WO2011162073A1 - Synthetic fiber treatment agent for airbag, synthetic fiber filament for airbag, and base fabric for airbag - Google Patents
Synthetic fiber treatment agent for airbag, synthetic fiber filament for airbag, and base fabric for airbag Download PDFInfo
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- WO2011162073A1 WO2011162073A1 PCT/JP2011/062318 JP2011062318W WO2011162073A1 WO 2011162073 A1 WO2011162073 A1 WO 2011162073A1 JP 2011062318 W JP2011062318 W JP 2011062318W WO 2011162073 A1 WO2011162073 A1 WO 2011162073A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2243—Mono-, di-, or triglycerides
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
- D03D1/02—Inflatable articles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2246—Esters of unsaturated carboxylic acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Definitions
- the present invention relates to a synthetic fiber treatment agent for airbags, a synthetic fiber filament for airbags, and a base fabric for airbags.
- Driver airbags, passenger airbags, side airbags, and knee airbags are formed by forming a heat-resistant polymer film on one side of a flat woven fabric, then cutting it out into a circle and stacking it so that the coating faces each other. Sewn items are used.
- Such a bag is rapidly inflated by high-pressure gas supplied from the gas generator due to a shock such as an accident, and restrains the occupant. At the same time, in order to absorb the impact between the occupant and the bag, the gas is designed to be released so that the internal pressure is instantaneously reduced. Degassing after the deployment of the bag is performed by controlling the air permeability of the bag base fabric by using a vent hole in a coated airbag and by using a non-coated airbag (see Patent Document 1).
- the inflatable curtain airbag is connected to a gas generator connected to a sensor that senses when the vehicle collides or rolls over, and usually consists of a plurality of elongated bags.
- the inflatable curtain airbag is designed so that the inner pressure is maintained for several seconds to 10 seconds after the bag is deployed, and the bag becomes a cushion to protect the occupant even if the vehicle rolls over.
- inflatable curtain airbags are usually used by further improving the airtightness by coating the elastomer resin on the surface of a high-density fabric that has a sufficiently low air permeability even in a non-coated state that is sewn into a bag or bag shape. (See Patent Document 2).
- airbags are required to have characteristics such as strength, airtightness, storage property, safety and low cost.
- inflatable curtain airbags are required to have airtightness and storage.
- the airbags need to be sewn compactly and firmly with a small seam allowance. By increasing the sliding resistance of the airbag base fabric, it is possible to obtain the high stitchability required for such an airbag.
- an airbag base fabric is obtained through a scouring process after weaving a synthetic fiber filament provided with a synthetic fiber treating agent with a water jet loom loom or a known mechanical loom.
- Patent Document 3 has been proposed as a treatment agent for synthetic fibers related to an airbag base fabric obtained by a water jet loom loom.
- This treating agent for synthetic fibers increases the confounding property and entanglement retention property of each single yarn by adjusting the coefficient of friction between each single yarn of the synthetic fiber, and improves the converging property of the original yarn (enhances the yarn-making property).
- the purpose of the invention is to improve the weaving property by water jet loom weaving, and to efficiently deoil in the scouring step after weaving synthetic fibers.
- this synthetic fiber treatment agent is intended to be removed by scouring after improving the yarn-making property and weaving property, and the strength and airtightness of the airbag fabric itself can be improved. There wasn't.
- An object of the present invention is obtained by using an air bag synthetic fiber treatment agent capable of imparting excellent strength and airtightness to an air bag base fabric, an air bag synthetic fiber filament provided with the treatment agent, and the filament. It is providing the base fabric for airbags.
- the present inventors have woven synthetic fiber filaments to which a synthetic fiber treating agent has been applied, and then a scouring step (in the case of water jet loom weaving, there is no scouring step).
- a scouring step in the case of water jet loom weaving, there is no scouring step.
- the friction characteristics of the treating agent component remaining on the base fabric without being removed by the water pressure during the scouring process or during water jet loom weaving It has been found to have an effect on strength and airtightness.
- the synthetic fiber treatment agent essentially contains the specific ester compounds (A) and (B) at a specific ratio, the strength and airtightness of the airbag fabric are improved.
- the present invention is at least one polyvalent ester selected from an ester of an aliphatic polyhydric alcohol and a fatty acid and an ester of an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid, and has a molecular weight of 200 to 200.
- An ester compound (B) that is essential, and the weight ratio (A / B) of the ester compound (A) to the ester compound (B) is 1/1 to 40/1. It is a fiber treatment agent.
