WO2021133116A1 - Agrégat de fibres pour matériau d'habitacle de véhicule, et matériau d'habitacle de véhicule comprenant celui-ci - Google Patents

Agrégat de fibres pour matériau d'habitacle de véhicule, et matériau d'habitacle de véhicule comprenant celui-ci Download PDF

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WO2021133116A1
WO2021133116A1 PCT/KR2020/019131 KR2020019131W WO2021133116A1 WO 2021133116 A1 WO2021133116 A1 WO 2021133116A1 KR 2020019131 W KR2020019131 W KR 2020019131W WO 2021133116 A1 WO2021133116 A1 WO 2021133116A1
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Prior art keywords
fiber
formula
compound represented
adhesive
mol
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PCT/KR2020/019131
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English (en)
Korean (ko)
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한송정
이주현
김도현
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도레이첨단소재 주식회사
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Priority claimed from KR1020190177036A external-priority patent/KR102410331B1/ko
Priority claimed from KR1020190177032A external-priority patent/KR102415149B1/ko
Application filed by 도레이첨단소재 주식회사 filed Critical 도레이첨단소재 주식회사
Priority to JP2022539448A priority Critical patent/JP7419540B2/ja
Priority to CN202080090307.9A priority patent/CN114901882B/zh
Publication of WO2021133116A1 publication Critical patent/WO2021133116A1/fr

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/55—Polyesters

Definitions

  • the present invention relates to a fiber assembly for automotive interior materials, and more particularly, it has excellent touch, sound absorption rate, adhesive strength, rebound modulus and workability, minimizes change over time due to excellent heat resistance, and significantly reduces the emission of VOCs in a closed environment It relates to a fiber assembly for automobile interior materials particularly suitable for automobiles in which this is implemented, and automobile interior materials including the same.
  • synthetic fibers have a high melting point, which limits their use in many cases.
  • the textile fabric itself may be deteriorated by heating, and special equipment such as a high-frequency sewing machine must be used. Since there is a cumbersome process, it is desired to easily adhere by a simple ordinary hot press without using such special equipment.
  • polyester fibers Conventional low-melting polyester fibers have been widely used as hot melt type binder fibers for the purpose of bonding different types of fibers in mutual fiber structures used for manufacturing mattresses, interior materials for automobiles, or various non-woven fabrics.
  • U.S. Patent No. 4,129,675 discloses a low-melting polyester copolymerized using terephthalic acid (TPA) and isophthalic acid (IPA), and also, Korean Patent Registration No. 10-1216690 No. discloses a low-melting polyester fiber comprising isophthalic acid and diethylene glycol to improve adhesion.
  • TPA terephthalic acid
  • IPA isophthalic acid
  • Korean Patent Registration No. 10-1216690 No. discloses a low-melting polyester fiber comprising isophthalic acid and diethylene glycol to improve adhesion.
  • the conventional low-melting polyester fiber as described above may have spinnability and adhesiveness above a certain level, but there is a problem in that an interior material for automobiles having a hard feeling is implemented after heat bonding due to the ring structure of the rigid modifier.
  • VOCs volatile organic compounds
  • the present invention was devised in consideration of the above points, and it has excellent tactile feel, sound absorption rate, adhesive strength, rebound modulus and workability, minimizes change over time due to excellent heat resistance, and realizes a closed environment by remarkably reducing the emission of VOCs
  • An object of the present invention is to provide a fiber assembly for automobile interior materials particularly suitable for automobiles, and automobile interior materials including the same.
  • the present invention provides an esterified compound in which an acid component containing terephthalic acid, and ethylene glycol, and a diol component containing a compound represented by the following Chemical Formula 1 and Chemical Formula 2 are reacted are polycondensed.
  • the total content of the compound represented by Formula 1 and the compound represented by Formula 2 may be included in an amount of 30 to 45 mol% of the diol component.
  • the content (mol %) of the compound represented by Formula 1 among the diol components may be greater than the content (mol %) of the compound represented by Formula 2 .
  • the diol component may not include diethylene glycol substantially.
  • the acid component may be further included in an amount of 1 to 10 mol% of isophthalic acid based on the acid component.
  • 1 to 40 mol% of the compound represented by Formula 1 among the diol components 0.8 to 20 mol% of the compound represented by Formula 2 may be included, and more preferably, the compound represented by Formula 1 among the diol components
  • the compound represented by 20 to 40 mol%, the compound represented by Formula 2 is 0.8 to 10 mol%, more preferably, the compound represented by Formula 1 is 30 to 40 mol%, the compound represented by Formula 2 is It may be included in 0.8 to 6 mol%.
