at the time of suction drawing with a high-speed suction gas.

  In the long fiber nonwoven fabric of the present invention, it is important that 1 to 500 ppm of a component derived from 1,2 propanediol is contained in the polyester forming at least a part of the surface of the filament constituting the long fiber nonwoven fabric. Thereby, the adhesiveness of the filaments which comprise a long fiber improves, and it becomes a long fiber nonwoven fabric excellent in abrasion resistance and intensity | strength.

  The part of the surface in the present invention is preferably 10% or more of the entire filament surface, more preferably 30% or more, and further preferably 50% or more. Moreover, the raw material containing the component derived from the said 1, 2 propanediol can also be blended and used.

  The filament made of the thermoplastic resin constituting the long-fiber nonwoven fabric may be a thermoplastic filament composed of a single component or a composite thermoplastic filament composed of a plurality of components, but at least the low melting point component adheres to some fibers. In particular, it is composed of a composite thermoplastic filament in which a low melting point polymer having a melting point lower by 10 to 140 ° C. than the melting point of the high melting point polymer is arranged around the high melting point polymer. It is preferable that it is a long-fiber nonwoven fabric.

  A filament which forms a non-woven fabric by forming a long-fiber non-woven fabric by thermocompression bonding by disposing a low-melting-point polymer having a melting point 10 to 140 ° C. lower than the melting point of the high-melting polymer around the high-melting polymer. They can be firmly bonded to each other. When used as a separation membrane support, it is possible to suppress non-uniformity during casting of a polymer solution due to fluffing and membrane defects. By using such a composite thermoplastic filament, the filaments constituting the long-fiber nonwoven fabric are firmly bonded to each other, and the number of adhesion points is increased compared to the mixed fiber type. In particular, it leads to dimensional stability and durability when used as a semipermeable membrane support to which high pressure is applied during use.

  If the melting point difference between the high melting point polymer and the low melting point polymer is 10 ° C. or higher, the desired thermal adhesiveness can be obtained. It can suppress that a melting-point polymer component fuse | melts and productivity falls. A more preferable range of the melting point difference between the high melting point polymer and the low melting point polymer is 20 to 120 ° C, and a more preferable range is 30 to 100 ° C.

  Further, the filament made of the thermoplastic resin constituting the fiber nonwoven fabric of the present invention has a low melting point polymer having a melting point lower by 10 to 140 ° C. than the melting point of the high melting point polymer around the high melting point polymer. The melting point of the high-melting polymer in the case of the long-fiber nonwoven fabric composed of composite thermoplastic filaments is preferably in the range of 160 to 320 ° C. when used as a separation membrane support. If the melting point of the high-melting polymer is 160 ° C. or higher, it is excellent in form stability even if it passes through the process of applying heat during the production of the separation membrane or fluid separation element, and if the melting point is 320 ° C. or lower, the long fiber nonwoven fabric It is possible to suppress a great reduction in productivity by consuming a great deal of heat energy for melting during production. A more preferable range of the melting point of the high melting point polymer is 170 to 300 ° C, and a more preferable range is 180 to 280 ° C.

  The proportion of the low-melting polymer in the case where the fiber constituting the long-fiber nonwoven fabric of the present invention is a composite filament is not limited at all, but is preferably 10 to 70% by mass, and preferably 15 to 60% by mass. It is more preferable that it is 20-50 mass%. If the proportion of the low-melting polymer is 10% by mass or more, sufficient thermal adhesiveness can be obtained. If the proportion is 70% by mass or less, the low-melting polymer is applied to the thermocompression-bonding roll during thermocompression bonding. It can suppress that a component fuse | melts and productivity falls.

  Examples of the composite form of the composite filament include, for example, composite forms such as a concentric core-sheath type, an eccentric core-sheath type, and a sea-island type, and the filament cross-sectional shape includes a circular cross-section, a flat cross-section, a polygonal cross-section, Cross-sectional shapes such as a multilobal cross section and a hollow cross section can be mentioned. Among them, since the filaments can be firmly bonded to each other by thermocompression bonding, it is preferable to use a concentric core-sheath type for the composite form and to use a circular cross section or a flat cross section as the filament shape.

  In the long-fiber nonwoven fabric of the present invention, a crystal nucleating agent, a matting agent, a lubricant, a pigment, an antifungal agent, an antibacterial agent, a flame retardant, a hydrophilic agent and the like are added and contained within a range that does not impair the effects of the present invention. Or it can be applied. In particular, during thermocompression molding of long-fiber nonwoven fabrics, metal oxides such as titanium oxide, which have the effect of improving the adhesion of the long-fiber nonwoven fabric, and separation between the thermocompression-bonding roll and the fiber web by increasing the thermal conductivity. It is a preferred embodiment to add an aliphatic bisamide such as ethylenebisstearic acid amide and / or an alkyl-substituted aliphatic monoamide, which has an effect of improving adhesion stability by increasing moldability. These various additives may be present in the thermoplastic filament or may be present on the surface thereof.

  The single fiber fineness of the filament constituting the long fiber nonwoven fabric is preferably 0.1 to 3.0 dtex, more preferably 0.3 to 2.5 dtex, and still more preferably 0.5 to 2.0 dtex. is there. If the single fiber fineness of the filaments constituting the long fiber nonwoven fabric is 0.1 dtex or more, the spinnability is less likely to deteriorate during the production of the long fiber nonwoven fabric, and when used as a separation membrane support, air permeability can be maintained. Therefore, there is little film peeling at the time of casting of the polymer solution, and good film forming properties can be obtained. On the other hand, if the single fiber fineness of the filaments constituting the long-fiber nonwoven fabric is 3.0 dtex or less, when used as a separation membrane support, it can be densified, so that it does not cause excessive permeation at the time of casting a polymer solution and is good. Film properties can be obtained.