- the ester compound (A) is preferably a compound having an unsaturated bond. Moreover, it is preferable that the said ester compound (A) is a compound which has a 3 or more ester group in a molecule
- the ester compound (A) is preferably an ester of a trihydric or higher aliphatic polyhydric alcohol and an unsaturated fatty acid having 8 to 24 carbon atoms.
- the ester compound (B) is preferably a compound having two or more ester groups in the molecule.
- the ester compound (B) is preferably an ester of an aromatic carboxylic acid and an aliphatic alcohol having 8 to 24 carbon atoms.
- the weight ratio of the ester compound (A) in the non-volatile content of the treating agent is preferably 30 to 80% by weight, and the weight ratio of the ester compound (B) is preferably 2 to 30% by weight.
- the synthetic fiber filament for airbag of the present invention is obtained by adding the above-mentioned synthetic fiber treatment agent for airbag to the synthetic fiber filament.
- the synthetic fiber filament is preferably a nylon 6,6, nylon 6, or polyester synthetic fiber filament.
- the airbag fabric of the present invention is made by weaving the above synthetic fiber filaments.
- the synthetic fiber treating agent for an air bag of the present invention can impart excellent strength and air tightness to an air bag base fabric.
- an airbag base fabric excellent in strength and airtightness can be obtained.
- the base fabric for an air bag of the present invention is excellent in strength and airtightness.
- the synthetic fiber treatment agent for an airbag of the present invention essentially contains the specific ester compounds (A) and (B) at a specific ratio. This will be described in detail below.
- the ester compound (A) of the present invention contains at least one polyvalent alcohol selected from an ester (A1) of an aliphatic polyhydric alcohol and a fatty acid and an ester (A2) of an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid. And a molecular weight of 200 to 1300.
- the ester compound (A) is a polyvalent ester having two or more ester groups in the molecule, and is a compound having no polyoxyalkylene group in the molecule. You may use 1 type (s) or 2 or more types of ester compounds (A).
- the ester compound (A) is a component that suppresses high friction due to the ester compound (B) to be described later, and provides lubricity and convergence necessary for yarn production and weaving. Furthermore, since the ester compound (A) has an action of reducing the slip resistance of the airbag base fabric, it is easily removed by scouring after weaving the airbag base fabric or water pressure during weaving the water jet loom (hereinafter referred to as scouring property). Is necessary). Esters containing polyoxyalkylene groups are not preferred because of increased friction.
- the aliphatic polyhydric alcohol constituting the ester (A1) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used.
- the aliphatic polyhydric alcohol is preferably trivalent or more, more preferably 3 to 4 from the viewpoint of further suppressing high friction due to the ester compound (B) and further improving the lubricity and convergence during spinning and weaving. Trivalent is more preferable.
- Trivalent is more preferable.
- high friction due to the ester compound (B) described later cannot be suppressed, so that the yarn making and weaving passability cannot be satisfied.
- Aliphatic polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol, erythritol, Examples include diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, triglycerin, tetraglycerin, and sucrose.
- glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose are preferable, and glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan Are more preferable, and glycerin and trimethylolpropane are more preferable.
- the fatty acid (aliphatic monovalent carboxylic acid) constituting the ester (A1) may be saturated or unsaturated.
- the fatty acid is preferably an unsaturated fatty acid from the viewpoint of scourability. There is no particular limitation on the number of unsaturated bonds, but when there are two or more, one is preferable because deterioration proceeds due to oxidation and the treatment agent is thickened to impair scourability.
- the number of carbon atoms of the fatty acid is preferably from 8 to 24, more preferably from 14 to 24, and even more preferably from 18 to 22 from the standpoint of both the spinning property and the scouring property. 1 type, or 2 or more types may be used for a fatty acid, and a saturated fatty acid and an unsaturated fatty acid may be used together.
- Fatty acids include butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, pentadecylic acid, palmitic acid, palmitoleic acid, isocetyl acid, margarine Acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoserine
- Examples include acids, isotetradocosanoic acid, nervonic acid, serotic acid, montanic acid, melicic acid and the like.
- the aliphatic monohydric alcohol constituting the ester (A2) is not particularly limited, and one or more kinds can be used.
- the aliphatic monohydric alcohol may be saturated or unsaturated.
- the aliphatic monohydric alcohol is preferably an unsaturated aliphatic monohydric alcohol from the viewpoint of scourability. There is no particular limitation on the number of unsaturated bonds, but when there are two or more, one is preferable because deterioration proceeds due to oxidation and the treatment agent is thickened to impair scourability.
