WO2022074966A1 - フィラメント、構造体、樹脂組成物、および、フィラメントの製造方法 - Google Patents
フィラメント、構造体、樹脂組成物、および、フィラメントの製造方法 Download PDFInfo
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- WO2022074966A1 WO2022074966A1 PCT/JP2021/032063 JP2021032063W WO2022074966A1 WO 2022074966 A1 WO2022074966 A1 WO 2022074966A1 JP 2021032063 W JP2021032063 W JP 2021032063W WO 2022074966 A1 WO2022074966 A1 WO 2022074966A1
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Classifications
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
Definitions
- the present invention relates to a filament, a structure containing the filament, a resin composition suitable as a raw material for the filament, and a method for producing the filament.
- the present invention relates to a filament whose main raw material is a polyamide resin.
- filaments made of polyamide resin as a main raw material have been used for various purposes. Since such a polyamide filament has high strength, it is highly useful. Therefore, it is considered to use the polyamide filament as a structure such as a non-woven fabric, an adsorbent, a filter cloth, a filter paper or a filter.
- the conventional polyamide filament for example, a polyamide filament whose main raw material is polyamide 66
- Patent Document 1 a polyamide resin composed of methylylenediamine and adipic acid as a main raw material is also disclosed (Patent Document 1). However, it cannot be said that it is sufficient in terms of the decrease in strength after water absorption.
- the present invention is intended to solve the above problems, and is a filament containing a polyamide resin, which has high strength and a high retention rate of mechanical properties after water absorption, a filament, a structure, and a resin composition.
- an object of the present invention is to provide a method for producing a filament.
- the polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine.
- 70 mol% or more of the constituent unit derived from dicarboxylic acid is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, and the content of the compound having a molecular weight of 310 or more and 1000 or less is 0.1% by mass or more.
- the compound having a molecular weight of 310 or more and 1000 or less includes a cyclic compound formed from one molecule of xylylene diamine and one molecule of ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms.
- ⁇ 1> Or the filament according to ⁇ 2>.
- ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, in which 30 to 100 mol% of the constituent unit derived from the diamine is derived from m-xylylenediamine and 0 to 70 mol% is derived from paraxylylenediamine. Filament described in.
- ⁇ 5> The filament according to any one of ⁇ 1> to ⁇ 4>, wherein 70 mol% or more of the constituent unit derived from the dicarboxylic acid is 1,12-dodecanedioic acid.
- ⁇ 6> The retention rate from the tensile strength before immersion in the chemical solution when the filament is immersed in hydrochloric acid having a concentration of 10% by mass for 1 week after humidity adjustment in an environment of 23 ° C. and 50% relative humidity for 1 week. After adjusting the humidity of the filament for 1 week in an environment of 90% or more and 50% relative humidity, before immersing the filament in a 10% by mass aqueous solution of sodium hydroxide for 1 week.
- the filament according to any one of ⁇ 1> to ⁇ 5> which has a retention rate from tensile strength of 90% or more.
- the filament according to any one of ⁇ 1> to ⁇ 6> which has a single yarn fineness of 2.0 ⁇ 10 -5 to 50 dtex.
- the filament according to any one of ⁇ 1> to ⁇ 7> which is a multifilament.
- a structure comprising the filament according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 10> The structure according to ⁇ 9>, wherein the structure is a non-woven fabric, an adsorbent, a filter cloth, a filter paper, or a filter.
- a resin composition having a compound content of 310 or more and 1000 or less is 0.1% by mass or more and 1.5% by mass or less, and a compound having a molecular weight of less than 310 is 0.1% by mass or less.
- the resin composition according to ⁇ 11> which is used for filaments, non-woven fabrics, adsorbents, filter cloths, filter papers or filters.
- the present embodiment will be described in detail.
- the following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
- "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
- various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
- the filament of the present embodiment contains a polyamide resin, and the polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is xylylene diamine.
- 70 mol% or more of the constituent unit derived from the dicarboxylic acid is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, and the content of the compound having a molecular weight of 310 or more and 1000 or less is 0. It is characterized in that the content of the compound having a molecular weight of less than 310 is 0.1% by mass or less and is 1% by mass or more and 1.5% by mass or less.
- a filament having high strength and a high retention rate of mechanical properties after water absorption can be obtained. More specifically, a product having excellent linear strength and a high retention rate of elastic modulus and tensile strength after water absorption can be obtained. Further, those having excellent continuous productivity and chemical resistance can be obtained.
- the reason for this is presumed to be as follows. That is, in the filament of the present embodiment, xylylenediamine and ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms are used as the raw material monomer of the polyamide resin. By using a polyamide resin composed of such a raw material, it was possible to make it difficult for the filament to absorb water and to suppress deterioration of mechanical properties.
- the polyamide resin used in the present embodiment is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine and is derived from the dicarboxylic acid. 70 mol% or more of the constituent units of the above are derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, and the content of the compound having a molecular weight of 310 or more and 1000 or less is 0.1% by mass or more and 1.5. The content of the compound having a molecular weight of less than 310 by mass% or less is 0.1% by mass or less.
- polyamide resin (A) such a polyamide resin
- 70 mol% or more of the constituent unit derived from diamine is derived from xylylenediamine, but it is preferably 80 mol% or more, more preferably 90 mol% or more, and 95. It is more preferably mol% or more, and even more preferably 99 mol% or more. The upper limit is 100 mol%.
- Xylylenediamine is 10 to 100 mol% of metaxylylenediamine and 90 to 0 mol% of paraxylylenediamine (however, the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol%. ) Is preferably contained, and 30 to 100 mol% of metaxylylenediamine and 70 to 0 mol% of paraxylylenediamine are more preferably contained, and 50 to 100 mol% of metaxylylenediamine and 0 to 0 to It is more preferred to contain 50 mol% paraxylylenediamine.
- the total of the metaxylylenediamine and the paraxylylenediamine preferably occupies 95 mol% or more, more preferably 99 mol% or more, still more preferably 100 mol%.
- Diamine components other than xylylenediamine include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2, Aliphatic diamines such as 2,4-trimethyl-hexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1, 3-Diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, etc.
- diamines having an aromatic ring such as alicyclic diamine, bis (4-aminophenyl) ether, paraphenylenediamine, and bis (aminomethyl) naphthalene can be exemplified. Can be used.
- 70 mol% or more of the constituent unit derived from the dicarboxylic acid is ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms (preferably ⁇ , ⁇ having 12 to 14 carbon atoms).
- -It is derived from a linear aliphatic dicarboxylic acid, more preferably 1,12-dodecanedioic acid).
- the ratio of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms in the constituent unit derived from the dicarboxylic acid is preferably 80 mol% or more, more preferably 90 mol% or more. It is more preferably 95 mol% or more, and even more preferably 99 mol% or more.
- the upper limit is 100 mol%.
- dicarboxylic acid component other than the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms examples include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, and sebacic acid having 10 or less carbon atoms.
- ⁇ , ⁇ -Linear aliphatic dicarboxylic acid isophthalic acid, terephthalic acid, orthophthalic acid and other phthalic acid compounds, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, A naphthalenedicarboxylic acid such as 7-naphthalenedicarboxylic acid can be exemplified, and one kind or a mixture of two or more kinds can be used.
- amide bond constituting the polyamide resin (A) is formed by the bond between the dicarboxylic acid and the diamine.
- the polyamide resin (A) contains other sites such as a terminal group in addition to the structural unit derived from a dicarboxylic acid and the structural unit derived from a diamine. Further, it may contain repeating units having an amide bond not derived from the bond between the dicarboxylic acid and the diamine, a trace amount of impurities, and the like.