  Moreover, when the long fiber nonwoven fabric of the present invention is used by laminating the long fiber nonwoven fabric, the long fiber nonwoven fabric can be laminated more firmly and has excellent mechanical strength. The number of laminated long fiber nonwoven fabrics is preferably 2 to 5 layers. If the number of laminated layers is two or more, the texture is improved as compared with a single layer, and sufficient uniformity can be obtained. Moreover, if the number of laminated layers is 5 or less, it is possible to suppress wrinkling during lamination and peeling between layers. Even when the long-fiber nonwoven fabric laminate laminated in this way is used as a separation membrane support, the presence of interlayers prevents over-penetration during casting of a polymer solution and reduces back-through. Are preferably used.

  As a form of the combination of the laminated nonwoven fabrics constituting the long-fiber nonwoven fabric laminate, for example, a laminated nonwoven fabric composed of two layers of spunbond nonwoven fabric, or a laminate of a three-layer structure in which a meltblown nonwoven fabric is arranged between two layers of spunbond nonwoven fabric Nonwoven fabrics and the like can be mentioned, and the configuration differs depending on the application, but at least one layer is preferably a spunbonded nonwoven fabric from the viewpoint of mechanical strength and dimensional stability.

  Examples of the method of laminating the long-fiber nonwoven fabric include thermal bonding using a combination of a flat roll and an engraving roll, and entanglement such as needle punch and water jet punch. Moreover, when using as a separation membrane support body, it is preferable that the surface which forms a film of the nonwoven fabric surface is smooth from the point of film forming property. The smooth surface referred to in the present invention means a surface having no intentional unevenness by an engraving roll or the like, and means a surface treated by a flat roll or the like, for example. In applications where air permeability is required, such as filter materials, it is preferable to laminate by partial thermocompression bonding using an engraving roll or the like.

  Moreover, even if the single fiber fineness of the filament which comprises each long fiber nonwoven fabric to laminate | stack is in the range of 0.1-3.0 dtex, even if it is a single fiber fineness which changes with each layer laminated | stacked. For example, in a separation membrane support constituted by laminating two long fiber nonwoven fabrics, the single fiber fineness of the filament of one long fiber nonwoven fabric is 1.0 dtex, and the single fiber fineness of the filament of the other long fiber nonwoven fabric is 3 .0 dtex, which are appropriately determined according to the product design.

Basis weight of the long fiber nonwoven fabric of the present invention is intended to be determined as appropriate depending on the application and product design, is preferably 15 to 50 g / ^{m 2,} more preferably from 20 to 400 g / ^{m 2.} If the basis weight is 15 g / m ² or more, sufficient mechanical strength can be obtained, and production can be performed without any problem in operability such as sheet cutting at the time of fabric production. On the other hand, when the basis weight is 400 g / m ² or less, the obtained long fiber nonwoven fabric can be sufficiently handled, and the production cost is excellent. When used as a separation membrane support, basis weight is preferably from 20 to 150 g / ^{m 2,} more preferably from 30 to 120 g / ^{m 2,} more preferably from 40~90g / ^{m 2.} When the basis weight of the separation membrane support is 20 g / m ² or more, a separation membrane with excellent mechanical strength and durability can be obtained with less permeation and the like when casting a polymer solution. Can be obtained. On the other hand, if the basis weight of the separation membrane support is 150 g / m ² or less, the thickness of the separation membrane can be reduced and the separation membrane area per fluid separation element unit can be increased. The basis weight of each long-fiber nonwoven fabric to be laminated is not limited as long as the basis weight of the final separation membrane support is in the range of ²⁰ to 150 g / m ^2. For example, the basis weight is 10 g / m ² 3 It is determined as appropriate according to the product design, such as sheet lamination or 30 g / m ² lamination. Here, the basis weight of the long-fiber nonwoven fabric refers to that measured by the method described in Example (4) below.

  Although the thickness of the long-fiber nonwoven fabric of the present invention is appropriately determined according to the use and product design, it is preferably 0.01 to 1.00 mm, more preferably 0.03 to 0.80 mm. is there. If the long fiber nonwoven fabric has a thickness of 0.01 mm or more, a long fiber nonwoven fabric excellent in mechanical strength and durability can be obtained. On the other hand, if the thickness of the long-fiber nonwoven fabric is 1.00 mm or less, the rigidity does not become too high and the handling property is excellent. When used as a separation membrane support, the thickness is preferably 0.03 to 0.20 mm, more preferably 0.04 to 0.16 mm, and even more preferably 0.05 to 0.00. 12 mm. If the thickness of the separation membrane support is 0.03 mm or more, a separation membrane excellent in mechanical strength and durability can be obtained with less excessive permeation at the time of casting a polymer solution and having good film-forming properties. Can be obtained. On the other hand, if the thickness of the separation membrane support is 0.20 mm or less, the thickness of the separation membrane can be reduced and the separation membrane area per fluid separation element unit can be increased.

  Next, an embodiment in which the long fiber nonwoven fabric of the present invention is used as a separation membrane support will be described.

  The separation membrane support made of the long-fiber nonwoven fabric of the present invention preferably has a boiling water curl height of 0 to 2.0 mm in the vertical direction after being treated in boiling water for 5 minutes, more preferably 0 to 1.mm. It is 8 mm, more preferably 0 to 1.0 mm. Moreover, it is preferable that it is 0-4.0 mm in a horizontal direction, More preferably, it is 0-3.6 mm, More preferably, it is 0-2.5 mm. By doing so, the membrane does not bend or curl when receiving heat due to drying or the like in the process of manufacturing the separation membrane, and also in the fluid separation element manufacturing process. Excellent film stability and processability can be obtained with excellent stability.