- the number of carbon atoms of the aliphatic monohydric alcohol is preferably 8 to 24, more preferably 14 to 24, and still more preferably 18 to 22 from the standpoint of both the spinning property and the scourability.
- One or more aliphatic monohydric alcohols may be used, and a saturated aliphatic monohydric alcohol and an unsaturated aliphatic monohydric alcohol may be used in combination.
- Examples of the aliphatic monohydric alcohol include octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Bacenyl alcohol, gadreyl alcohol, argidinyl alcohol, isoiconanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetradocosanyl alcohol, nerbonyl alcohol, Examples include serotonyl alcohol, montanyl alcohol, and melinyl alcohol.
- octyl alcohol isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, vacenyl alcohol Gadreyl alcohol, argidinyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignoserinyl alcohol, isotetradocosanyl alcohol, nerbonyl alcohol are preferred, Trail alcohol, palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, baxenyl Alcohol, gadoleyl alcohol, eicosyl cell noil alcohol, erucic alkenyl alcohol, more preferably flannel isobornyl alcohol, oleyl alcohol, e
- the aliphatic polyvalent carboxylic acid constituting the ester (A2) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used.
- the aliphatic polyvalent carboxylic acid used in the present invention does not contain a sulfur-containing polyvalent carboxylic acid such as thiodipropionic acid.
- the aliphatic polyvalent carboxylic acid is more preferably divalent from the standpoint of further suppressing high friction due to the ester compound (B) and further improving the lubricity and convergence during spinning and weaving. Similarly, it is preferable that no hydroxyl group is contained in the molecule.
- Aliphatic polycarboxylic acids include citric acid, isocitric acid, malic acid, aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain An acid, sebacic acid, etc. are mentioned.
- aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are preferred, and succinic acid, fumaric acid, maleic acid are preferred.
- Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are more preferable.
- the molecular weight of the ester compound (A) is 200 to 1300. As a result, it becomes possible to stabilize the yarn-making property and perform high-strength drawing, and to obtain a high-strength synthetic fiber.
- the molecular weight is preferably 400 to 1300, more preferably 600 to 1000.
- the extreme pressure property of the synthetic fiber to which the treatment agent is applied is low, and an oil film is cut between the yarn and the drawing roller during drawing, and the friction between the yarn and the drawing roller increases. As a result, the spinning property is lowered and the synthetic fiber cannot be stretched at a high magnification, and a high-strength synthetic fiber cannot be obtained.
- the viscosity (25 ° C.) of the ester compound (A) is preferably 40 to 90 mm 2 / s from the viewpoint of suppressing high friction due to the ester compound (B) and improving lubricity and convergence during yarn production and weaving. 50 to 80 mm 2 / s is more preferable, and 60 to 70 mm 2 / s is more preferable.
- the ester compound (A) is preferably one having three or more ester groups in the molecule from the viewpoint of suppressing high friction due to the ester compound (B) and improving lubricity and convergence during yarn production and weaving. Three is more preferable.
- an ester compound has an unsaturated bond in a molecule
- the number of unsaturated bonds is not particularly limited, but if there are two or more unsaturated bonds in the same alkyl chain, the deterioration proceeds due to the acid value and the treating agent is thickened to impair the scouring properties. One is preferred.
- an ester (A1) of an aliphatic polyhydric alcohol and a fatty acid is preferable from the viewpoint of more exerting the above-described effects and cost, and among the esters (A1), trivalent or more An ester of an aliphatic polyhydric alcohol and an unsaturated fatty acid having 8 to 24 carbon atoms is more preferred, and an ester of an aliphatic trivalent alcohol and an unsaturated fatty acid having 18 to 22 carbon atoms is particularly preferred.
- the ester compound (B) of the present invention is an ester having at least one aromatic ring selected from an ester (B1) of an aromatic carboxylic acid and an alcohol and an ester (B2) of an aromatic alcohol and a carboxylic acid,
- the molecular weight is 200-2600.
- the ester compound (B) is a compound having at least one aromatic ring in the molecule and having no polyoxyalkylene group in the molecule. 1 type (s) or 2 or more types may be used for an ester compound (B).
- the ester compound (B) is a component that enhances the slip resistance of the airbag base fabric, and is not easily removed by water pressure during scouring or water jet loom weaving after weaving the airbag base fabric (hereinafter sometimes referred to as persistence). )is required.
- persistence water pressure during scouring or water jet loom weaving after weaving the airbag base fabric
- the aromatic carboxylic acid constituting the ester (B1) may be a monocarboxylic acid or a polyvalent carboxylic acid. You may use 1 type, or 2 or more types. Aromatic polyvalent carboxylic acids are preferred and aromatic trivalent carboxylic acids are more preferred from the standpoint of slip-off resistance and yarn production. Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, melittic acid, cinnamic acid, trimellitic acid and the like. Among these, trimellitic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and trimellitic acid is more preferable.