  • the copolyester may have a glass transition temperature of 60 ⁇ 75 °C, more preferably 65 ⁇ 72 °C.
  • the copolyester may have an intrinsic viscosity of 0.500 to 0.800 dl/g.
  • heat-adhesive fiber and the support fiber may be included in a weight ratio of 30:70 to 40:60.
  • the average sound absorption coefficient may be 0.35 or more within the frequency range of 400 ⁇ 2000Hz.
  • the sound absorption coefficient according to KS F 2805 (1) at a frequency of 1000 Hz, at a frequency of more than 0.53, (2) at a frequency of 2000 Hz, at least 0.73, (3) at a frequency of 3000 Hz, at a rate of 0.83 or more, (4) at a frequency of 4000 Hz
  • the sound absorption coefficient may be 0.92 or more.
  • the heat-adhesive fiber may have a VOCs emission amount of 2600 ppb or less, more preferably 2200 ppb or less, measured according to the US EPA TO-14 method.
  • the adhesive strength according to KS M ISO 36 may be 130 ⁇ 200N/25mm.
  • the rebound modulus may be 45 to 60%.
  • the present invention provides an automobile interior material comprising the fiber assembly for automobile interior material according to the present invention.
  • the fiber aggregate for automobile interior materials according to the present invention is very excellent in touch, sound absorption, adhesive strength, rebound modulus and workability. In addition, it is very suitable for use as an interior material for automobiles where a high indoor temperature is formed during outdoor parking in summer as the change over time is minimized with excellent heat resistance. Furthermore, since the emission of VOCs is significantly reduced, it can be widely applied in related fields as it is very suitable for automobile interior materials that are operated in a closed environment.
  • FIG. 1 is a schematic cross-sectional view of a heat-adhesive fiber included in an embodiment of the present invention.
  • the fiber assembly for automobile interior materials is an esterified compound in which an acid component containing terephthalic acid, and ethylene glycol, and a diol component containing a compound represented by the following Chemical Formula 1 and Chemical Formula 2 are reacted are polycondensed. It is implemented by including the heat-adhesive fiber containing the copolyester and the polyester-based support fiber having a melting point higher than 250° C. in a weight ratio of 20:80 to 50:50.
  • the heat-adhesive fiber is a copolyester obtained by polycondensation of an acid component containing terephthalic acid, and an esterified compound in which ethylene glycol and a diol component containing a compound represented by the following Chemical Formula 1 and Chemical Formula 2 are reacted.
  • a fiber formed by including it serves to attach the polyester-based support fibers to be described later through thermal fusion, and is a fiber that guarantees the shape realization and mechanical strength of the fiber aggregate itself.
  • the acid component includes terephthalic acid, and other than terephthalic acid, an aromatic polyhydric carboxylic acid having 6 to 14 carbon atoms, or an aliphatic polyhydric carboxylic acid having 2 to 14 carbon atoms and/or a sulfonic acid metal salt.
  • the aromatic polyhydric carboxylic acid having 6 to 14 carbon atoms may be used without limitation as an acid component used for the production of polyester, but is preferably selected from the group consisting of dimethyl terephthalate, isophthalic acid and dimethyl isophthalate. It may be one or more, and more preferably may be isophthalic acid in terms of reaction stability with terephthalic acid, ease of handling and economical aspects.
  • the aliphatic polyhydric carboxylic acid having 2 to 14 carbon atoms may be used without limitation as an acid component used for the production of polyester, but as a non-limiting example thereof, oxalic acid, malonic acid, succinic acid, glutar Acid, adipic acid, suberic acid, citric acid, pimeric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid and hexanodecanophosphoric acid may be at least one selected from the group consisting of.
  • the sulfonic acid metal salt may be sodium 3,5-dicarbomethoxybenzene sulfonate.
  • the acidic component other components that may be included in addition to terephthalic acid may reduce the heat resistance of the copolyester, so it is preferable not to include it.
  • an acid component such as isophthalic acid or dimethyl isophthalate
  • the content of VOCs generated in the polycondensation process of the copolyester for example, the content of acetaldehyde may increase, whereas the melting point of the copolyester
  • the content of acetaldehyde in the resulting fiber may be high because it is further lowered and it is difficult to vaporize and remove acetaldehyde generated in the polymerization process through a subsequent process such as heat treatment.
  • isophthalic acid When isophthalic acid is further included, it may be provided in an amount of 1 to 10 mol% based on the acid content, and when it is provided in excess of 10 mol%, there is a risk that the acetaldehyde content may be excessively increased, and the heat-adhesive fiber implemented by this may not be suitable for automotive interior applications.