  The boiling water curl height as used in the present invention refers to taking a sample of 25 cm in length and 25 cm in width from an arbitrary part of a long-fiber nonwoven fabric, immersing it in boiling water for 5 minutes, taking it out, and taking the long fiber on a flat table. After the nonwoven fabric is naturally dried with the smooth surface of the nonwoven fabric facing up, the height (distance from the platform) of the center of both sides in the vertical and horizontal directions is measured in units of 0.5 mm for each of the three samples. They are obtained by averaging each of the vertical and horizontal directions. The average curl height in the vertical and horizontal directions was defined as the average curl height.

  Next, a production method in the case where the long fiber nonwoven fabric of the present invention is used as a separation membrane support will be described.

  The separation membrane support composed of the long-fiber nonwoven fabric of the present invention can obtain a separation membrane with good film forming properties and excellent durability when the separation membrane is formed on the support, As described above, a long fiber nonwoven fabric obtained by a spunbond method or a melt blow method is used. Among them, it is preferable to use a long fiber nonwoven fabric obtained by a spunbond method because of excellent mechanical strength.

  In addition, as a method of laminating long fiber nonwoven fabrics, a temporarily bonded long fiber nonwoven fabric is produced by the spunbond method, and the spunbond nonwoven fabrics are bonded to each other by post-processing, or the bonded spunbond nonwoven fabrics are bonded to each other. For example, the former is a preferred method because it is easy to reduce workability and thickness.

  As a method of thermocompression bonding, since it is preferable to have a smooth surface in terms of improving film forming properties and suppressing fuzzing, it is preferable to perform thermocompression bonding with a pair of upper and lower flat rolls for integration. It is. In addition, by suppressing the fusion of fibers on the surface of the long-fiber nonwoven fabric and maintaining the form, it is possible to obtain a anchoring effect that suppresses separation of the separation membrane when used as a separation membrane support. A thermocompression bonding method using an unheated elastic roll is also preferably used. Examples of the elastic roll include so-called paper rolls such as paper, cotton, and aramid paper, and resin rolls such as urethane resin, silicon resin, and hard rubber.

  When the long fiber nonwoven fabric is collected in a temporarily bonded state, the density of the long fiber nonwoven fabric can be further increased at the time of thermocompression bonding at the time of lamination. At that time, the temperature of the heated flat roll is preferably 180 to 60 ° C lower than the melting point of the thermoplastic filament constituting the long-fiber nonwoven fabric, more preferably 160 to 80 ° C, and further preferably 140 to 100 ° C. This is a preferred embodiment.

  In the case of a composite thermoplastic filament in which a low melting point polymer having a melting point lower by 10 to 140 ° C. than the melting point of the high melting point polymer is disposed around the high melting point polymer, the melting point of the low melting point polymer is 180 to 60 ° C. Low is preferable, 160 to 80 ° C. is more preferable, and 140 to 100 ° C. is further preferable. The above conditions can also be preferably applied to the case where the composite form is a core-sheath type.

  The linear pressure is preferably 100 kg / cm or less, more preferably 80 kg / cm or less, and still more preferably 60 kg / cm or less.

  On the other hand, when the long fiber nonwoven fabric is collected in the bonded state, the temperature of the heated flat roll is preferably 80 to 20 ° C. lower than the melting point of the thermoplastic filament constituting the long fiber nonwoven fabric, and 70 to 30 ° C. lower. Is a more preferred embodiment. In the case of a composite thermoplastic filament in which a low melting point polymer having a melting point lower by 10 to 140 ° C. than the melting point of the high melting point polymer is disposed around the high melting point polymer, the melting point of the low melting point polymer It is preferably lower by 80 to 20 ° C, and more preferably by 70 to 30 ° C. The above conditions can also be preferably applied to the case where the composite form is a core-sheath type.

  The linear pressure of the flat roll is preferably 50 kg / cm or more, more preferably 100 kg / cm or more.

  As for the lamination method, for example, in the case of laminating 2 to 5 layers of the temporarily bonded spunbond nonwoven fabric collected by the above-mentioned means, after overlapping, a pair of upper and lower flat rolls or a heated metal roll and non-layered A method of thermocompression bonding with a heated elastic roll is preferably used. The temperature of the heated roll at this time is preferably 80 to 20 ° C. lower than the melting point of the thermoplastic filament constituting the long fiber nonwoven fabric, and more preferably 70 to 30 ° C.

  In the case of a composite thermoplastic filament in which a low melting point polymer having a melting point lower by 10 to 140 ° C. than the melting point of the high melting point polymer is disposed around the high melting point polymer, the melting point of the low melting point polymer It is preferably lower by 80 to 20 ° C, and more preferably by 70 to 30 ° C. Moreover, it is preferable that the linear pressure of a roll is 50 kg / cm or more, More preferably, it is 100 kg / cm or more.

  In addition, as a lamination method of a three-layer structure in which a melt blown nonwoven fabric is disposed between two layers of a temporarily bonded spunbond nonwoven fabric, a separate line is provided between the two layers of the temporarily bonded spunbond nonwoven fabric obtained by the above method. After the melt blown nonwoven fabric manufactured in step 1 is sandwiched, and the method of thermocompression bonding under the same conditions as the two layers of the above-mentioned temporarily bonded spunbond nonwoven fabric, and the upper part of a series of collection conveyors. Preferably used is a method of sequentially collecting and laminating fiber webs extruded and spun from the spunbond nozzle, meltblown nozzle, and spunbond nozzle, respectively, and then thermocompression bonding under the above-mentioned conditions during lamination.