- the polyamide resin (A) is a component constituting the polyamide resin in addition to the diamine component and the dicarboxylic acid component, and is a lactam such as ⁇ -caprolactam or laurolactam as long as the effect of the present embodiment is not impaired.
- Aminocaproic acid, aminoundecanoic acid and other aliphatic aminocarboxylic acids can also be used as the copolymerization component.
- 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more of the polyamide resin (A) is a diamine-derived structural unit or a dicarboxylic acid-derived structural unit. ..
- the polyamide resin (A) used in the present embodiment has a content of a compound having a molecular weight of 310 or more and 1000 or less of 0.1% by mass or more and 1.5% by mass or less.
- a compound having a molecular weight of 310 or more and 1000 or less is difficult to be removed from the filament, so that it is possible to maintain high mechanical properties.
- the type of the compound having a molecular weight of 310 or more and 1000 or less is not particularly specified, and is a raw material monomer of the polyamide resin (A) or an oligomer derived from another component added during the production of the polyamide resin (A). ..
- the compound having a molecular weight of 310 or more and 1000 or less preferably contains a cyclic compound formed from one molecule of xylylene diamine and one molecule of ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms. .. By including a predetermined amount of such a cyclic compound, the effect of the present invention is more effectively achieved.
- the molecular weight of the cyclic compound formed from one molecule of xylylene diamine and one molecule of sebacic acid is small. Since the filament has a thin morphology in the first place, such a cyclic compound easily exudes from the filament when immersed in water, and the strength retention rate tends to decrease. In this embodiment, this point is avoided by increasing the carbon number of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid.
- the polyamide resin (A) preferably contains a compound having a molecular weight of at least 310 to 700 as a compound having a molecular weight of 310 or more and 1000 or less, and more preferably contains a compound having a molecular weight of at least 310 to 500.
- the content of the compound having a molecular weight of 310 or more and 1000 or less in the polyamide resin (A) is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and 0.6% by mass. % Or more, more preferably 1.2% by mass or less, still more preferably 1.0% by mass or less.
- the polyamide resin (A) may contain only one compound having a molecular weight of 310 or more and 1000 or less, or may contain two or more compounds. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the polyamide resin (A) used in this embodiment also has a content of a compound having a molecular weight of less than 310 of 0.1% by mass or less.
- a content of a compound having a molecular weight of less than 310 of 0.1% by mass or less With such a configuration, elution of low molecular weight components when immersed in water can be effectively suppressed.
- the filament of the present embodiment is used as a filter for filtering an aqueous solution, if the low molecular weight component contained in the filament easily flows out when immersed in water, it may cause a problem in the performance as a filter. be.
- the lower limit of the content of a compound having a molecular weight of less than 310 is ideally 0% by mass, and the detection limit will be a practical lower limit.
- the polyamide resin (A) used in the present embodiment preferably has a number average molecular weight (Mn) of 6,000 to 50,000, more preferably 8,000 to 48,000, and even more preferably 9, It is 000 to 46,000. Within such a range, the molding processability becomes better.
- Mn number average molecular weight
- the number average molecular weight (Mn) referred to here can be obtained from the standard polymethylmethacrylate (PMMA) conversion value measured by gel permeation chromatography (GPC).
- PMMA polymethylmethacrylate
- the polyamide resin (A) used in this embodiment may or may not have a melting point.
- the melting point is preferably 170 to 280 ° C, more preferably 170 to 250 ° C. Within such a range, a filament having excellent moldability to a structure and excellent heat resistance can be obtained.
- the melting point in the present invention means the temperature of the peak top of the endothermic peak at the time of temperature rise observed by the DSC (differential scanning calorimetry) method. Specifically, using a DSC device, the sample amount is 1 mg, nitrogen is flowed at 30 mL / min as the atmospheric gas, and the temperature rise rate is 10 ° C / min, which is higher than the melting point expected from room temperature (25 ° C). The temperature of the peak top of the heat absorption peak observed when the molten polyamide resin is rapidly cooled with dry ice and then heated again to a temperature above the melting point at a rate of 10 ° C./min. To say.
- the polyamide resin (A) preferably occupies 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. , 95% by mass or more, more preferably 98% by mass or more.
- the filament of the present embodiment may contain only one type of polyamide resin (A), or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the filament of the present embodiment may contain a polyamide resin other than the polyamide resin (A), a thermoplastic resin other than the polyamide resin, a resin additive, and the like, as long as the effects of the present embodiment are not significantly deviated.
- polyamide resin other than the polyamide resin (A) examples include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 6/66, polyamide 610, polyamide 612, and polyhexamethylene terephthalamide (polyamide 6T).
- Polyamide methylene isophthalamide Polyamide 6I
- Polyamide 66 / 6T Polyamide 9T
- Polyamide 9MT Polyamide 6I / 6T
- Polyamide XD6 Polyamide lylen adipamide
- Polyamide XD10 Polyamide lylen sevasamide
- Polyamide 10T 1,3-BAC10I (polyamide resin composed of 1,3-bisaminomethylcyclohexane, sebacic acid and isophthalic acid), 1,4-BAC10I (1,4-bisaminomethylcyclohexane and sebacic acid).
- the filament of the present embodiment may contain only one type of polyamide resin other than the polyamide resin (A), or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the thermoplastic resin other than the polyamide resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyoxymethylene resins, polyether ketones, polyether sulfones, and thermoplastics.
- the filament of the present embodiment can be configured to substantially not contain a thermoplastic resin other than the polyamide resin (A).
- substantially free means that, for example, in the filament of the present embodiment, the content of the thermoplastic resin other than the polyamide resin (A) is 5% by mass or less of the content of the polyamide resin (A). 3, 3% by mass or less is preferable, and 1% by mass or less is more preferable.
- the filament of the present embodiment contains an antioxidant, a heat stabilizer, a hydrolysis resistance improver, a weathering stabilizer, a matting agent, an ultraviolet absorber, and a nucleating agent as long as the purpose and effect of the present embodiment are not impaired.
- Additives such as plasticizers, dispersants, flame retardants, antistatic agents, anticolorants, antigelling agents, colorants, mold release agents, surfactants, stains, etc. can be added.
- Additives such as plasticizers, dispersants, flame retardants, antistatic agents, anticolorants, antigelling agents, colorants, mold release agents, surfactants, stains, etc.
- the filament of the present embodiment does not contain a plasticizer, or the content of the plasticizer may be less than 0.5 parts by mass and 0.4 parts by mass or less with respect to 100 parts by mass of the polyamide resin. preferable.
- a compound having a molecular weight of 310 or more and 1000 or less serves as a plasticizer, and thus such a configuration can be obtained.
- the filament of the present embodiment has a total of 100% by mass of the polyamide resin (A), a compound having a molecular weight of 310 or more and 1000 or less, and other components (thermoplastic resin, additives, etc.) blended as necessary. It is adjusted to be.
- the filament of the present embodiment may be a monofilament or a multifilament, but is preferably a multifilament.
- the multifilament facilitates processing into a structure.
- the number of filaments constituting one multifilament is preferably 10 or more, more preferably 20 or more, and may be 30 or more.
- the upper limit of the number of filaments constituting one multifilament is preferably 100 or less, more preferably 60 or less, and further preferably 55 or less.
- the cross section of the filament of this embodiment is usually circular.
- the term "circle” as used herein means not only a circle in a geometrical sense but also a circle in the technical field of the present embodiment, which is generally recognized as a circle.
- the cross section of the filament in the present embodiment may have a shape other than a circular shape, and may be a flat shape such as an elliptical shape or an oval shape.
- the filament of the present embodiment preferably has a single yarn fineness of 2.0 ⁇ 10-5 to 50 dtex.