  • the diol component includes ethylene glycol, a compound represented by the following formula (1) and a compound represented by the formula (2).
  • the compound represented by Chemical Formula 1 may lower the crystallinity and the glass transition temperature of the copolyester to exhibit excellent thermal bonding performance. In addition, it makes the dyeing process easier by enabling dyeing under normal pressure conditions in the dyeing process after being manufactured into fibers, and has excellent dyeing properties to improve wash fastness, and to improve the tactile feel of the fiber aggregate.
  • the compound represented by Formula 1 among the diol components may be included in an amount of preferably 20 to 40 mol%, more preferably 30 to 40 mol%.
  • the copolyester implemented with the compound represented by the formula (2) which will be described later, further increases and improves the thermal adhesive properties at low temperatures, and the copolyester When manufactured as a chip, the drying time can be significantly shortened, and there is an advantage that a synergistic effect can be expressed in reducing the content of VOCs emitted from the heat adhesive fiber.
  • the spinnability is excellent, but there is a concern that the adhesive temperature is increased or the thermal adhesive property is lowered, and the use may be limited. In addition, there is a concern that the content of VOCs emitted from the implemented heat-adhesive fiber increases. In addition, if the compound represented by Formula 1 is provided in excess of 40 mol%, it may be difficult to commercialize due to poor spinnability into the heat-adhesive fiber, and on the contrary, the crystallinity may be increased and the heat-adhesive property may be lowered. There are concerns.
  • the compound represented by Formula 2 further improves the thermal adhesive properties of the copolyester prepared together with the compound represented by Formula 1, and prevents the glass transition temperature of the compound represented by Formula 1 from significantly lowering at 40°C. It is possible to minimize the change over time and improve the storage stability despite the above storage temperature and the vehicle interior temperature rising to 60°C or higher in summer. With respect to thermal adhesiveness, the compound represented by Formula 2 exhibits appropriate shrinkage properties in the heat-adhesive fiber using copolyester realized as it is mixed with the compound represented by Formula 1, and due to this characteristic expression, By further increasing the point adhesive force, it is possible to express more elevated thermal bonding properties.
  • the compound represented by Formula 2 may be included in an amount of preferably 0.8 to 10 mol%, more preferably 0.8 to 6 mol%.
  • the compound represented by Formula 2 is contained in an amount of less than 0.8 mol% based on the diol component, it is difficult to improve the desired heat resistance, so storage stability is not good, and there is a concern that the change over time may be very large. In addition, there is a concern that the content of VOCs emitted from the implemented heat-adhesive fiber increases.
  • the compound represented by Formula 2 is included in excess of 10 mol%, considering that it is used together with the compound represented by Formula 1 described above, it is difficult to commercialize due to poor spinning to the heat-adhesive fiber.
  • the crystallinity is sufficiently lowered and the improvement in adhesiveness is insignificant, and when the content of added isophthalic acid is increased, the crystallinity is rather increased, resulting in excellent thermal adhesive properties at the desired temperature.
  • the object of the invention may not be achieved, such as this may be significantly reduced.
  • the contractility is significantly expressed, so that it is difficult to process into a fiber aggregate or an interior material.
  • the total content of the compound represented by Formula 1 and the compound represented by Formula 2 is preferably included in an amount of 30 to 45 mol% of the diol component, more preferably 33 to It may be included in 41 mol%. If they are included in less than 30 mol%, the crystallinity of the copolyester increases and a high melting point is expressed or it becomes difficult to implement a softening point at a low temperature, so that the heat-bonding temperature is significantly increased, and excellent heat-adhesive properties are expressed at a low temperature it may not be In addition, there is a concern that the content of VOCs emitted from the implemented heat-adhesive fiber increases.
  • the compound represented by the above-described formula 1 may be included in a larger content (mol%) than the compound represented by the formula 2. If the compound represented by Formula 1 is included in less or the same amount than the compound represented by Formula 2, it is difficult to express the desired thermal adhesive properties, and as it must be adhered at a high temperature, the use of the developed product may be limited. In addition, there is a fear that it is difficult to process into a developed product due to the expression of excessive shrinkage characteristics.
  • the diol component may further include other types of diol components in addition to the compound represented by Formula 1, the compound represented by Formula 2, and ethylene glycol.
  • the other type of diol component may be a known diol component used in the production of polyester, the present invention is not particularly limited thereto, but as a non-limiting example thereof, it may be an aliphatic diol component having 2 to 14 carbon atoms, , specifically 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol , may be any one or more selected from the group consisting of nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol and tridecamethylene glycol.