  Further, the spunbond nozzle, melt blow nozzle, and spunbond nozzle arranged on the top of the series of collection conveyors are respectively collected and laminated in order to collect and laminate the fiber web. Also preferred is a method in which a web is thermocompression bonded between a heat roll installed on a collection conveyor and the collection conveyor, a sheet in a temporarily bonded state is produced and wound, and then thermocompression bonding is performed according to the above-described conditions during lamination. Can be used.

  The separation membrane made of the long nonwoven fabric of the present invention is a separation membrane formed by forming a membrane having a separation function on the above-mentioned separation membrane support, and examples include a microfiltration membrane, an ultrafiltration membrane, Examples thereof include nanofiltration membranes and semipermeable membranes such as reverse osmosis membranes. As a method for producing the separation membrane, a method of forming a membrane having a separation function by casting a polymer solution on at least one surface of the above-mentioned separation membrane support is preferably used. In the case where the separation membrane is a semipermeable membrane, it is also a preferred form that the membrane having a separation function is a composite membrane including a support layer and a semipermeable membrane layer (in this case, the support layer has a separation function). You don't have to.)

  The polymer solution cast on the separation membrane support has a separation function when it becomes a membrane, such as polysulfone, polyarylethersulfone such as polyethersulfone, polyimide, polyvinylidene fluoride, and cellulose acetate. The solution of is preferably used. Among these, from the viewpoint of chemical, mechanical and thermal stability, a solution of polysulfone and polyarylethersulfone is preferably used. The solvent can be appropriately selected according to the film-forming substance. As the semipermeable membrane when the separation membrane is a composite membrane comprising a support layer and a semipermeable membrane layer, a crosslinked polyamide membrane obtained by polycondensation of a polyfunctional acid halide and a polyfunctional amine is preferably used.

  Applications of the long-fiber nonwoven fabric of the present invention include, for example, industrial materials such as filters, filter base materials, and wire wrapping materials, wallpaper, moisture-permeable waterproof sheets, roofing roofing materials, sound insulation materials, heat insulating materials, and sound absorbing materials. Agricultural materials such as materials, wrapping materials, bag materials, signage materials, printing materials, etc., grass protection sheets, drainage materials, ground reinforcement materials, sound insulation materials, sound absorbing materials, etc., solid materials, light shielding sheets, etc. It can be suitably used for vehicle materials such as ceiling materials and spare tire cover materials.

  Next, based on an Example, the long fiber nonwoven fabric of this invention is demonstrated concretely. The characteristic values of the separation membrane support, the long-fiber nonwoven fabric constituting the separation membrane support, and the thermoplastic filament constituting the long-fiber nonwoven fabric, and the characteristic values in the examples were measured by the following methods. It is.

(1) Melting point of resin (° C):
The melting point of the resin was measured using a differential scanning calorimeter DSC-2 manufactured by Perkin Elma Co., Ltd. under the condition of a temperature increase rate of 20 ° C./min. did. Further, in the differential scanning calorimeter, for a resin whose melting endotherm curve does not show an extreme value, the resin was heated on a hot plate, and the temperature at which the resin was completely melted by microscopic observation was taken as the melting point.

(2) Intrinsic viscosity (IV):
The intrinsic viscosity IV of polyethylene terephthalate (PET) resin was measured by the following method. 8 g of a sample was dissolved in 100 ml of orthochlorophenol, and the relative viscosity η _r was determined by the following formula using an Ostwald viscometer at a temperature of 25 ° C.
Η _r = η / η ₀ = (t × d) / (t ₀ × d ₀ )
(Where η is the viscosity of the polymer solution, η ₀ is the viscosity of the orthochlorophenol, t is the drop time of the solution (seconds), d is the density of the solution (g / cm ³ ), and t ₀ is the drop of the orthochlorophenol. (Time (second), d ₀ represents the density (g / cm ³ ) of orthochlorophenol, respectively)
Next, the intrinsic viscosity IV was calculated from the above relative viscosity η _r by the following formula.
IV = 0.0242η _r +0.2634.

(3) Content of components derived from 1,2-propanediol in the polymer (ppm):
First, a 1000 μg / ml aqueous solution of 1,2-butanediol was prepared and used as an internal standard solution A. 0.1 g of a sample was weighed into a vial, 0.006 ml of an internal standard solution and 1 ml of aqueous ammonia were added and sealed, heated at a temperature of 150 ° C. for 3 hours, and then allowed to cool to room temperature (25 ° C.). Subsequently, 2 ml of methanol and 2.0 g of terephthalic acid were added, and the mixture was shaken for 15 minutes and centrifuged at 3500 G for 3 minutes. The supernatant was taken out, measured with a gas chromatograph (GC 6890, manufactured by Agilent Technologies) under the following setting conditions, and the content was determined using a calibration curve described later.

  Split ratio: 1/20, carrier gas flow rate: 2 mL / min, inlet temperature: 220 ° C., injection volume: 1 μL, MS: SX-102A manufactured by JEOL, monitor ion: m / z 61.0290.

  A calibration curve for 1,2-propanediol was prepared by the following procedure. After preparing a 1000 μg / ml aqueous solution of 1,2-propanediol as standard mother liquor B, the amount of the standard mother liquor B was changed and diluted with a mixed solvent (methanol: water = 2: 1 (mass ratio)). Thus, five types of standard solutions C were prepared. In addition, an internal standard solution A was added so that each solution contained 2.00 μg / ml of 1,2 butanediol as an internal standard. After measuring the prepared standard solution C under the above-mentioned conditions by gas chromatography, the peak area ratio of the obtained 1,2-propanediol and the internal standard substance and the concentration of 1,2-propanediol in the standard solution C were obtained. Was plotted on a graph to prepare a calibration curve for 1,2-propanediol.