- the alcohol constituting the ester (B1) may be a monohydric alcohol or a polyhydric alcohol. Moreover, any of aliphatic alcohol, alicyclic alcohol, and aromatic alcohol may be sufficient. You may use 1 type, or 2 or more types. Among these, monohydric alcohols are preferable, and aliphatic monohydric alcohols are more preferable.
- the aliphatic monohydric alcohol is preferably saturated from the viewpoint of persistence.
- the aliphatic monohydric alcohol may be linear or branched.
- the number of carbon atoms of the aliphatic monohydric alcohol is preferably 8 to 24, more preferably 12 to 24, and still more preferably 18 to 24, from the standpoint of both the spinning property and the persistence.
- Monohydric alcohols include alkylbenzene alcohol, dialkylbenzene alcohol, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol , Elidyl alcohol, bacenyl alcohol, gadrel alcohol, argidinyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetradocosanyl Alcohol, nerbonyl alcohol, serotinyl alcohol, montanyl alcohol, meli Alkenyl alcohol.
- the aromatic alcohol which comprises ester (B2) may use 1 type (s) or 2 or more types.
- Aromatic polyhydric alcohols are preferred and aromatic trihydric alcohols are more preferred from the standpoint of slip-off resistance and yarn production.
- Examples of the aromatic alcohol include aromatic monohydric alcohols such as alkylbenzene alcohols, aromatic polyhydric alcohols such as dialkylbenzene alcohols, bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene. Among these, bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene are preferable, and 1,3,5-trihydroxymethylbenzene is more preferable.
- the carboxylic acid constituting the ester (B2) may be either an aliphatic carboxylic acid or an aromatic carboxylic acid. Either a monovalent carboxylic acid or a polyvalent carboxylic acid may be used. You may use 1 type, or 2 or more types. Among these, monovalent carboxylic acids are preferable, and fatty acids are more preferable.
- the fatty acid is preferably saturated from the viewpoint of persistence.
- the fatty acid may be linear or branched.
- the number of carbon atoms of the fatty acid is preferably from 8 to 24, more preferably from 12 to 24, and even more preferably from 18 to 24, from the standpoint of both the spinning properties and the persistence.
- Monovalent carboxylic acids include alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristic acid, Pentadecylic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, Examples include eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetradocosanoic acid, nervonic
- alkylbenzene carboxylic acid dialkylbenzene carboxylic acid
- stearic acid isostearic acid
- tuberculosic More preferred are stearic acid, arachidic acid, isoicosanoic acid, behenic acid, isodocosanoic acid, lignoceric acid, isotetradocosanoic acid and the like.
- polyvalent carboxylic acid include the aliphatic polyvalent carboxylic acid described in the ester (A2) and the aromatic polyvalent carboxylic acid described in the ester (B1).
- the molecular weight of the ester compound (B) is 200-2600. This makes it possible to achieve both the stability of the yarn production and the high resistance to slipping out of the fabric (edge comb resistance), and to obtain desirable characteristics as a synthetic fiber for an airbag.
- the molecular weight is preferably 400 to 2000, and more preferably 600 to 1500. When the molecular weight is less than 200, the static friction force between the warp and the weft of each warp and weft when the completed airbag base fabric is disassembled becomes low, and the base fabric sliding resistance (edge comb resistance) becomes small.
- the ester compound (B) preferably has two or more ester groups in the molecule from the viewpoint of enhancing slipping resistance, and more preferably 2 to 3 from the viewpoint of the stability of yarn production.
- an ester (B1) of an aromatic carboxylic acid and an alcohol is preferable from the viewpoint of achieving both slipping resistance and yarn-making property.
- an ester of an aromatic carboxylic acid and an aliphatic alcohol is preferable, an ester of an aromatic polyvalent carboxylic acid and an aliphatic monohydric alcohol is preferable, and then an aromatic trivalent carboxylic acid and Esters with aliphatic monohydric alcohols are preferred, followed by aromatic trivalent carboxylic acids and aliphatic monohydric alcohols having 8 to 24 carbon atoms, and then aromatic trivalent carboxylic acids and fatty acids having 12 to 24 carbon atoms.
- aromatic monohydric alcohols and most preferred are aromatic trivalent carboxylic acids and aliphatic monohydric alcohols having 18 to 24 carbon atoms.