- the lower limit of the single yarn fineness is preferably 8.0 ⁇ 10 -5 dtex or more, more preferably 9.0 ⁇ 10 -3 dtex or more, and 1.0 ⁇ 10 -2 dtex or more. More preferably, it is more preferably 0.5 dtex or more, and even more preferably 1 dtex or more.
- the upper limit of the single yarn fineness is preferably 40 dtex or less, more preferably 30 dtex or less, further preferably 25 dtex or less, further preferably 20 dtex or less, and 18 dtex or less. Is even more preferable. Further, when the filament of the present embodiment is a multifilament, the fineness is preferably 10 to 1000 dtex.
- the value to the lower limit or more stable spinning is possible, and when the structure is processed, the structure can be given sufficient strength. Further, by setting the value to the upper limit or less, the pore size when the structure is formed can be reduced, not only the dust collecting performance can be improved, but also the pressure loss can be effectively suppressed.
- the lower limit of the fineness of the multifilament is preferably 40 dtex or more, more preferably 60 dtex or more, and further preferably 100 dtex or more.
- the upper limit of the fineness of the multifilament is preferably 800 dtex or less, more preferably 600 dtex or less, and further preferably 400 dtex or less. Fineness is measured according to the method described in Examples described below.
- the filament length (mass average length) of the present embodiment is not particularly specified, but is preferably 5 mm or more, more preferably 0.1 m or more, still more preferably 1 m or more, still more preferably 100 m or more. be.
- the upper limit of the filament length (mass average length) is preferably 20,000 m or less, more preferably 1,000 m or less, and further preferably 100 m or less.
- the filament of the present embodiment may or may not be stretched, but it is preferably stretched. By being stretched, a filament having higher mechanical strength can be obtained.
- the stretching is preferably in the longitudinal direction of the filament (filament length direction).
- the draw ratio is preferably 2.0 times or more, more preferably 2.5 times or more, further preferably 3.0 times or more, still more preferably 3.5 times or more. ..
- the upper limit of the draw ratio is preferably 6.5 times or less, more preferably 6.0 times or less, further preferably 5.5 times or less, and 5.0 times or less. Is more preferable.
- the filament of the present embodiment is preferably excellent in strength.
- the linear strength of the filament is preferably 4.25 cN / dtex or more, more preferably 4.30 cN / dtex or more, and 4.35 cN / dtex or more. Is more preferable.
- the upper limit of the linear strength is not particularly determined, but is practically 6.50 cN / dtex or less.
- the filament of the present embodiment is preferably excellent in water absorption and physical characteristics. Specifically, the tensile strength retention rate when the filament is dried at 80 ° C. for 24 hours and immersed in water at 23 ° C. for 1 week is preferably 85% or more, more preferably 90% or more. preferable. The ideal upper limit of the retention rate is 100%, but 99.9% or less is practical.
- the filament of the present embodiment is also preferably excellent in chemical resistance.
- the retention rate from the tensile strength before immersion in the chemical solution when the filament is dipped in hydrochloric acid having a concentration of 10% by mass for 1 week after humidity adjustment in an environment of 23 ° C. and a relative humidity of 50% for 1 week. Is preferably 90% or more, and more preferably 91% or more.
- the ideal upper limit of the retention rate is 100%, but 99.9% or less is practical.
- the ideal upper limit of the retention rate is 100%, but 99.9% or less is practical.
- either one of the retention rate after immersion in hydrochloric acid and the retention rate after immersion in sodium hydroxide aqueous solution may be satisfied, but it is preferable that both are satisfied. Further, it is preferable that the retention rate after water absorption is also satisfied.
- the filament in this embodiment is obtained by molding the above resin composition.
- the molding method is arbitrary, and it may be molded into a desired shape by any conventionally known molding method.
- the description in paragraphs 0051 to 0058 of International Publication No. 2017/010389 can be taken into consideration, and these contents are incorporated in the present specification.
- the filament is produced by a melt spinning method or an electrolytic spinning method.
- the melt spinning method is a method of extruding from a multi-hole die with an extruder and drawing through a roll.
- the electrolytic spinning method when a resin is dissolved in a solvent and the dissolved resin solution is discharged from a thin nozzle, there is an electric field at the tip of the resin solution, the resin solution itself is charged, and the resin solution is stretched by a potential difference. At the same time, it is a method of volatilizing the solvent.
- the structure of the present embodiment includes the filament of the present embodiment.
- the structure of the present embodiment includes a structure in which the filament of the present embodiment retains the form of the filament.
- holding means that the filament shape is generally maintained, and a part of the filament (for example, 10% by volume or less thereof) may be melted and contained in another filament or a structure. It is intended to include those that are bonded to the constituent materials (other fibers, base materials, etc.) of.
- the structure of the present embodiment may be a thread-like material such as a mixed fiber yarn containing the filament of the present embodiment, a braid, a twisted cord, a spun yarn, and a yarn having a core-sheath structure.
- the structure of the present embodiment is also preferably a filament containing the filament of the present embodiment, a non-woven fabric, an adsorbent, a filter cloth, a filter paper or a filter.
- the filament, non-woven fabric, adsorbent, filter cloth, filter paper or filter in the present embodiment includes filaments such as mixed yarns, braids and twisted cords using the filament of the present embodiment, non-woven fabric, adsorbent, filter cloth and filter paper. Or the purpose is to include filters and the like.
- An example of the structure of the present embodiment is a flat plate-like structure composed of only a layer containing the filament of the present embodiment as a main component.
- another example of the structure of the present embodiment is a layer containing the filament of the present embodiment as a main component and a multilayer body of a base material.
- the structure of the present embodiment may be a multilayer body of a layer containing the filament of the present embodiment as a main component and another non-woven fabric, a filter or the like.
- the layer containing the filament of the present embodiment as a main component means that the component having the highest content among the constituent structures of the layer is the filament of the present embodiment.
- examples of other non-woven fabrics and filters include non-woven fabrics and filters made of polyolefin (preferably polypropylene).
- the target substance is not particularly specified, but examples thereof include slime, gel, protein for water treatment, LPS, a polysaccharide substance that needs to be removed in seawater recycling, and the like. ..
- the density is preferably 1.10 to 1.25 g / cm 3 .
- the pore diameter of the filter is preferably 0.001 to 500 ⁇ m.
- the method for manufacturing the filter include an air blow method and a melt blow method.
- the air blow method is a method in which a filament is extruded from a multi-hole die, melted and solidified, and then blown onto a base material in a mesh pattern.
- Melt blow is a method in which a resin composition is extruded in a molten state and sprayed onto a substrate in a mesh pattern.
- the resin composition of the present embodiment is a resin composition containing a polyamide resin and a compound having a molecular weight of 310 or more and 1000 or less, and the polyamide resin is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid. 70 mol% or more of the constituent unit derived from the diamine is derived from xylylene diamine, and 70 mol% or more of the constituent unit derived from the dicarboxylic acid is an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms.
- the content of the compound having a molecular weight of 310 or more and 1000 or less is 0.1% by mass or more and 1.5% by mass or less, and the content of the compound having a molecular weight of less than 310 is 0.1% by mass or less.
- Such a resin composition is preferably used for producing the filament of the present embodiment, a non-woven fabric, an adsorbent, a filter cloth, a filter paper or a filter.
- the details of the polyamide resin (A) in the resin composition of the present embodiment and the like are the same as those of the filament of the present embodiment described above, and the preferred range is also the same.
- Example 1 ⁇ Synthesis of polyamide MP12>
- a reaction can with a jacket equipped with a stirrer, a splitter, a cooler, a thermometer, a dropping tank and a nitrogen gas introduction tube, 60.00 mol of the precisely weighed 1,12-dodecane diic acid was placed and sufficiently replaced with nitrogen. Further, the temperature was raised to 180 ° C. under a small amount of nitrogen stream to dissolve 1,12-dodecanedic acid to obtain a uniform flow state.