(4) Bioration rate measurement method:
Biotization rate was determined according to ASTM D6866.

Specifically, after pulverizing a sample (nonwoven fabric) with sandpaper and a pulverizer, the sample is heated together with copper oxide to be completely oxidized to carbon dioxide, and this is reduced to graphite with iron powder. Converted to one compound. The obtained graphite sample was introduced into an AMS apparatus, and the ¹⁴ C concentration was measured. In addition, the ¹⁴ C concentration of oxalic acid (supplied by American Standards and Science and Technology Association NIST), which is a standard substance, was also measured. Here, the ratio of ¹⁴ C and ¹² C of the sample ( ¹⁴ C / ¹² C) is ¹⁴ As, and the ratio of ¹⁴ C and ¹² C of the standard substance ( ¹⁴ C / ¹² C) is ¹⁴ Ar. ¹⁴ C was determined.
Δ ¹⁴ C = {( ¹⁴ As− ¹⁴ Ar) / ¹⁴ Ar} × 1000
From this Δ ¹⁴ C, pMC (percent Modern Carbon) was determined by the following equation.
PMC = Δ ¹⁴ C / 10 + 100
In accordance with US Material Test Standard (ASTM) D6866, the pMC was multiplied by 0.95 (= 100/105) as shown in the following formula to obtain the biotinylation rate.
-Bioration rate (%) = 0.95 x pMC.

(5) Single fiber fineness (dtex):
The single fiber fineness is obtained by randomly collecting 10 small sample pieces from a nonwoven fabric, taking 500 to 3000 times photographs with a scanning electron microscope, and measuring the diameter of 100 single fibers, 10 from each sample. These average values were corrected by the density of the polymer and rounded off to the second decimal place.

(6) Fabric weight of nonwoven fabric (g / m ² ):
Three non-woven fabrics of 30 cm × 50 cm were collected, the weight of each sample was measured, the average value of the obtained values was converted per unit area, and the first decimal place was rounded off.

(7) Non-woven fabric thickness (mm):
The thickness of the nonwoven fabric is based on JIS L 1906 (2000 version) 5.1, using a pressurizer with a diameter of 10 mm, and 10 points in 0.01 mm increments per 1 m width direction of the nonwoven fabric with a load of 10 kPa. The average value was rounded off to the second decimal place.

(8) Tensile strength of nonwoven fabric (N / 5 cm):
The tensile strength of the nonwoven fabric is based on 6.3.1 of JIS L1913 (2010 edition)
For a nonwoven fabric sample of 5 cm × 30 cm, the strength was measured at 5 points in each of the machine direction and the transverse direction at a gripping distance of 20 cm and a tensile speed of 10 cm / min, and the strength at break was read. The value obtained by rounding off the places was taken as the tensile strength in the longitudinal and transverse directions.

(9) Boiling water curl height of non-woven fabric (mm):
The boiling water curl height of the non-woven fabric is taken from any part of the non-woven fabric, 3 samples of 25 cm in length (non-woven fabric length direction) × 25 cm in width (non-woven fabric width direction), immersed in boiling water for 5 minutes, taken out, On a flat table, the nonwoven fabric is air-dried with the smooth surface of the nonwoven fabric facing up. For each of the three samples, measure the height of the central part (distance from the platform) on both sides in units of 0.5 mm, average them, and round off the second decimal place to obtain the boiling water curl height. Calculated.

(10) Abrasion resistance (class) of nonwoven fabric:
Using a non-woven fabric as a sample using a Gakushin dyeing dyeing fastness tester, the friction cloth is rubbed with a gold width No. 3 and rubbed at a load of 500 gf with a frequency of 100 reciprocations, and fuzzed and worn on the surface of the non-woven fabric. Visual evaluation was evaluated based on the following criteria, and grades 4 and 5 were accepted (average value of n = 5).
0 grade: Large damage 1 grade: Medium damage 2 grade: Small damage 3 grade: No damage, fluff generation Small 4 grade: No damage, fluff occurrence Micro 5 grade: No damage, no fluff

Example 1
The melting point of dried to a moisture content of 50 ppm or less is 260 ° C., the intrinsic viscosity IV is 0.65, the component derived from 1,2-propanediol is 0 ppm of fossil resource-derived ethylene glycol and terephthalic acid, 0.3 mass of titanium oxide. % Polyethylene terephthalate resin, melting point dried to a moisture content of 50 ppm or less is 230 ° C., intrinsic viscosity IV is 0.65, content of 1,2-propanediol-derived component is 23 ppm, and bioavailability is 20%. A copolymer polyester resin composed of biomass-derived ethylene glycol and terephthalic acid with a copolymerization rate of 10 mol% and containing 0.2% by mass of titanium oxide was melted at temperatures of 295 ° C. and 280 ° C., respectively, and a polyethylene terephthalate resin was obtained. As a core component, a copolymer polyester resin as a sheath component, a die temperature of 300 ° C., : Spindle = After spinning from pores at a mass ratio of 80:20, spinning with an ejector at a spinning speed of 4500 m / min, the entire surface is covered with polyethylene terephthalate containing a component derived from 1,2-propanediol. Concentric core-sheath filaments (circular in section) were collected as fiber webs on a moving net conveyor. The collected fiber web is thermocompression bonded with a pair of upper and lower flat rolls at a flat roll surface temperature of 140 ° C. and a linear pressure of 60 kg / cm, the single filament fineness of the constituent filaments is 1.2 dtex, the basis weight is 35 g / m ² , A spunbond nonwoven fabric having a thickness of 0.15 mm was produced.