- the weight ratio (A / B) of the ester compound (A) to the ester compound (B) is 1/1 to 40/1.
- the weight ratio is preferably 2/1 to 15/1, more preferably 2/1 to 10/1, and further preferably 3/1 to 5/1.
- the production method of the ester compound (A) and the ester compound (B) is not particularly limited, and a known esterification method can be employed.
- the synthetic fiber treating agent for an airbag of the present invention includes an ester compound (A) and an ester compound (B) which are essential components, a diester compound (C) of thiodipropionic acid and an aliphatic alcohol, and an aromatic ring. It is preferable to contain at least 1 sort (s) chosen from a silicone compound (D), the below-mentioned nonionic surfactant (E), and the below-mentioned nonionic surfactant (F).
- Diester compound (C) of thiodipropionic acid and aliphatic alcohol is a component having antioxidant ability.
- the heat resistance of a processing agent can be improved by using a diester compound (C). You may use 1 type, or 2 or more types.
- the molecular weight of the thiodipropionic acid constituting the diester compound (C) is preferably 400 to 1000, more preferably 500 to 900, and still more preferably 600 to 800.
- the aliphatic alcohol constituting the diester compound (C) may be saturated or unsaturated, and may be linear or branched.
- the aliphatic alcohol preferably has 8 to 24 carbon atoms, more preferably 12 to 24, and still more preferably 18 to 24.
- Examples of the aliphatic alcohol include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, isocetyl alcohol, oleyl alcohol and isostearyl alcohol. Among these, oleyl alcohol and isostearyl alcohol are exemplified. preferable.
- the aromatic ring-containing silicone compound (D) is a component that increases sliding resistance like the ester compound (B), and is more likely to remain on the airbag base fabric than the ester compound (B). By using the aromatic ring-containing silicone compound (D) in combination, the slip resistance can be further increased.
- the aromatic ring-containing silicone compound (D) is a group having an aromatic ring such as a phenyl group or a naphthalene group at at least one of both ends, one end, side chain, and both side ends of a polysiloxane such as dimethylpolysiloxane. This refers to a modified silicone modified with One or more aromatic ring-containing silicone compounds (D) may be used.
- the aromatic ring-containing silicone compound (D) phenyl-modified dimethylpolysiloxane, diphenylpolysiloxane and the like are used. From both the spinnability and slippage resistance, viscosity (25 ° C.) is preferably 200 ⁇ 600mm 2 / s, more preferably 300 ⁇ 500mm 2 / s, more preferably 350 ⁇ 450mm 2 / s.
- the molar ratio (M / P) of the methyl group (M) constituting the polysiloxane chain and the group (P) having an aromatic ring is preferably 10 or less, more preferably 5 or less, further preferably 2 or less, particularly preferably 0. preferable.
- Nonionic surfactant (E) includes polyoxyalkylene aliphatic alcohol ether (E1), polyhydric alcohol partial ester type nonionic surfactant (E2), and polyoxyalkylene polyhydric alcohol fatty acid ester type nonionic surfactant. At least one selected from (E3).
- the nonionic surfactant (E) is a component that improves the uniform adhesion of the treatment agent to the raw yarn, imparts convergence to the raw yarn, and improves the yarn-making property and weaving property.
- the polyoxyalkylene aliphatic alcohol ether (E1) is obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to an aliphatic monohydric alcohol. It plays a role of giving uniform adhesion to the raw yarn of the treatment agent.
- ester compound (A) including diester compound (C) and aromatic ring-containing silicone compound (D) in some cases
- the group monohydric alcohol preferably has 11 to 15 carbon atoms. Moreover, what has a branched chain is preferable.
- polyoxyalkylene aliphatic alcohol ether examples include alkylene oxides of aliphatic alcohols such as octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. Addenda may be mentioned. Among these, an alkylene oxide adduct of lauryl alcohol and tridecyl alcohol is preferable, and an alkylene oxide adduct of tridecyl alcohol is more preferable.
- the number of moles of alkylene oxide added is preferably 2 to 30 moles, more preferably 4 to 20 moles, and even more preferably 6 to 15 moles.
- the polyhydric alcohol partial ester type nonionic surfactant (E2) is a compound obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to a polyhydric alcohol in a range of 1 mol to less than 50 mol, and a monovalent It is an ester with an aliphatic carboxylic acid (fatty acid).
- the polyhydric alcohol partial ester type nonionic surfactant (E2) mainly plays a role of increasing the convergence of the raw yarn, but it is preferable that the polyhydric alcohol partial ester type nonionic surfactant does not remain on the base fabric in order to reduce the slip-off resistance, that is, has high scourability. .