  • diethylene glycol may not be included in the diol components. If diethylene glycol is included in the diol component, it may cause a rapid decrease in the glass transition temperature, so that even when the compound represented by Formula 2 is included, the desired level of heat resistance may not be achieved. In addition, there is a concern that the content of VOCs emitted during use will greatly increase.
  • diethylene glycol is not included in the diol component
  • diethylene glycol is not intentionally added as a monomer for the production of copolyester, and esterification reaction, polymerization/condensation of the acid component and the diol component It does not mean that even diethylene glycol generated as a by-product in the reaction is not included.
  • diethylene glycol can occur naturally as a by-product, according to an embodiment of the present invention, diethylene glycol generated as a by-product may be included in the sheath formed including the copolyester, and the content of the included diethylene glycol is the copolyester. It may be less than 4% by weight based on the weight of the chip or copolyester alone.
  • the pack pressure increases when spinning into fibers, and the spinnability may be significantly reduced by causing frequent thread cutting, and the content of emitted VOCs, especially acetaldehyde There is a possibility that the emission amount is significantly increased.
  • the above-mentioned acid component and diol component can be prepared as copolyester through esterification reaction and polycondensation using known synthesis conditions in the field of polyester synthesis.
  • the acid component and the diol component may be added to react in a molar ratio of 1: 1.0 to 5.0, preferably 1: 1.0 to 2.0, but is not limited thereto.
  • the acid component and the diol component are mixed at a time in an appropriate molar ratio as described above, and then undergo esterification reaction and polycondensation to prepare a copolyester, or between ethylene glycol and the compound represented by Formula 1 among the acid component and the diol component.
  • the compound represented by Chemical Formula 2 may be added during the esterification reaction, and the copolyester may be prepared through an esterification reaction and polycondensation, and the present invention is not particularly limited thereto.
  • a catalyst may be further included in the esterification reaction.
  • the catalyst may be a catalyst typically used in the production of polyester, and as a non-limiting example thereof, may be prepared under a metal acetate catalyst.
  • the esterification reaction may be preferably performed at a temperature of 200 to 270° C. and a pressure of 1100 to 1350 Torr. If the above conditions are not satisfied, there may be problems in that an esterification compound suitable for a polycondensation reaction cannot be formed due to a prolonged esterification reaction time or reduced reactivity.
  • the polycondensation reaction may be carried out at a temperature of 250 to 300 ° C and a pressure of 0.3 to 1.0 Torr, and if the above conditions are not satisfied, there may be problems such as a reaction time delay, a decrease in polymerization degree, and thermal decomposition. .
  • a catalyst may be further included in the polycondensation reaction.
  • the catalyst may be used without limitation in the case of known catalysts used in the production of polyester resins. However, preferably, it may be a titanium-based polymerization catalyst, and more specifically may be a titanium-based polymerization catalyst represented by the following formula (3).
  • the titanium-based polymerization catalyst represented by Chemical Formula 3 is stable even in the presence of water molecules, it is not deactivated even if it is added before the esterification reaction in which a large amount of water is by-produced, so the esterification reaction and polycondensation reaction within a shorter time than before. The reaction may proceed, thereby suppressing coloring due to yellowing.
  • the catalyst may be included in an amount of 5 to 40 ppm in terms of titanium atoms based on the total weight of the obtained copolyester, which is preferable because thermal stability or color tone of the copolyester is improved.
  • the esterification reaction may be preferably performed at a temperature of 200 to 270° C. and a pressure of 1100 to 1350 Torr. If the above conditions are not satisfied, there may be problems in that an esterification compound suitable for a polycondensation reaction cannot be formed due to a prolonged esterification reaction time or reduced reactivity.
  • the polycondensation reaction may be carried out at a temperature of 250 to 300 ° C and a pressure of 0.3 to 1.0 Torr, and if the above conditions are not satisfied, there may be problems such as a reaction time delay, a decrease in polymerization degree, and thermal decomposition. .
  • a thermal stabilizer may be further included during the polycondensation reaction.
  • the thermal stabilizer is to prevent discoloration of color through thermal decomposition at high temperature, and a phosphorus-based compound may be used.
  • the phosphorus compound is preferably phosphoric acid, monomethyl phosphoric acid, trimethyl phosphoric acid, triethyl phosphoric acid, etc. and derivatives thereof. Among them, trimethyl phosphoric acid or triethyl phosphoric acid is more preferable because of its excellent effect.
  • the amount of the phosphorus compound used is preferably 10 to 30 ppm in terms of phosphorus atoms based on the total weight of the finally obtained copolyester.