Two layers of the obtained spunbond nonwoven fabric are superposed, using a pair of flat rolls with a steel roll on the upper side and a resin roll on the lower side, only the upper steel roll is heated to a temperature of 170 ° C., and the linear pressure is 170 kg / cm. Furthermore, thermocompression bonding was performed to produce a spunbonded nonwoven fabric having a basis weight of 70 g / m ² and a thickness of 0.08 mm to obtain a long-fiber nonwoven fabric laminate. The tensile strength of the obtained long fiber nonwoven fabric laminate was 452 N / 5 cm in length and 221 N / 5 cm in width, and the boiling water curl was 0.3 mm in length and 1.7 mm in width. The results are shown in Table 1.

(Example 2)
The sheath component is composed of a biomass resource-derived ethylene glycol and terephthalic acid with a content of 1,2-propanediol derived from 207 ppm, a bioconversion rate of 20% and an isophthalic acid copolymerization rate of 10 mol%, and 0.2 mass of titanium oxide. A single filament of a constituent filament which was carried out in the same manner as in Example 1 except that a copolyester resin containing 1% was used, and the entire surface was covered with polyethylene terephthalate containing a component derived from 1,2-propanediol. A spunbonded nonwoven fabric having a fineness of 1.2 dtex, a basis weight of 35 g / m ² and a thickness of 0.13 mm was produced.

Two sheets of the obtained spunbonded nonwoven fabric were overlapped and laminated by the same method as in Example 1 to obtain a long fiber nonwoven fabric laminate. The basis weight of the obtained long fiber nonwoven fabric laminate is 70 g / m ² , the thickness is 0.07 mm, the tensile strength is 442 N / 5 cm in length, 207 N / 5 cm in width, and boiling water curl is The length was 0.3 mm and the width was 1.8 mm. The results are shown in Table 1.

(Example 3)
The core component is derived from a biomass resource having a melting point of 260 ° C. dried to a moisture content of 50 ppm or less, an intrinsic viscosity IV of 0.65, a content of components derived from 1,2-propanediol of 25 ppm, and a bioavailability of 20%. Except having used polyethylene terephthalate resin which consists of ethylene glycol and terephthalic acid and contains 0.3% by mass of titanium oxide, it is carried out in the same manner as in Example 1 and contains components derived from 1,2-propanediol. A spunbonded nonwoven fabric having a single filament fineness of 1.2 dtex, a basis weight of 35 g / m ² , and a thickness of 0.14 mm was produced with a constituent filament whose entire surface was covered with polyethylene terephthalate.

Two sheets of the obtained spunbonded nonwoven fabric were overlapped and laminated by the same method as in Example 1 to obtain a long fiber nonwoven fabric laminate. The basis weight of the obtained long fiber nonwoven fabric laminate is 70 g / m ² , the thickness is 0.09 mm, the tensile strength is 420 N / 5 cm in length, 194 N / 5 cm in width, and boiling water curl is The length was 0.4 mm and the width was 2.0 mm. The results are shown in Table 1.

(Example 4)
A spunbonded nonwoven fabric was produced by the same method as in Example 1, and the single filament fineness of the constituent filament whose entire surface was covered with polyethylene terephthalate containing a component derived from 1,2-propanediol was 1.2 dtex, and the basis weight was 30 g / A spunbonded nonwoven fabric of m ² and a thickness of 0.12 mm was produced.

Three sheets of the obtained spunbonded nonwoven fabric were overlapped and laminated by the same method as in Example 1 to obtain a long fiber nonwoven fabric laminate. The basis weight of the obtained long fiber nonwoven fabric laminate is 90 g / m ² , the thickness is 0.10 mm, the tensile strength is 542 N / 5 cm in length, 247 N / 5 cm in width, and boiling water curl is The length was 0.7 mm and the width was 2.2 mm. The results are shown in Table 1.

(Example 5)
A spunbonded nonwoven fabric was produced in the same manner as in Example 1, and the single filament fineness of the constituent filament whose entire surface was covered with polyethylene terephthalate containing a component derived from 1,2-propanediol was 1.2 dtex, and the basis weight was 20 g / A spunbonded nonwoven fabric of m ² and a thickness of 0.08 mm was produced.

Five sheets of the obtained spunbonded nonwoven fabric were overlapped and laminated by the same method as in Example 1 to obtain a long fiber nonwoven fabric laminate. The basis weight of the obtained long fiber nonwoven fabric laminate is 100 g / m ² , the thickness is 0.11 mm, the tensile strength is 632 N / 5 cm in length, 284 N / 5 cm in width, and boiling water curl is The length was 1.5 mm and the width was 2.9 mm. The results are shown in Table 1.

  The properties of the obtained temporary bonded nonwoven fabric and the long fiber nonwoven fabric laminate are as shown in Table 1. Both have good spinnability, and the obtained long fiber nonwoven fabric laminate has excellent adhesiveness and mechanical strength. It was excellent in wear resistance and thermal dimensional stability. Moreover, although these long fiber nonwoven fabric laminated bodies are as having shown in Table 1, the long fiber nonwoven fabric laminated body of Examples 1-5 is fixed on a glass plate, Polysulfone (made by Solvay Advanced Polymers company) on it. "Udel" (registered trademark) -P3500) in a 15 wt% dimethylformamide solution (cast solution) having a thickness of 50 µm, cast at room temperature (20 ° C), and immediately immersed in pure water at room temperature for 5 minutes. As a result, a polysulfone separation membrane was formed, and in all cases, the casting liquid was on the inner surface from the back side plane of the separation membrane support and there was no back-through, and peeling and non-uniform pinhole defects were all Further, the film-forming property was good, curling after film formation was suppressed, and the film could be suitably used as a separation membrane support.