- Examples of the polyhydric alcohol used in the nonionic surfactant (E2) include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose.
- the monovalent aliphatic carboxylic acid used for the nonionic surfactant (E2) may be saturated or unsaturated.
- Examples include stearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetradocosanoic acid, and nervonic acid.
- polyhydric alcohol glycerin, trimethylolpropane, pentaerythritol, erythritol, sorbitan, and monovalent aliphatic carboxylic acid as palmitic acid, palmitoleic acid, isocetylic acid, margaric acid, stearic acid, isostearic acid Oleic acid, elaidic acid, and vaccenic acid are preferable, and as the polyhydric alcohol, glycerin, sorbitan, and monovalent aliphatic carboxylic acid are more preferably stearic acid, isostearic acid, oleic acid, elaidic acid, and vaccenic acid.
- the number of added moles of alkylene oxide is preferably 5 to 35, more preferably 10 to 30, and still more preferably 15 to 25.
- the molecular weight of the nonionic surfactant (E2) is preferably from 1000 to 3000, more preferably from 1200 to 2800, still more preferably from 1500 to 2500.
- the polyoxyalkylene polyhydric alcohol fatty acid ester type nonionic surfactant (E3) is a compound obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to an ester of an aliphatic hydroxy monohydric carboxylic acid and a polyhydric alcohol.
- the polyoxyalkylene polyhydric alcohol fatty acid ester type nonionic surfactant (E3) mainly plays a role of increasing the convergence of the raw yarn, but it is difficult to remain on the base fabric in order to reduce the slip-off resistance, that is, it has a high scouring property. It is preferable.
- Examples of the polyhydric alcohol used in the nonionic surfactant (E3) include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose.
- Examples of the aliphatic hydroxy monovalent carboxylic acid used for the nonionic surfactant (E3) include ricinoleic acid, ricineraidic acid, hydroxystearic acid, cerebuloic acid, and hydroxylignoceric acid.
- glycerin, trimethylolpropane, pentaerythritol, erythritol, sorbitan, and aliphatic hydroxy monovalent carboxylic acid are preferable as polyhydric alcohol, and ricinoleic acid, ricinaleic acid, and cerebronic acid are preferable.
- ricinoleic acid is more preferable.
- the number of moles of alkylene oxide added is preferably 1 to 50, more preferably 5 to 35, still more preferably 10 to 30, and particularly preferably 15 to 25.
- the molecular weight of the nonionic surfactant (E3) is preferably from 1000 to 3000, more preferably from 1200 to 2800, still more preferably from 1500 to 2500.
- the nonionic surfactant (F) reacts a fatty acid having 8 to 24 carbon atoms with the polyhydric alcohol alkylene oxide adduct (F1) and polyhydric alcohol alkylene oxide adduct (F1) to which 50 mol or more of alkylene oxide is added. It is at least 1 sort (s) chosen from the nonionic surfactant (F2) obtained by these.
- the nonionic surfactant (F) is a component that imparts convergence to the raw yarn and improves the spinning property and weaving property, while remaining on the airbag base fabric to increase the slip resistance.
- the slip resistance of the airbag base fabric can be increased more than the nonionic surfactant (E2) and the nonionic surfactant (E3).
- the polyhydric alcohol alkylene oxide adduct (F1) is obtained by adding 50 mol or more of alkylene oxide such as propylene oxide or ethylene oxide to the polyhydric alcohol.
- alkylene oxide such as propylene oxide or ethylene oxide
- Examples include adducts, sorbitol propylene oxide ethylene oxide adducts, and the like. Among these, trimethylolpropane propylene oxide ethylene oxide adduct is preferable.
- the number of moles of alkylene oxide added is preferably 60 to 200, more preferably 80 to 180, and still more preferably 100 to 160.
- a nonionic surfactant (F) contains 50 mol% or more of propylene oxide with respect to the whole alkylene oxide in a molecule
- numerator 65 mol% or more is more preferable, and 80 mol% or more is further more preferable.
- the propylene oxide content is less than 50 mol%, the static friction force between the warp and weft yarns when the finished airbag base fabric is disassembled is reduced, and the fabric slip resistance (edge comb resistance) Is not preferable because it becomes smaller.
- the nonionic surfactant (F2) is obtained by reacting an alkylene oxide adduct (F1) of the polyhydric alcohol with a monovalent carboxylic acid having 8 to 24 carbon atoms.
- the monovalent carboxylic acid may be either an aliphatic carboxylic acid or an aromatic carboxylic acid.