  • the phosphorus-based thermal stabilizer is used at less than 10 ppm, it is difficult to prevent high-temperature thermal decomposition, so the copolyester may be discolored. If it exceeds 30 ppm, it may be disadvantageous in terms of manufacturing cost and inhibit catalyst activity by the thermal stabilizer during polycondensation reaction. Therefore, there may be a problem that a reaction delay phenomenon occurs.
  • the copolyester may further include a complementary colorant.
  • the complementary colorant is for adjusting the color tone to make the color of the dyed dye stronger and better in the dyeing process proceeding after being spun into the fiber, and it can be added to one known in the textile field, and as a non-limiting example thereof, There are wear dyes, pigments, vat dyes, disperse dyes, and organic pigments. However, preferably, a mixture of blue and red dyes may be used. This is because a cobalt compound generally used as a complementary colorant is undesirable because it is harmful to the human body, whereas a complementary colorant containing blue and red dyes is harmless to the human body and is preferable.
  • the blue dye may include, for example, solvent blue 104, solvent blue 122, and solvent blue 45
  • the red dye may include, for example, solvent red 111, solvent red 179, and solvent red 195.
  • the blue dye and the red dye can be mixed in a weight ratio of 1: 1.0 to 3.0, which is advantageous to express a remarkable effect in a desired fine color tone control.
  • the complementary color agent may be provided in an amount of 1 to 10 ppm based on the total weight of the copolyester. If the amount is less than 1 ppm, it may be difficult to achieve a desired level of complementary color properties, and if it exceeds 10 ppm, the L value is reduced. Therefore, there may be a problem that transparency is lowered and a dark color is displayed.
  • the copolyester according to the present invention prepared through the above-described method may have an intrinsic viscosity of 0.5 to 0.8 dl/g. If the intrinsic viscosity is less than 0.5 dl/g, there may be problems such as not being easy to form a cross-section, and if the intrinsic viscosity exceeds 0.8 dl/g, there may be a problem in spinning due to high pack pressure.
  • the copolyester may have a glass transition temperature of 60 ⁇ 75 °C, through which it may be more advantageous to achieve the object of the present invention. If the glass transition temperature is less than 60 °C, the heat-adhesive fiber embodied with copolyester or the embodied article including the same has a large change with time even in temperature conditions exceeding 40 °C, such as in summer, especially in summer. Considering the interior temperature of the vehicle, the change over time can be significantly increased. In addition, when the heat-adhesive fiber is produced, the occurrence of bonds between the copolyester chips increases, which may cause spinning defects. Furthermore, there is a risk that the shrinkage characteristic is excessively expressed after being implemented with fibers, etc. In addition, due to the limitation of heat treatment required for the drying process after chip formation, the post-processing process after spinning into fibers, etc., there may be a problem in that the process duration is prolonged or the process cannot be smoothly performed.
  • the glass transition temperature exceeds 75 °C, there is a fear that the thermal bonding properties are significantly lowered, there is a fear that the performance temperature of the bonding process may be limited to a high temperature.
  • the above-mentioned copolyester can form a heat-adhesive fiber alone.
  • the above-described copolyester may be provided as a sheath 12 surrounding the core 11 as shown in FIG. 1 to form a core sheath-type heat-adhesive fiber 10 .
  • the core 21 may be a well-known polyester having high heat resistance and mechanical strength compared to the copolyester which is a sheath, and may be, for example, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, etc. It is not limited.
  • the core-sheath heat-adhesive fiber may be, for example, a composite spun of a core and a sheath at a weight ratio of 8:2 to 2:8, but is not limited thereto, and may be spun by appropriately adjusting the ratio according to the purpose. The spinning conditions of the composite fiber, the spinning device and the cooling, stretching, etc.
  • the composite fiber after spinning can be performed through well-known conditions, devices and processes in the art or by appropriately modifying them, so the present invention relates to this It is not particularly limited.
  • the composite fiber may be spun at a spinning temperature of 270 to 290° C., and may be stretched 2.5 to 4.0 times after spinning.
  • the heat-adhesive fiber may have, for example, a fineness of 1 to 15 denier, and a fiber length of, for example, 1 to 100 mm, but is not limited thereto.
  • the heat-adhesive fiber has a VOCs generation amount of 2600 ppb or less, more preferably 2200 ppb or less according to the US EPA TO-14 method, and through this, the amount of harmful components to the human body in a closed environment such as the inside of a car is significantly reduced It can be very useful as a vehicle interior material, and there is an advantage in that the interior material smell can be reduced.
  • the support fiber is implemented by including a polyester-based component for compatibility with the heat-adhesive fiber, and serves to guarantee the mechanical strength, shape maintenance, and heat resistance of the fiber assembly.