- 60 mol of para / m-xylylenediamine in which 30 mol% of the diamine component was paraxylylenediamine and 70 mol% was metaxylylenediamine was added dropwise over 160 minutes under stirring.
- the internal pressure of the reaction system was set to normal pressure, the internal temperature was continuously raised to 250 ° C., and the water distilled with the dropping of para / m-xylylenediamine was removed from the system through a condenser and a cooler. .. After completion of the addition of para / m-xylylenediamine, the reaction was continued for 10 minutes while maintaining the liquid temperature of 250 ° C. Then, the internal pressure of the reaction system was continuously reduced to 600 Torr for 10 minutes, and then the reaction was continued for 30 minutes to adjust the amount of components having a molecular weight of 1,000 or less. During this time, the reaction temperature was continuously raised to 260 ° C.
- a pressure of 0.3 MPa was applied to the inside of the reaction can with nitrogen gas, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization tank, cooled with water and cut into pellets to obtain pellets of a molten polymer product.
- the obtained pellets were placed in a tumbler (rotary vacuum chamber) having a heat medium heating cloak at room temperature.
- the inside of the tank was depressurized (0.5 to 10 Torr) while rotating the tumbler, the flow heat medium was heated to 150 ° C., the pellet temperature was raised to 130 ° C., and the temperature was maintained at that temperature for 3 hours. After that, nitrogen was introduced again to bring it to normal pressure, and cooling was started. When the temperature of the pellet became 70 ° C. or lower, the pellet was taken out from the tank to obtain a solid phase polymer product.
- the melting point of the obtained polyamide resin (MP12) was 206 ° C.
- the polyamide resin shown in Table 1 was melted using a single-screw extruder and spun through a spinneret (the number of holes is shown in Table 1) at a spinning temperature of 290 ° C. After passing the spun polyamide filament through the hot zone and cooling zone, the polyamide filament that has reached room temperature (hereinafter, may be referred to as "pre-stretched filament") is used as a sizing agent (Derion PP, manufactured by Takemoto Oil & Fat Co., Ltd.). After being immersed in ⁇ 807) to form a bundle, it was taken up by a non-heated roll 1 and continuously stretched without being wound once.
- the pre-stretched filament taken up by the roll 1 is heated by passing it through a roller 2 heated to 80 ° C., subsequently passed through a roller 2 and a roller 3 and a roller 4 heated to 170 ° C., and then wound up by a winder. rice field.
- stretching was performed by providing a speed ratio between the roller 2 and the roller 3, and the speed ratio was adjusted so as to have the stretching ratio shown in Table 1. Further, the speed ratio was set between the roller 3 and the roller 4 to relax the speed, and the rotation speed of the roller 4 was set to be 4% slower than that of the roller 3.
- the amount of oligomers having a molecular weight of less than 310 and the amount of oligomers having a molecular weight of 310 to 1000 were determined from the standard polymethylmethacrylate (PMMA) conversion values measured by gel permeation chromatography (GPC) as follows. As the column, two fillers filled with a styrene polymer were used, and hexafluoroisopropanol (HFIP) having a sodium trifluoroacetate concentration of 2 mmol / L was used as a solvent, and the resin concentration was 0.02% by mass.
- PMMA polymethylmethacrylate
- GPC gel permeation chromatography
- the temperature was 40 ° C., the flow velocity was 0.3 mL / min, and the measurement was performed with a refractive index detector (RI).
- the calibration curve was prepared by dissolving 6 levels of PMMA in HFIP, measuring and measuring.
- the amount of oligomers having a molecular weight of less than 310 and the amount of oligomers having a molecular weight of 310 to 1000 are shown as the amount (% by mass) with respect to the total amount of the polyamide resin having a molecular weight of more than 1000.
- each component obtained by GPC is obtained as% by area, but since area% can be regarded as equivalent to% by mass, such a value is described as% by mass.
- the gel permeation chromatography apparatus used in this example is "HLC-8320GPC" manufactured by Tosoh Corporation (TOSOH CORPORATION), and the measurement column is "TSKgel SuperHM-H".
- Filament fineness (single yarn fineness, multifilament fineness) was measured according to JIS L 1013: 2010. The unit is shown by dtex.
- Example 2 In Example 1, the same procedure was carried out except that the polyamide resin was changed to the polyamide MXD12 shown in the synthetic example below.
- ⁇ Synthesis of polyamide MXD12> In a reaction can with a jacket equipped with a stirrer, a splitter, a cooler, a thermometer, a dropping tank and a nitrogen gas introduction tube, 60.00 mol of the precisely weighed 1,12-dodecane diic acid was placed and sufficiently replaced with nitrogen. Further, the temperature was raised to 180 ° C. under a small amount of nitrogen stream to dissolve 1,12-dodecanedic acid to obtain a uniform flow state. To this, 60 mol of m-xylylenediamine was added dropwise over 160 minutes with stirring.
- the internal pressure of the reaction system was set to normal pressure, the internal temperature was continuously raised to 250 ° C., and the water distilled with the dropping of m-xylylenediamine was removed from the system through a condenser and a cooler. After the addition of m-xylylenediamine was completed, the reaction was continued for 10 minutes while maintaining the liquid temperature of 250 ° C. Then, the internal pressure of the reaction system was continuously reduced to 600 Torr for 10 minutes, and then the reaction was continued for 30 minutes to adjust the amount of components having a molecular weight of 1,000 or less. During this time, the reaction temperature was continuously raised to 260 ° C.
- a pressure of 0.3 MPa was applied to the inside of the reaction can with nitrogen gas, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization tank, cooled with water and cut into pellets to obtain pellets of a molten polymer product.
- the obtained pellets were placed in a tumbler (rotary vacuum chamber) having a heat medium heating cloak at room temperature.
- the inside of the tank was depressurized (0.5 to 10 Torr) while rotating the tumbler, the flow heat medium was heated to 150 ° C., the pellet temperature was raised to 130 ° C., and the temperature was maintained at that temperature for 3 hours. After that, nitrogen was introduced again to bring it to normal pressure, and cooling was started. When the temperature of the pellet became 70 ° C. or lower, the pellet was taken out from the tank to obtain a solid phase polymer product.
- the melting point of the obtained polyamide resin (MXD12) was 190 ° C.
- Example 1 Comparative Example 1 In Example 1, the same procedure was carried out except that the polyamide resin was changed to the polyamide MP10 shown in the synthetic example below.
- ⁇ Synthesis example of polyamide MP10 (M / P ratio 7: 3)> Sevacinic acid is placed in a reaction can with a jacket equipped with a stirrer, a splitter, a cooler, a thermometer, a dropping tank and a nitrogen gas introduction tube, and after heating and dissolving in a nitrogen atmosphere, the contents are stirred while stirring.
- a mixed diamine (manufactured by Mitsubishi Gas Chemicals Co., Ltd.) having a molar ratio of m-xylylenediamine and paraxylylenediamine of 7: 3 is used, and the molar ratio of diamine to sebacic acid is about 1: 1 under pressure (0.35 MPa).
- the melting point of the obtained polyamide resin (MP10) was 215 ° C.
- Example 2 Comparative Example 2 In Example 1, the same procedure was carried out except that the polyamide resin was changed to PA66 (nylon 66, manufactured by Toray Industries, Inc., Amylan CM3001, melting point: 265 ° C.).
- PA66 nylon 66, manufactured by Toray Industries, Inc., Amylan CM3001, melting point: 265 ° C.