- the carbon number of the monovalent carboxylic acid is preferably 12 to 24, and more preferably 18 to 24.
- the monovalent carboxylic acid having 8 to 24 carbon atoms, which may be saturated or unsaturated, is a saturated alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid.
- Acid isocetylic acid, margaric acid, stearic acid, isostearic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, behenic acid, isodocosanoic acid, lignoceric acid, isotetradocosanoic acid and the like are preferable.
- Fatty acids with one unsaturated bond myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid can be used in combination with saturated carboxylic acids, but unsaturated Fatty acids having two or more bonds, such as linoleic acid and linolenic acid, are not preferred because degradation proceeds by auto-oxidation.
- the molecular weight of the nonionic surfactant (F) is preferably 3000 to 10,000, more preferably 4000 to 9000, and further preferably 5000 to 8000.
- the molecular weight of the nonionic surfactant (F) is less than 3000, tar-like stains are likely to be generated on the surface of a heated body such as a hot roller when a synthetic fiber is hot stretched at a high magnification, and a lot of smoke is generated. There is a case.
- the molecular weight exceeds 10,000, the friction between the yarn and the drawing roller, that is, the friction against metal becomes high, and high-strength synthetic fibers may not be obtained because high-stretching cannot be performed.
- the weight ratio of the ester compound (A) in the nonvolatile content of the synthetic fiber treating agent for airbag is preferably 30 to 80% by weight, more preferably 45 to 80% by weight, and further preferably 60 to 80% by weight. If it is less than 30% by weight, the friction between the yarn and the drawing roller, that is, the friction against the metal becomes high, and high-strength synthetic fibers may not be obtained because high-stretching cannot be performed. If it exceeds 80% by weight, the sliding resistance of the airbag base fabric may be lowered.
- the weight ratio of the ester compound (B) in the non-volatile content of the treating agent is preferably 2 to 30% by weight, more preferably 5 to 20% by weight, and even more preferably 10 to 20% by weight. If it is less than 2% by weight, the slip resistance of the airbag fabric may be lowered. If it exceeds 30% by weight, the friction between the yarn and the drawing roller, that is, the friction against the metal becomes high, and high-strength synthetic fibers may not be obtained because high-stretching cannot be performed.
- the non-volatile content in the present invention refers to an absolutely dry component when the treatment agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
- the weight proportion of the diester compound (C) in the nonvolatile content of the treating agent is preferably 1 to 20% by weight, more preferably 1 to 15% by weight. 3 to 12% by weight is more preferable. If it exceeds 20% by weight, the occurrence of contamination on the surface of a heating element such as a heat roller may increase.
- the weight ratio of the silicone compound (D) in the nonvolatile content of the treating agent is preferably 1 to 20% by weight, and 5 to 20% by weight. Is more preferably 10 to 20% by weight. If it exceeds 20% by weight, the residual oil content of the fabric obtained in the weaving process increases, and it may be difficult to coat the elastomer resin on the fabric.
- the weight ratio of the nonionic surfactant (E) to the non-volatile content of the treatment agent is preferably 1 to 40% by weight, preferably 5 to 30% by weight is more preferable, and 10 to 20% by weight is further preferable. If it exceeds 40% by weight, smoke may be generated in the vicinity of a heated body such as a heat roller.
- the weight ratio of the nonionic surfactant (F) to the non-volatile content of the treatment agent is preferably 1 to 20% by weight. 10 wt% is more preferable, and 5 to 10 wt% is more preferable. If it exceeds 20% by weight, the residual oil content of the fabric obtained in the weaving process increases, and it may be difficult to coat the elastomer resin on the fabric.
- the total weight of the ester compound (A) and the ester compound (B) in the nonvolatile content of the treatment agent (including the above-mentioned other components) is 90% by weight or more. Preferably there is. By this weight ratio, the yarn-making property of the synthetic fiber and the weaving property of the obtained synthetic fiber can be maintained, and the effects of each component can be sufficiently exhibited.
- the treatment agent of the present invention is a component other than the above-described components as long as the effects of the present invention are not impaired, such as an antioxidant, a pH adjuster, an antistatic agent, a viscosity stabilizer, and an extreme pressure agent. You may contain a regulator.
- the weight ratio of these modifiers to the non-volatile content of the treatment agent is preferably less than 10% by weight.
- the synthetic fiber treatment agent for airbags of the present invention may be composed of the above-mentioned components consisting only of non-volatile components, or may be prepared by diluting the above non-volatile components with a low-viscosity mineral oil, and emulsifies the non-volatile components in water. It may be a water-based emulsion. Among these, for the reason of uniform adhesion, those obtained by diluting the aforementioned non-volatile content with a low-viscosity mineral oil and adjusting to an arbitrary viscosity suitable for the oil supply device are preferable.