  • the polyester-based component may be a component having a melting point higher than 250° C., and through this, it may be more advantageous to achieve the object of the present invention.
  • the support fiber may have, for example, a fineness of 1 to 10 denier, and a fiber length may be, for example, 1 to 100 mm, but is not limited thereto.
  • the support fiber may be used without limitation in the case of a known polyester-based component having a melting point of more than 250° C., and may be, for example, polyethylene terephthalate, but is not limited thereto.
  • the above-described heat-adhesive fibers and support fibers form a fiber aggregate in a weight ratio of 20:80 to 50:50, and preferably may be in a weight ratio of 30:70 to 40:60. If the support fiber is provided at a weight exceeding 4 times the weight of the heat-adhesive fiber, there may be a problem in that the bonding strength of the fiber aggregate is reduced and the adhesive properties are not sufficiently expressed. In addition, when the support fiber is provided at a weight of less than one time based on the weight of the heat-adhesive fiber, the sound absorption rate, feel, and shape stability of the fiber aggregate are significantly reduced, and there is a risk that workability such as initial openability or carding performance is significantly reduced. There is a problem that it is difficult to commercialize due to poor radioactivity, and there is a concern that a nonwoven fabric or fabric having a hard feeling may be realized after thermal bonding due to the ring structure of the rigid modifier.
  • the fiber aggregate including the heat-adhesive fiber and the support fiber may be in the form of a known fabric, for example, a woven fabric, a knitted fabric or a nonwoven fabric, and may be, for example, a nonwoven fabric having no directionality based on the fiber length direction.
  • the nonwoven fabric may be manufactured by a known dry or wet nonwoven manufacturing method, and the present invention is not particularly limited thereto.
  • the heat-adhesive fiber and the support fiber may be manufactured as short fibers having a predetermined length, and then the short fibers are mixed and opened and then heat-treated to be implemented as a fiber aggregate.
  • the heat treatment may be 100 ⁇ 180 °C, more preferably 120 ⁇ 180 °C, through which it is possible to express more improved adhesive properties.
  • the fiber assembly for automobile interior materials may have a sound absorption coefficient of 0.35 or more within a frequency range of 400 to 2000 Hz measured in accordance with KS F 2805.
  • the sound absorption coefficient at a frequency of 1000 Hz may be 0.53 or more, more preferably 0.53 to 0.75.
  • the sound absorption coefficient at a frequency of 2000 Hz may be 0.73 or more, more preferably 0.73 to 0.85.
  • condition (3) may be a sound absorption coefficient of 0.83 or more at a frequency of 3000 Hz, more preferably 0.83 to 0.95, and as the condition (4), a sound absorption coefficient of 0.92 or more at a frequency of 4000 Hz, more preferably 0.92 to 0.99.
  • the fiber assembly for automobile interior materials may satisfy an adhesive strength of 130 to 200N/25mm, more preferably 140 to 200N/25mm, based on KS M ISO 36.
  • a fiber aggregate satisfying such adhesive strength exhibits excellent mechanical strength, and through this, adhesiveness is advantageous even at the same processing temperature, and thus moldability can be facilitated during processing.
  • the rebound modulus may be 45 to 60%, which may be more suitable for interior materials for automobiles, particularly floor carpets.
  • the above-mentioned fiber aggregate for automobile interior materials may be implemented as automobile interior materials by further including single or regenerated denim, melt-blown nonwoven fabric, and the like.
  • the vehicle interior material may be a known type of interior material, and preferably, it may be particularly suitable for flow carpets, iso dash pads, trunk mats, etc. in consideration of excellent sound absorption coefficient, adhesive strength, heat resistance and low VOCs emission.
  • the formed ester reactant is transferred to a polycondensation reactor, 15 ppm of the compound represented by the following Chemical Formula 3 (based on Ti element) as a polycondensation catalyst and 25 ppm of triethyl phosphoric acid (based on P element) as a heat stabilizer are added to a final pressure of 0.5 Torr
  • the copolyester was prepared by carrying out a polycondensation reaction by gradually increasing the temperature to 285° C. under reduced pressure, and then the copolyester was prepared into polyester chips each having a width, length, and height of 2 mm ⁇ 4 mm ⁇ 3 mm in a conventional manner. did.
  • the copolyester chip and the PET chip are placed in a hopper, respectively. After input, melted and put into a core-sheath spinneret, respectively, and then composite spun so that the core and the sheath part at a spinning speed of 1000mpm under 275°C in a weight ratio of 5:5, and stretched 3.0 times to obtain a fiber length of 51 mm and a fineness of 4.0de.