- Example 3 In Example 1, the same procedure was carried out except that the polyamide resin was changed to the polyamide MP12 shown in the synthetic example below. ⁇ Synthesis of polyamide MP12> 1 kg of polyamide resin (MP12) obtained by the same synthesis method as the method described in Example 1 is placed in a SUS separable flask having a content of 3 L, 1.5 L of methanol is added, and the contents are stirred. , The liquid temperature of methanol was heated to 60 ° C. by a mantle heater. After heating for 5 hours from the time when the liquid temperature of methanol reached 60 ° C., the mixture was cooled to room temperature, and then passed through a 40-mesh wire mesh to separate the methanol phase and pellets. The separated pellets were dried at 120 ° C. for 5 hours in a vacuum dryer after repeating the above operation a total of 3 times to obtain the resin used in Comparative Example 3.
- Comparative Example 4 In Example 1, the same procedure was carried out except that the polyamide resin was changed to the polyamide MP12 shown in the synthetic example below. ⁇ Synthesis of polyamide MP12> The resin used in Comparative Example 4 was obtained by adding 1% by mass of an oligomer having a molecular weight of 310 to 1000 to the polyamide resin (MP12) obtained by the same synthesis method as the method described in Example 1 and dry-blending. rice field. As the oligomer having a molecular weight of 310 to 1000, the oligomer obtained by evaporating and drying the methanol phase after the treatment described in Comparative Example 3 was used.
- the filament of the present invention was excellent in linear strength and had a high retention rate of tensile strength after water absorption (Examples 1 and 2). Furthermore, it was also excellent in continuous productivity and chemical resistance.
- a polyamide resin composed of xylylenediamine and sebacic acid ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 10 carbon atoms
- linear strength and tension after water absorption are used. Both strength retention rates were inferior. Furthermore, it was inferior in continuous productivity.
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Abstract
Description
しかしながら、従来のポリアミドフィラメント(例えば、ポリアミド66を主原料とするポリアミドフィラメント)は吸水による強度低下が大きく、水系の薬液処理フィルターとして用いた際に、初期状態からの強度低下が著しかった。
具体的には、下記手段により、上記課題は解決された。
<1>ポリアミド樹脂を含み、前記ポリアミド樹脂は、ジアミン由来の構成単位とジカルボン酸由来の構成単位とから構成され、前記ジアミン由来の構成単位の70モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸に由来し、分子量が310以上1000以下の化合物の含有率が0.1質量%以上1.5質量%以下であり、分子量310未満の化合物の含有率が0.1質量%以下である、フィラメント。
<2>延伸されている、<1>に記載のフィラメント。
<3>前記分子量が310以上1000以下の化合物が、キシリレンジアミン1分子と炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸1分子から形成された環状化合物を含む、<1>または<2>に記載のフィラメント。
<4>前記ジアミン由来の構成単位の30~100モル%がメタキシリレンジアミンに由来し、0~70モル%がパラキシリレンジアミンに由来する、<1>~<3>のいずれか1つに記載のフィラメント。
<5>前記ジカルボン酸由来の構成単位の70モル%以上が1,12-ドデカン二酸である、<1>~<4>のいずれか1つに記載のフィラメント。
<6>前記フィラメントを、23℃、相対湿度50%の環境下で1週間調湿後、10質量%の濃度の塩酸に1週間浸漬したときの薬液浸漬前の引張強さからの保持率が90%以上であり、かつ、前記フィラメントを、23℃、相対湿度50%の環境下で1週間調湿後、10質量%の濃度の水酸化ナトリウム水溶液に1週間浸漬したときの薬液浸漬前の引張強さからの保持率が90%以上である、<1>~<5>のいずれか1つに記載のフィラメント。
<7>単糸繊度が2.0×10-5~50dtexである、<1>~<6>のいずれか1つに記載のフィラメント。
<8>マルチフィラメントである、<1>~<7>のいずれか1つに記載のフィラメント。
<9><1>~<8>のいずれか1つに記載のフィラメントを含む、構造体。
<10>前記構造体が、不織布、吸着体、濾布、濾紙またはフィルターである、<9>に記載の構造体。
<11>ポリアミド樹脂と、分子量が310以上1000以下の化合物を含む樹脂組成物であって、前記ポリアミド樹脂は、ジアミン由来の構成単位とジカルボン酸由来の構成単位とから構成され、前記ジアミン由来の構成単位の70モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸に由来し、前記分子量が310以上1000以下の化合物の含有率が0.1質量%以上1.5質量%以下であり、さらに、分子量310未満の化合物の含有率が0.1質量%以下である、樹脂組成物。
<12>フィラメント、不織布、吸着体、濾布、濾紙またはフィルター用である、<11>に記載の樹脂組成物。
<13><11>に記載の樹脂組成物を、溶融紡糸法または電解紡糸法により、紡糸することを含む、<1>~<8>のいずれか1つに記載のフィラメントの製造方法。
なお、本明細書において「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
本明細書において、各種物性値および特性値は、特に述べない限り、23℃におけるものとする。