(Comparative Example 1)
Titanium oxide consisting of fossil resource-derived ethylene glycol and terephthalic acid having a core component dried at a moisture content of 50 ppm or less, a melting point of 260 ° C., an intrinsic viscosity IV of 0.65, and a component derived from 1,2-propanediol of 0 ppm Of polyethylene terephthalate resin containing 0.3% by mass, a sheath component, a melting point of 230 ° C. dried to a moisture content of 50 ppm or less, an intrinsic viscosity IV of 0.65, and a content of a component derived from 1,2-propanediol of 0 ppm The fossil resource-derived ethylene glycol was used in the same manner as in Example 1 except that a copolymerized polyester resin containing 10 mol% of isophthalic acid and 0.2% by mass of titanium oxide was used. , 2-filament monofilament fiber whose surface is not covered with polyethylene terephthalate containing a component derived from 2-propanediol But 1.2 dtex, basis weight 35 g / ^{m 2,} thickness was produced 0.15mm spunbond nonwoven.

Two sheets of the obtained spunbonded nonwoven fabric were overlapped and laminated by the same method as in Example 1 to obtain a long fiber nonwoven fabric laminate. The basis weight of the obtained long fiber nonwoven fabric laminate is 70 g / m ² , the thickness is 0.10 mm, the tensile strength is 421 N / 5 cm in length, 193 N / 5 cm in width, and boiling water curl is The length was 4.0 m and the width was 5.6 mm. The results are shown in Table 2.

(Comparative Example 2)
A biomass component-derived ethylene glycol having a melting point of 255 ° C., an intrinsic viscosity IV of 0.65, a content of 1,2-propanediol-derived component of 645 ppm, and a bioavailability of 20%, dried to a moisture content of 50 ppm or less as a core component Polyethylene terephthalate resin containing 0.3% by mass of titanium oxide and a melting point of 225 ° C. dried to a moisture content of 50 ppm or less, an intrinsic viscosity IV of 0.65, and a sheath component derived from 1,2-propanediol. Other than using a polyester resin containing 0.2 mass% of titanium oxide, composed of biomass-derived ethylene glycol and terephthalic acid with an isophthalic acid copolymerization rate of 10 mol% with a component content of 668 ppm and a bioavailability of 20% Is carried out in the same manner as in Example 1 and contains a 1,2-propanediol-derived component. Single fiber fineness of structure filaments entire surface by Chi terephthalate are covered is 1.2 dtex, weight per unit area 35 g / ^{m 2,} thickness was prepared spunbonded nonwoven fabric 0.14 mm.

Two sheets of the obtained spunbonded nonwoven fabric were overlapped and laminated by the same method as in Example 1 to obtain a long fiber nonwoven fabric laminate. The basis weight of the obtained long fiber nonwoven fabric laminate is 70 g / m ² , the thickness is 0.09 mm, the tensile strength is 381 N / 5 cm in length, 187 N / 5 cm in width, and boiling water curl is The length was 0.3 mm and the width was 1.7 mm. The results are shown in Table 2.

(Comparative Example 3)
Spinned using the polyethylene terephthalate resin described in Example 1, drawn polyethylene terephthalate short fiber having a single fiber fineness of 1.0 dtex and a length of 10 mm, and drawn polyethylene terephthalate having a single fiber fineness of 1.7 dtex and a length of 10 mm Short fibers and unstretched polyethylene terephthalate short fibers having a single fiber fineness of 1.2 dtex and a length of 5 mm are mixed in water at a mass ratio of 20:40:40, respectively, and then sufficiently dispersed so that the fiber concentration is 0. A 05% aqueous slurry was prepared. This is sent to a circular paper machine, and after paper making, dried with a Yankee dryer at a temperature of 120 ° C. and wound up to produce a paper web whose entire surface is covered with polyethylene terephthalate containing components derived from 1,2-propanediol. did.

  Using the pair of flat rolls having a steel roll on the upper side and a cotton roll on the lower side, only the upper steel roll was heated to a temperature of 150 ° C. and thermocompression bonded at a linear pressure of 150 kg / cm. A papermaking nonwoven fabric was produced.

The resulting paper-made nonwoven fabric has a basis weight of 70 g / m ² , a thickness of 0.10 mm, a tensile strength of 162 N / 5 cm in the vertical direction and 77 N / 5 cm in the horizontal direction, and the boiling water curl has a vertical length of 0.00. It was 3 mm and the width was 0.7 mm. The results are shown in Table 2.

  The characteristics of the obtained long fiber nonwoven fabric and the long fiber nonwoven fabric laminate are as shown in Table 2, but the long fiber nonwoven fabric of Comparative Example 1 uses a resin in which 1,2-propanediol was not detected. In this case, the mechanical strength was inferior. Moreover, the boiling water curl height of the long-fiber nonwoven fabric laminate was high, and when used as a separation membrane support, it curled after membrane formation. Further, the long-fiber nonwoven fabric of Comparative Example 2 contained a large amount of 1,2-propanediol, had many defects during spinning, and had poor mechanical strength. Further, the papermaking nonwoven fabric of Comparative Example 3 was inferior in mechanical strength and boiling water curl height. Further, when used as a separation membrane support, it curls after membrane formation.