  • a core-sheath type heat-adhesive composite fiber as shown in Table 1 was prepared.
  • the prepared core-sheath composite fiber and polyethylene terephthalate (PET) short fiber were mixed and fiberd in a 5: 5 ratio and then heat treated at a temperature of 120°C, 140°C and 160°C, respectively.
  • a total of three types of fiber aggregates with a basis weight of 35 g/m2 were realized.
  • Example 2 It was prepared in the same manner as in Example 1, but by changing the composition ratio of the monomer for preparing the copolyester as shown in Table 1, Table 2, or Table 3 below, core-sheath composite fiber as shown in Table 1, Table 2 or Table 3 was manufactured and a fiber aggregate was implemented using this.
  • copolyester chip or core-sheath type heat-adhesive composite fiber which is an intermediate during the manufacture of three types of fiber aggregates or fiber aggregates implemented according to Examples and Comparative Examples, and the results are shown in Tables 1 to Table 3 shows.
  • ortho-chlorophenol (Ortho-Chloro Phenol) as a solvent was melted at 110°C, 2.0 g/25ml concentration for 30 minutes, followed by constant temperature at 25°C for 30 minutes, to which a CANON viscometer was connected. Analyzed from an automatic viscometer.
  • the glass transition temperature and melting point of the copolyester were measured using a differential calorimeter, and the analysis condition was a temperature increase rate of 20° C./min.
  • the moisture content was measured in a vacuum dryer at 55° C., every 4 hours, and when the moisture content was measured to be less than 100 ppm as a result of the measurement, the time was indicated as the drying time.
  • Spinning workability occurs during spinning processing for core-sheath composite fibers spun at the same content in Examples and Comparative Examples (meaning a lump formed by partially fusion of the fiber strands passing through the slit or irregular fusion of the strands after trimming)
  • the number was counted through a drip detector, and the number of drips generated in the remaining preparation examples and comparative preparation examples was expressed as a relative percentage based on the drip occurrence value in Preparation Example 1 as 100.
  • the Total K/S value which is an index of the amount of dyeing based on the CIE 1976 standard, is calculated. The color yield of the dye was evaluated.
  • Each of the three fiber aggregates was implemented as a specimen having a width, length, and thickness of 100 mm ⁇ 20 mm ⁇ 10 mm, respectively, and the adhesive strength was measured using a universal testing machine (UTM) according to the KS M ISO 36 method.
  • UTM universal testing machine
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 acid (mole%) TPA 100 100 100 100 100 100 100 100 IPA 0 0 0 0 0 0 total 100 100 100 100 100 100 100 100 100 100 100 Dior ingredient (mole%) EG 59 56 53.5 50 66 69.5 71.5 compound of formula 1 38 39 40 47 32.8 27.5 25.5 compound of formula 2 3 5 6.5 3 1.2 3 3 DEG 0 0 0 0 0 0 0 total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Example 8 Example 9 Example 10 Example 11 Example 12 acid (mole%) TPA 100 100 100 100 100 IPA 0 0 0 0 0 total 100 100 100 100 0 Dior Ingredients (mol%) EG 69.5 69.5 67 72 66 compound of formula 1 21 18.5 21 18.5 33.5 compound of formula 2 9.5 12 12 9.5 0.5 DEG 0 0 0 0 total 100 100 100 100 100 100 Formula 1 + Formula 2 30.5 30.5 33 28 34 polyester chips IV 0.643 0.640 0.642 0.643 0.638 Melting point (°C) none none none none none none 187 none Tg(°C) 72 73 72 73 67 Drying time (Hr) 24 20 24 20 48 composite fiber Spinning workability (%) 86 84 98 81 108 Short fiber storage stability ⁇ ⁇ ⁇ ⁇ ⁇ Dyeing rate (%) 13 11 13 11 15 fiber aggregate 120°C Adhesive Strength (N) 72 46 60 non-adhesive 43 140°C Adhesive Strength (N) 113 89
  • Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 acid (mole%) TPA 100 97 100 100 80 100 IPA 0 3 0 0 20 0 total 100 100 100 100 100 100 100 100 Dior Ingredients (mol%) EG 60 62 63 60 80 63 compound of formula 1 15 35 37 33 0 0 compound of formula 2 22 3 0 0 10 37 DEG 0 0 0 7 10 0 total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Formula 1 + Formula 2 37 38 37 33 10 37 polyester chips IV 0.653 0.635 0.642 0.640 0.638 0.638 Melting point (°C) none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none
  • Comparative Examples have significantly prolonged drying time (Comparative Examples 1 to 3), remarkably poor spinning workability (Comparative Example 2, Comparative Example 3), or very poor short fiber storage stability (Comparative Example 2, Comparative Example 3) ), it can be seen that the shape is deformed (Comparative Example 4) in the evaluation of adhesive strength by temperature, so it can be confirmed that all physical properties cannot be satisfied at the same time, but it can be confirmed that the Examples express all the physical properties at an excellent level .