この理由は、以下の通りであると推測される。すなわち、本実施形態のフィラメントでは、ポリアミド樹脂の原料モノマーとして、キシリレンジアミンと炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸を用いている。このような原料から構成されるポリアミド樹脂を用いることで、フィラメントを吸水しにくくし、機械物性の低下を抑制できた。また、加水分解が起こりにくく、耐薬品性を低くできたと推測される。さらに、このようなポリアミド樹脂において、分子量が310以上1000以下の化合物の含有率を0.1質量%以上1.5質量%以下とすることにより、延伸性が高まり、フィラメントの強度を高くすることができたと推測される。加えて、分子量が310以上1000以下の化合物は、分子量が310未満の化合物と比較して、格段に、水に浸漬した後に抜けにくいため、吸水後の機械物性を高く維持することができたと推測される。
本実施形態で用いられるポリアミド樹脂は、ジアミン由来の構成単位とジカルボン酸由来の構成単位とから構成され、前記ジアミン由来の構成単位の70モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸に由来し、分子量が310以上1000以下の化合物の含有率が0.1質量%以上1.5質量%以下であり、分子量310未満の化合物の含有率が0.1質量%以下である。以下、本明細書では、このようなポリアミド樹脂を「ポリアミド樹脂(A)」ということがある。
分子量が310以上1000以下の化合物は、その種類等特に定めるものではなく、ポリアミド樹脂(A)の原料モノマーやポリアミド樹脂(A)の製造の際に添加される他の成分由来のオリゴマー等である。本実施形態では、分子量が310以上1000以下の化合物として、キシリレンジアミン1分子と炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸1分子から形成された環状化合物を含むことが好ましい。このような環状化合物を所定量含むことにより、本発明の効果がより効果的に達成される。特に、ポリアミド樹脂の原料ジカルボン酸がセバシン酸の場合、キシリレンジアミン1分子とセバシン酸1分子から形成された環状化合物の分子量が小さい。そして、フィラメントはその形態がそもそも細いものであるため、水に浸漬したときにこのような環状化合物が容易にフィラメントから滲出してしまい、強度保持率が低下しやすくなっていた。本実施形態では、α,ω-直鎖脂肪族ジカルボン酸の炭素数を大きくすることにより、この点を回避している。
また、ポリアミド樹脂(A)は、分子量が310以上1000以下の化合物として、少なくとも分子量が310~700の化合物を含むことが好ましく、少なくとも分子量が310~500の化合物を含むことがより好ましい。
また、ポリアミド樹脂(A)における分子量が310以上1000以下の化合物の含有量は、0.3質量%以上であることが好ましく、0.5質量%以上であることがより好ましく、0.6質量%以上であることがさらに好ましく、また、1.2質量%以下であることがより好ましく、1.0質量%以下であることがさらに好ましい。
ポリアミド樹脂(A)は、分子量が310以上1000以下の化合物を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
なお、本発明における融点とは、DSC(示差走査熱量測定)法により観測される昇温時の吸熱ピークのピークトップの温度を意味する。具体的には、DSC装置を用い、試料量は1mgとし、雰囲気ガスとしては窒素を30mL/分で流し、昇温速度は10℃/分の条件で室温(25℃)から予想される融点以上の温度まで加熱し溶融させ、次いで、溶融したポリアミド樹脂を、ドライアイスで急冷し、10℃/分の速度で融点以上の温度まで再度昇温した際に観測される吸熱ピークのピークトップの温度をいう。
本実施形態のフィラメントは、ポリアミド樹脂(A)を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本実施形態のフィラメントは、本実施形態の効果を著しく逸脱しない範囲で、ポリアミド樹脂(A)以外のポリアミド樹脂、ポリアミド樹脂以外の熱可塑性樹脂、および、樹脂添加剤等を含んでいてもよい。
本実施形態のフィラメントは、ポリアミド樹脂(A)以外のポリアミド樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
前記ポリアミド樹脂以外の他の熱可塑性樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリカーボネート樹脂、ポリオキシメチレン樹脂、ポリエーテルケトン、ポリエーテルスルフォン、熱可塑性ポリエーテルイミド等の1種または2種以上が例示される。
また、本実施形態のフィラメントでは、ポリアミド樹脂(A)以外の熱可塑性樹脂を実質的に含まない構成とすることができる。実質的に含まないとは、例えば、本実施形態のフィラメントにおいて、ポリアミド樹脂(A)以外の熱可塑性樹脂の含有量が、ポリアミド樹脂(A)の含有量の5質量%以下であることをいい、3質量%以下が好ましく、1質量%以下がより好ましい。
本実施形態のフィラメントは、可塑剤を含まないか、可塑剤の含有量がポリアミド樹脂100質量部に対し、0.5質量部未満であってもよく、0.4質量部以下であることが好ましい。本実施形態では、分子量が310以上1000以下の化合物が可塑剤としての役割を果たすため、このような構成とすることができる。
本実施形態のフィラメントは、ポリアミド樹脂(A)、分子量が310以上1000以下の化合物、および、必要に応じて配合される、他の成分(熱可塑性樹脂、添加剤等)の合計が100質量%となるように調整される。
本実施形態のフィラメントは、モノフィラメントであってもよいし、マルチフィラメントであってもよいが、マルチフィラメントであることが好ましい。マルチフィラメントとすることにより、構造体への加工が容易となる。
本実施形態のフィラメントがマルチフィラメントである場合、一本のマルチフィラメントを構成するフィラメントの数は、10以上であることが好ましく、20以上であることがより好ましく、30以上であってもよい。また、一本のマルチフィラメントを構成するフィラメントの数の上限は、100以下であることが好ましく、60以下であることがより好ましく、55以下であることがさらに好ましい。このような範囲とすることにより、紡糸時の単糸繊度の斑を抑制できるほか、紡糸時の単糸間の融着を防ぐことができる。
本実施形態のフィラメントの断面は、通常円形である。ここでの円形とは、幾何学的な意味での円形の他、本実施形態の技術分野において、概ね円形と認められるものも含む趣旨である。また、本実施形態におけるフィラメントの断面は、円形以外の形状であってもよく、例えば、楕円形、長円形などの扁平形状であってもよい。
また、本実施形態のフィラメントは、マルチフィラメントである場合の繊度は、10~1000dtexであることが好ましい。前記下限値以上とすることにより、安定的な紡糸が可能であり、かつ、構造体へ加工した際に、構造体に十分な強度を持たせることができる。また、前記上限値以下とすることにより、構造体を形成した際の空孔サイズを小さくすることができ、集塵性能が向上するだけでなく、圧力損失を効果的に抑制することができる。前記マルチフィラメントの繊度の下限は、40dtex以上であることが好ましく、60dtex以上であることがより好ましく、100dtex以上であることがさらに好ましい。また、前記マルチフィラメントの繊度の上限は、800dtex以下であることが好ましく、600dtex以下であることがより好ましく、400dtex以下であることがさらに好ましい。
繊度は後述する実施例に記載の方法に従って測定される。
具体的には、JIS L 1013:2010に従い、フィラメントの直線強さが、4.25cN/dtex以上であることが好ましく、4.30cN/dtex以上であることがより好ましく、4.35cN/dtex以上であることがさらに好ましい。前記直線強さの上限値は、特に定めるものではないが、6.50cN/dtex以下が実際的である。
具体的には、フィラメントを80℃、24時間乾燥させ、23℃の水に1週間浸漬したときの引張強さ保持率が、85%以上であることが好ましく、90%以上であることがより好ましい。前記保持率の上限値の理想は100%であるが、99.9%以下が実際的である。
具体的には、フィラメントを、23℃、相対湿度50%の環境下で1週間調湿後、10質量%の濃度の塩酸に1週間浸漬したときの薬液浸漬前の引張強さからの保持率が90%以上であることが好ましく、91%以上であることがより好ましい。前記保持率の上限値の理想は100%であるが、99.9%以下が実際的である。
また、フィラメントを、23℃、相対湿度50%の環境下で1週間調湿後、10質量%の濃度の水酸化ナトリウム水溶液に1週間浸漬したときの薬液浸漬前の引張強さからの保持率が90%以上であることが好ましく、91%以上であることがより好ましい。前記保持率の上限値の理想は100%であるが、99.9%以下が実際的である。