(Example 6)
Titanium oxide made of fossil resource-derived ethylene glycol and terephthalic acid, which has a melting point of 260 ° C., an intrinsic viscosity of 0.65, a 1,2-propanediol-derived component that has been dried to a water content of 50 ppm or less, and 0 ppm, is not added. Polyethylene terephthalate resin containing 3% by mass, a melting point dried to a water content of 50 ppm or less at 230 ° C., an intrinsic viscosity IV of 0.65, a content of components derived from 1,2-propanediol of 23 ppm, and a bioavailability of 20% Polyethylene terephthalate resin, which is made of biomass resource-derived ethylene glycol and terephthalic acid with an isophthalic acid copolymerization rate of 10 mol% and melted at a temperature of 295 ° C and 280 ° C, respectively, containing 0.2% by mass of titanium oxide. With a core component and a copolymer polyester resin as a sheath component, with a die temperature of 3 After spinning from pores at a mass ratio of 0 ° C., core: sheath = 80: 20, spinning with an ejector at a spinning speed of 4500 m / min, and surface with polyethylene terephthalate containing a component derived from 1,2-propanediol The whole was covered with a concentric core-sheath filament (circular cross-section) and collected as a fiber web on a moving net conveyor. The collected fiber web was thermocompression bonded with a pair of upper and lower flat rolls at a flat roll surface temperature of 160 ° C. and a linear pressure of 60 kg / cm. Furthermore, the upper roll is an embossing roll in which the convex portions of the dot pattern are regularly arranged, and the lower roll is passed between a pair of upper and lower metal rolls that are flat rolls. Was subjected to partial thermocompression bonding under the condition of 70 kg / cm to obtain a long fiber nonwoven fabric. The obtained long fiber nonwoven fabric has a single fiber fineness of 2.0 dtex, a basis weight of 40 g / m ² , a thickness of 0.10 mm, and a tensile strength of 195 N / 5 cm in length and 118 N / in width. The wear resistance of the embossed roll surface was 4.4 grade, and the flat roll surface was 4.0 grade. The results are shown in Table 3.

(Comparative Example 4)
Isophthalic acid, which is fossil resource-derived ethylene glycol having a melting point of 230 ° C., an intrinsic viscosity of 0.65, and a content of 1,2-propanediol-derived component of 0 ppm, dried to a moisture content of 50 ppm or less as a sheath component A temporarily bonded spunbonded nonwoven fabric was produced in the same manner as in Example 5 except that a copolymerized polyester resin containing a copolymerization rate of 10 mol% and titanium oxide was 0.2 mass% was used. Embossing obtained by temporarily bonding a spunbond nonwoven fabric temporarily bonded with an upper roll of dot-patterned protrusions comprising a filament whose entire surface is covered with polyethylene terephthalate containing a component derived from 1,2-propanediol. It is a roll, and the lower roll is passed through a pair of upper and lower metal rolls, the roll surface temperature is set to 190 ° C., and partial thermocompression bonding is performed under the condition that the linear pressure is 70 kg / cm. Obtained. The obtained long fiber nonwoven fabric has a single fiber fineness of 2.0 dtex, a basis weight of 40 g / m ² , a thickness of 0.10 mm, and a tensile strength of 175 N / 5 cm in the vertical direction and 106 N / 5 cm in the horizontal direction. The wear resistance was 3.3 for the embossed roll surface and 3.0 for the flat roll surface. The results are shown in Table 3.

(Comparative Example 5)
Spinned using the polyethylene terephthalate resin described in Example 1, drawn polyethylene terephthalate short fiber having a single fiber fineness of 1.0 dtex and a length of 10 mm, and drawn polyethylene terephthalate having a single fiber fineness of 1.7 dtex and a length of 10 mm Short fibers and unstretched polyethylene terephthalate short fibers having a single fiber fineness of 1.2 dtex and a length of 5 mm were mixed in water at a mass ratio of 20:40:40, respectively, and then sufficiently dispersed to obtain a fiber concentration of 0.1. A 05% aqueous slurry was prepared. This is sent to a circular paper machine, and after paper making, dried with a Yankee dryer at a temperature of 120 ° C. and wound up to produce a paper web whose entire surface is covered with polyethylene terephthalate containing components derived from 1,2-propanediol. did.

  Using the pair of flat rolls, the upper side of which is a steel roll and the lower side is a cotton roll, the upper steel roll is heated to a temperature of 150 ° C. and thermocompression-bonded at a linear pressure of 150 kg / cm. Manufactured.

The resulting papermaking nonwoven fabric has a basis weight of 40 g / m ² , a thickness of 0.06 mm, a tensile strength of 104 N / 5 cm in length and 48 N / 5 cm in width, and wear resistance is an embossing roll. The surface was 2.3 grade and the flat roll surface was 1.1 grade. The results are shown in Table 3.

  The obtained non-woven fabric was as shown in Table 3, but in Example 6, it was a long-fiber non-woven fabric with good spinnability and excellent mechanical strength and wear resistance. On the other hand, the long-fiber nonwoven fabric using the petroleum-derived polyester resin of Comparative Example 4 was inferior in mechanical strength and wear resistance. Further, the papermaking nonwoven fabric of Comparative Example 5 was inferior in mechanical strength and wear resistance.

Claims (7)

  A long-fiber nonwoven fabric comprising a thermoplastic resin mainly composed of polyester, wherein at least a part of the polyester contains 1,2-propanediol-derived components in an amount of 1 to 500 ppm. .   The long fiber according to claim 1, wherein the polyester containing 1 to 500 ppm of a component derived from 1,2-propanediol forms at least part of the surface of the filament constituting the long fiber nonwoven fabric. Non-woven fabric.   A long-fiber non-woven fabric, characterized in that the filament constituting the long-fiber non-woven fabric comprises a core-sheath type composite fiber.   A long-fiber nonwoven fabric laminate comprising 2 to 5 layers of the long-fiber nonwoven fabric according to any one of claims 1 to 3.   The membrane base material which consists of a long-fiber nonwoven fabric or a long-fiber nonwoven fabric laminated body in any one of Claims 1-4.   A separation membrane support comprising the membrane substrate according to claim 5.     A bonded base material comprising the long fiber nonwoven fabric or the long fiber nonwoven fabric laminate according to any one of claims 1 to 4.