  • Example 13 in which the content of the compound represented by Formula 2 is higher than that of the compound represented by Formula 1 in the Examples, the shape is deformed in the adhesive strength evaluation by temperature compared to other Examples to achieve the desired physical properties. It can be confirmed that it is not suitable for
  • Example 2 It was prepared in the same manner as in Example 1, except that the composition ratio of the monomers for preparing the copolyester was changed as shown in Table 4 to prepare a copolyester, and a fiber assembly as shown in Table 4 was prepared using this. At this time, the heat treatment temperature for producing the fiber assembly was set to 140 °C.
  • Example 2 It was prepared in the same manner as in Example 1, except that the composition ratio of the monomers for preparing the copolyester was changed as shown in Table 4 to prepare a copolyester, and a fiber assembly as shown in Table 4 was prepared using this. At this time, the heat treatment temperature for producing the fiber assembly was set to 140 °C.
  • Intrinsic viscosity was measured in the same manner as in Experimental Example 1.
  • VOCs Volatile organic compounds
  • Example 15 100 0 25 0.5 0 0 0.644 2801 ⁇
  • Example 16 100 0 25 One 0 26 0.645 2702 ⁇
  • Example 17 100 0 25 3 0 28 0.641 2656 ⁇
  • Example 18 100 0 25 5 0 30 0.646 2292 ⁇
  • Example 19 100 0 30 One 0 31 0.655 2198 ⁇
  • Example 20 100 0 30 2 0 32 0.647 2168 ⁇
  • Example 21 100 0 30 3 0 33 0.652 2129 ⁇
  • Example 22 100 0 30 5 0 35 0.643 2007 ⁇
  • Example 23 100 0 40 One 0 41 0.625 1714 ⁇
  • Example 24 100 0 40 2 0 42 0.637 1673 ⁇
  • Example 25 100 0 40 3 0 43 0.639 1634
  • the test piece was made in a square shape with a side length of 50 mm or more and a thickness of 50 mm or more, and a steel ball weighing 16 g and a diameter of 16 mm was dropped from a height of 500 mm to the test piece to measure the maximum rebound height, and then three test pieces The rebound value was measured at least 3 times continuously within 1 minute in each, and the median value was determined as the rebound modulus (%).
  • the fiber aggregate according to an embodiment of the present invention is excellent in initial openness, carding property, adhesive strength, rebound modulus, workability and sound absorption coefficient as compared to the fiber aggregate according to the comparative example, so it can be confirmed that it is suitable for automobile interior materials.

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  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Nonwoven Fabrics (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne un agrégat de fibres pour un matériau d'habitacle de véhicule, et, plus particulièrement, un agrégat de fibres pour un matériau d'habitacle de véhicule et un matériau d'habitacle de véhicule comprenant celui-ci, l'agrégat de fibres pour un matériau d'habitacle de véhicule présentant un excellent toucher, ainsi que d'excellentes capacités d'absorption acoustique, de force adhésive et d'aptitude au traitement, subissant une variation réduite au minimum en fonction du temps grâce à une excellente résistance à la chaleur, et libérant significativement moins de COV et étant donc particulièrement approprié pour un véhicule possédant un environnement étanche.
PCT/KR2020/019131 2019-12-27 2020-12-24 Agrégat de fibres pour matériau d'habitacle de véhicule, et matériau d'habitacle de véhicule comprenant celui-ci WO2021133116A1 (fr)

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JP2022539448A JP7419540B2 (ja) 2019-12-27 2020-12-24 自動車内装材用繊維集合体及びこれを含む自動車内装材
CN202080090307.9A CN114901882B (zh) 2019-12-27 2020-12-24 汽车内饰材料用纤维集合体及包括其的汽车内饰材料

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KR10-2019-0177036 2019-12-27
KR10-2019-0177032 2019-12-27
KR1020190177036A KR102410331B1 (ko) 2019-12-27 2019-12-27 자동차 내장재용 섬유집합체 및 이를 포함하는 자동차 내장재
KR1020190177032A KR102415149B1 (ko) 2019-12-27 2019-12-27 자동차 내장재용 섬유집합체 및 이를 포함하는 자동차 내장재

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