本実施形態では、上記塩酸浸漬後の保持率と、水酸化ナトリウム水溶液浸漬後の保持率のいずれか一方を満たしていればよいが、両方を満たしていることが好ましい。さらに、上記吸水後の保持率も併せて満たしていることが好ましい。
次に、本実施形態のフィラメントの製造方法について説明する。
本実施形態におけるフィラメントは、上記樹脂組成物を成形して得られる。その成形方法は任意であり、従来公知の任意の成形方法により所望の形状に成形すればよい。例えば、国際公開第2017/010389号の段落0051~0058の記載を参酌でき、これらの内容は本明細書に組み込まれる。
本実施形態では特に、フィラメントが溶融紡糸法もしくは電解紡糸法により製造されることが好ましい。溶融紡糸法とは、多穴ダイから押出機で押出し、ロールを通して延伸する方法である。また、電解紡糸法とは、樹脂を溶剤に溶かし、溶かした樹脂溶液を細いノズルから吐出するとき、樹脂溶液が出た先に、電場があり、樹脂溶液自体も帯電させて、電位差で延伸しつつ、溶剤を揮発させる方法である。
本実施形態の構造体は、本実施形態のフィラメントを含む。本実施形態の構造体は、本実施形態のフィラメントがフィラメントの形態を保持しているものを含む。ここで、保持しているとは、概ねフィラメント形状を保っていることをいい、フィラメントの一部(例えば、その10体積%以下)が溶融して、他のフィラメントや構造体に含まれうる他の構成材料(他の繊維や基材等)と結合しているものも含まれる趣旨である。
本実施形態の構造体は、本実施形態のフィラメントを含む混繊糸、組紐、より紐、紡績糸、芯鞘構造を有する糸等の糸状材料であってもよい。混繊糸等とする場合、他の熱可塑性樹脂フィラメント、炭素繊維、ガラス繊維等の強化繊維(フィラメント)等と組み合わせることが好ましい。
本実施形態の構造体は、また、本実施形態のフィラメントを含むフィラメント、不織布、吸着体、濾布、濾紙またはフィルターであることが好ましい。本実施形態におけるフィラメント、不織布、吸着体、濾布、濾紙またはフィルターには、上記本実施形態のフィラメントを用いた混繊糸、組紐、より紐等のフィラメント、不織布、吸着体、濾布、濾紙またはフィルター等も含む趣旨である。
本実施形態の構造体をフィルターとして用いる場合、密度が1.10~1.25g/cm3であることが好ましい。また、フィルターの孔径は0.001~500μmであることが好ましい。
上記フィルターの製造方法としては、エアブロー法およびメルトブロー法が例示される。エアブロー法とは、多穴ダイからフィラメントを押出し、溶かして固化したものをエアブローにより、網目状に基材に吹き付ける方法である。メルトブローは、樹脂組成物を溶融状態で押出し、基材に網目状に吹き付ける方法である。
次に、本実施形態の樹脂組成物について説明する。
本実施形態の樹脂組成物は、ポリアミド樹脂と、分子量が310以上1000以下の化合物を含む樹脂組成物であって、前記ポリアミド樹脂は、ジアミン由来の構成単位とジカルボン酸由来の構成単位とから構成され、前記ジアミン由来の構成単位の70モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸に由来し、前記分子量が310以上1000以下の化合物の含有率が0.1質量%以上1.5質量%以下であり、さらに、分子量310未満の化合物の含有率が0.1質量%以下である。このような樹脂組成物は、本実施形態のフィラメントや、不織布、吸着体、濾布、濾紙またはフィルターの製造用として好ましく用いられる。
本実施形態の樹脂組成物におけるポリアミド樹脂(A)の詳細、その他については、上述の本実施形態のフィラメントと同様であり、好ましい範囲も同様である。
実施例で用いた測定機器等が廃番等により入手困難な場合、他の同等の性能を有する機器を用いて測定することができる。
<ポリアミドMP12の合成>
撹拌機、分縮器、冷却器、温度計、滴下槽および窒素ガス導入管を備えたジャケット付反応缶に、精秤した1,12-ドデカン二酸60.00molを入れ、十分窒素置換し、さらに少量の窒素気流下で180℃まで昇温し、1,12-ドデカン二酸を溶解させ均一な流動状態とした。これに、ジアミン成分の30mol%をパラキシリレンジアミン、70mol%をメタキシリレンジアミンとしたパラ/メタキシリレンジアミン60molを撹拌下に160分を要して滴下した。この間、反応系内圧は常圧とし、内温を連続的に250℃まで昇温させ、またパラ/メタキシリレンジアミンの滴下とともに留出する水は分縮器および冷却器を通して系外に除いた。パラ/メタキシリレンジアミン滴下終了後、250℃の液温を保持して10分間反応を継続した。その後、反応系内圧を600Torrまで10分間で連続的に減圧し、その後、30分間反応を継続することで、分子量1,000以下の成分量を調整した。この間、反応温度を260℃まで連続的に昇温させた。反応終了後、反応缶内を窒素ガスにて0.3MPaの圧力を掛けポリマーを重合槽下部のノズルよりストランドとして取出し、水冷後ペレット形状に切断し、溶融重合品のペレットを得た。得られたペレットを熱媒加熱の外套を有するタンブラー(回転式の真空槽)に、室温で仕込んだ。タンブラーを回転しながら槽内を減圧状態(0.5~10Torr)とし、流通熱媒を150℃まで加温し、ペレット温度130℃まで昇温してその温度で3時間保持した。その後、再び窒素を導入して常圧にし、冷却を開始した。ペレットの温度が70℃以下になったところで、槽からペレットを取り出し、固相重合品を得た。
得られたポリアミド樹脂(MP12)の融点は206℃であった。
表1に示すポリアミド樹脂を、単軸押出機を用いて溶融し、紡糸温度を290℃として紡糸口金(孔の数は表1に示した)を通して紡出した。紡糸したポリアミドフィラメントをホットゾーンおよび冷却ゾーンを通過させた後、概ね室温となったポリアミドフィラメント(以下、「延伸前フィラメント」と呼ぶことがある)を、集束剤(竹本油脂株式会社製、デリオン PP-807)に浸漬させて、束状にしたのちに、非加熱のロール1にて引き取り、一旦巻き取ることなく連続して延伸した。ロール1で引き取った延伸前フィラメントを80℃に加熱したローラー2を通過させることで加熱し、続いて170℃に加熱したローラー2およびローラー3およびローラー4を通過させた後、ワインダーにて巻き取った。このとき、ローラー2とローラー3の間で速度比を設けることで延伸を行い、表1に示す延伸倍率となるように速度比を調整した。また、ローラー3とローラー4の間で速度比を設けることで緩和させ、ローラー4の回転数をローラー3よりも4%遅く設定した。
分子量310未満のオリゴマー量と分子量310~1000のオリゴマー量は以下の通り、ゲルパーミエーションクロマトグラフィー(GPC)測定による標準ポリメチルメタクリレート(PMMA)換算値より求めた。
カラムとしては、充填剤として、スチレン系ポリマーを充填したものを2本用い、溶媒にはトリフルオロ酢酸ナトリウム濃度2mmol/Lのヘキサフルオロイソプロパノール(HFIP)を用い、樹脂濃度0.02質量%、カラム温度は40℃、流速0.3mL/分、屈折率検出器(RI)にて測定した。また、検量線は6水準のPMMAをHFIPに溶解させて測定し、作成した。分子量310未満のオリゴマー量と分子量310~1000のオリゴマー量は、分子量1000より大きいポリアミド樹脂の全量に対する量(質量%)として示した。ここで、GPCで得られる各成分は面積%として得られるが、面積%は質量%と同等とみなすことができるため、かかる値を質量%として記載する。
本実施例で用いたゲルパーミエーションクロマトグラフィー装置は、東ソー社(TOSOH CORPORATION)製「HLC-8320GPC」であり、測定用カラムは「TSKgel SuperHM-H」である。
JIS L 1013:2010の規定に従い、フィラメントの繊度(単糸繊度、マルチフィラメントの繊度)を測定した。単位は、dtexで示した。
紡糸後のノズルの汚れ付着具合を確認し、ノズルに分子量330以下の成分の付着物について以下の通り評価した。評価は5人の専門家が行い、多数決とした。
A:付着物がない、または、ほぼない。
B:上記A以外、例えば、付着物があり、連続紡糸性に影響を及ぼした等。
JIS L 1013:2010に従い、フィラメントの直線強さを測定した。
単位は、cN/dtexで示した。
真空乾燥機で80℃、24時間乾燥させたフィラメントを23℃の水に1週間浸漬し、水浸漬前の引張強さの保持率で評価した。引張強さは、JIS L 1013:2010に従って測定した。
引張強さ保持率=[(水浸漬前の引張強さ-水浸漬後の引張強さ)/水浸漬前の引張強さ]×100(単位:%)
単位は、%で示した。
フィラメントを23℃、相対湿度50%の環境下で1週間調湿後、薬液(10質量%の濃度の塩酸水溶液、または、10質量%の濃度の水酸化ナトリウム水溶液)に1週間浸漬し、薬液浸漬前の引張強さの保持率で評価した。引張強さは、JIS L 1013:2010に従って測定した。
引張強さ保持率=[(薬液浸漬前の引張強さ-薬液浸漬後の引張強さ)/薬液浸漬前の引張強さ]×100
単位は、%で示した。
実施例1において、ポリアミド樹脂を下記に合成例を示したポリアミドMXD12に変更した他は、同様に行った。
<ポリアミドMXD12の合成>
撹拌機、分縮器、冷却器、温度計、滴下槽および窒素ガス導入管を備えたジャケット付反応缶に、精秤した1,12-ドデカン二酸60.00molを入れ、十分窒素置換し、さらに少量の窒素気流下で180℃まで昇温し、1,12-ドデカン二酸を溶解させ均一な流動状態とした。これに、メタキシリレンジアミン60molを撹拌下に160分を要して滴下した。この間、反応系内圧は常圧とし、内温を連続的に250℃まで昇温させ、メタキシリレンジアミンの滴下とともに留出する水は分縮器および冷却器を通して系外に除いた。メタキシリレンジアミン滴下終了後、250℃の液温を保持して10分間反応を継続した。その後、反応系内圧を600Torrまで10分間で連続的に減圧し、その後、30分間反応を継続することで、分子量1,000以下の成分量を調整した。この間、反応温度を260℃まで連続的に昇温させた。反応終了後、反応缶内を窒素ガスにて0.3MPaの圧力を掛けポリマーを重合槽下部のノズルよりストランドとして取出し、水冷後ペレット形状に切断し、溶融重合品のペレットを得た。得られたペレットを熱媒加熱の外套を有するタンブラー(回転式の真空槽)に、室温で仕込んだ。タンブラーを回転しながら槽内を減圧状態(0.5~10Torr)とし、流通熱媒を150℃まで加温し、ペレット温度130℃まで昇温してその温度で3時間保持した。その後、再び窒素を導入して常圧にし、冷却を開始した。ペレットの温度が70℃以下になったところで、槽からペレットを取り出し、固相重合品を得た。
得られたポリアミド樹脂(MXD12)の融点は190℃であった。
実施例1において、ポリアミド樹脂を下記に合成例を示したポリアミドMP10に変更した他は、同様に行った。
<ポリアミドMP10の合成例(M/P比=7:3)>
撹拌機、分縮器、冷却器、温度計、滴下槽および窒素ガス導入管を備えたジャケット付反応缶に、セバシン酸を入れ、窒素雰囲気下で加熱溶解した後、内容物を撹拌しながら、メタキシリレンジアミンとパラキシリレンジアミンのモル比が7:3の混合ジアミン(三菱ガス化学社製)を、加圧(0.35MPa)下でジアミンとセバシン酸とのモル比が約1:1になるように徐々に滴下しながら、温度を235℃まで上昇させた。滴下終了後、60分間反応継続し、分子量1,000以下の成分量を調整した。反応終了後、内容物をストランド状に取り出し、ペレタイザーにてペレット化し、ポリアミド樹脂(MP10、M/P=7:3)を得た。
得られたポリアミド樹脂(MP10)の融点は215℃であった。
実施例1において、ポリアミド樹脂をPA66(ナイロン66、東レ社製、アミランCM3001、融点は265℃)に変更した他は、同様に行った。
実施例1において、ポリアミド樹脂を下記に合成例を示したポリアミドMP12に変更した他は、同様に行った。
<ポリアミドMP12の合成>
内容量3LのSUS製セパラブルフラスコに、実施例1に記載の方法と同様の合成方法により得られたポリアミド樹脂(MP12)1kgを入れ、メタノール1.5Lを投入し、内容物を撹拌しながら、マントルヒーターによりメタノールの液温が60℃となるよう加熱した。メタノールの液温が60℃に達した時点から5時間加熱した後、室温まで冷却した後、40メッシュの金網を通過させて、メタノール相とペレットを分離した。分離したペレットについて、上記操作を計3回繰り返したのち、真空乾燥機にて120℃、5時間乾燥させることにより、比較例3に用いる樹脂を得た。
実施例1において、ポリアミド樹脂を下記に合成例を示したポリアミドMP12に変更した他は、同様に行った。
<ポリアミドMP12の合成>
実施例1に記載の方法と同様の合成方法により得られたポリアミド樹脂(MP12)に対し、分子量310~1000のオリゴマーを1質量%添加し、ドライブレンドすることで比較例4に用いる樹脂を得た。なお、分子量310~1000のオリゴマーは比較例3記載の処理を行った後のメタノール相を、蒸発乾固することにより得られたものを使用した。
上記結果から明らかなとおり、本発明のフィラメントは、直線強さに優れ、かつ、吸水後の引張強さの保持率が高かった(実施例1、2)。さらに、連続生産性や耐薬品性にも優れていた。
一方、キシリレンジアミンとセバシン酸(炭素数10のα,ω-直鎖脂肪族ジカルボン酸)から構成されたポリアミド樹脂を用いた場合(比較例1)、直線強さ、および、吸水後の引張強さの保持率の両方が劣っていた。さらに、連続生産性にも劣っていた。
また、ポリアミド66を用いた場合(比較例2)、直線強さに優れていたが、吸水後の引張強さの保持率が著しく劣っていた。さらに、耐薬品性(塩酸耐性)も著しく劣っていた。
分子量が310以上1000以下の化合物の含有率が0.1質量%未満のポリアミド樹脂を用いた場合(比較例3)、および、1.5質量%超のポリアミド樹脂を用いた場合(比較例4)のいずれにおいても、直線強さが劣っていた。
Claims (13)
- ポリアミド樹脂を含み、
前記ポリアミド樹脂は、ジアミン由来の構成単位とジカルボン酸由来の構成単位とから構成され、前記ジアミン由来の構成単位の70モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸に由来し、
分子量が310以上1000以下の化合物の含有率が0.1質量%以上1.5質量%以下であり、
分子量310未満の化合物の含有率が0.1質量%以下である、
フィラメント。 - 延伸されている、請求項1に記載のフィラメント。
- 前記分子量が310以上1000以下の化合物が、キシリレンジアミン1分子と炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸1分子から形成された環状化合物を含む、請求項1または2に記載のフィラメント。
- 前記ジアミン由来の構成単位の30~100モル%がメタキシリレンジアミンに由来し、0~70モル%がパラキシリレンジアミンに由来する、請求項1~3のいずれか1項に記載のフィラメント。
- 前記ジカルボン酸由来の構成単位の70モル%以上が1,12-ドデカン二酸である、請求項1~4のいずれか1項に記載のフィラメント。
- 前記フィラメントを、23℃、相対湿度50%の環境下で1週間調湿後、10質量%の濃度の塩酸に1週間浸漬したときの薬液浸漬前の引張強さからの保持率が90%以上であり、かつ、前記フィラメントを、23℃、相対湿度50%の環境下で1週間調湿後、10質量%の濃度の水酸化ナトリウム水溶液に1週間浸漬したときの薬液浸漬前の引張強さからの保持率が90%以上である、請求項1~5のいずれか1項に記載のフィラメント。
- 単糸繊度が2.0×10-5~50dtexである、請求項1~6のいずれか1項に記載のフィラメント。
- マルチフィラメントである、請求項1~7のいずれか1項に記載のフィラメント。
- 請求項1~8のいずれか1項に記載のフィラメントを含む、構造体。
- 前記構造体が、不織布、吸着体、濾布、濾紙またはフィルターである、請求項9に記載の構造体。
- ポリアミド樹脂と、分子量が310以上1000以下の化合物を含む樹脂組成物であって、
前記ポリアミド樹脂は、ジアミン由来の構成単位とジカルボン酸由来の構成単位とから構成され、前記ジアミン由来の構成単位の70モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数11~14のα,ω-直鎖脂肪族ジカルボン酸に由来し、
前記分子量が310以上1000以下の化合物の含有率が0.1質量%以上1.5質量%以下であり、
さらに、分子量310未満の化合物の含有率が0.1質量%以下である、樹脂組成物。 - フィラメント、不織布、吸着体、濾布、濾紙またはフィルター用である、請求項11に記載の樹脂組成物。
- 請求項11に記載の樹脂組成物を、溶融紡糸法または電解紡糸法により、紡糸することを含む、請求項1~8のいずれか1項に記載のフィラメントの製造方法。
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EP4227346A4 (en) | 2024-04-17 |
EP4227346A1 (en) | 2023-08-16 |
JPWO2022074966A1 (ja) | 2022-04-14 |
KR20230084206A (ko) | 2023-06-12 |
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