- the viscosity (25 ° C.) of the mineral oil to be diluted is preferably 1 to 3 mm 2 / s.
- the concentration of the non-volatile content when diluted with mineral oil is preferably 30 to 99% by weight.
- the method for producing the synthetic fiber treating agent for an airbag of the present invention is not particularly limited, and a known method can be adopted.
- the treating agent is usually produced by adding and mixing the above-mentioned components constituting in any order.
- the synthetic fiber filament for airbag of the present invention is obtained by adding the synthetic fiber treating agent for airbag of the present invention to the (raw material) synthetic fiber filament.
- the amount of the synthetic fiber treating agent for airbag applied is preferably 0.01 to 2% by weight, more preferably 0.5 to 1.5% by weight, and more preferably 0.75 to 1% with respect to the (raw material) synthetic fiber filament. More preferred is .25% by weight.
- the method for applying the synthetic fiber treating agent for airbag of the present invention to the synthetic fiber filament is not particularly limited, and a known method can be adopted.
- Examples of the synthetic fiber filament to which the synthetic fiber treating agent for airbag according to the present invention is applied include synthetic fiber filaments such as polyester, nylon 6, 6, and nylon 6.
- synthetic fiber filaments such as polyester, nylon 6, 6, and nylon 6.
- nylon 6 and 6 synthetic fiber filaments are particularly suitable because of their durability to the high-pressure gas supplied from the gas generator.
- the airbag fabric of the present invention is made by weaving synthetic fiber filaments for airbags to which the synthetic fiber treatment agent for airbags of the present invention is applied.
- the method for producing the airbag fabric of the present invention includes a weaving step of weaving the synthetic fiber filament for airbag to which the synthetic fiber treatment agent for airbag of the present invention is applied.
- the weaving process is not particularly limited, and a known process / method can be employed. For example, weaving with a water jet loom, rapier weaving, air jet loom, weaving with a slewer loom and the like can be mentioned.
- a scouring process is usually required to remove spinning oil and weaving oil after weaving synthetic fiber filaments for airbag .
- a well-known method is employable. For example, it is carried out by impregnating in a hot water bath containing a scouring agent at 20 to 100 ° C., squeezing with mangle, and then drying at 80 to 150 ° C.
- a scouring process is carried out by impregnating in a hot water bath containing a scouring agent at 20 to 100 ° C., squeezing with mangle, and then drying at 80 to 150 ° C.
- most of the treatment agent is removed by water pressure at the time of weaving, so the scouring process is omitted.
- the airbag fabric of the present invention is an airbag fabric woven from the synthetic fiber filament of the airbag of the present invention, and the ester compound (B) is added in an amount of 0.01 to 0 to the entire fabric. .2% by weight is included.
- the treating agent component is removed by a scouring step or water pressure in a water jet loom.
- the ester compound (A) is selectively removed and the ester compound (B) is selectively left by the scouring step or the water pressure in the water jet loom.
- the high friction of the ester compound (B) can increase the static frictional force of the yarn and yarn while preventing the yarn from being damaged due to the wear of the yarn and yarn. Become.
- a diester compound (C) when a diester compound (C) is included, these components are also selectively removed.
- Examples 1 to 11, Comparative Examples 1 to 12 The components listed in Table 1 or 2 below were mixed and stirred to prepare the non-volatile content of the synthetic fiber treating agent for airbags of each Example and Comparative Example. Details of each symbol of the treating agent component in Table 1 are as shown in Table 3. These treatment agent non-volatile components and C13 paraffin oil were mixed at a weight ratio of 1: 1 to prepare a synthetic fiber treatment agent for airbags. Next, 470 decitex, 68 filament round section nylon 6,6 filament was melt-spun, and the prepared treating agent was applied to the obtained yarn at 1% by weight by the jet nozzle oiling method. Without being wound up, it was wound at 210 ° C. using a hot roller at a draw ratio of 5 times to obtain a synthetic fiber filament for airbag. The stretchability was evaluated by the following method. The results are shown in Tables 4 and 5.
- the obtained synthetic fiber filaments for each airbag are woven in (a) water jet loom so that the weaving density of warps and wefts is 54 / 2.54 cm, and (b) in a rapier loom. After weaving so that the weaving density of warps and wefts becomes 54 / 2.54 cm, bath bath scouring is performed by a known method, and two types of plain fabrics for air bags (a) and (b) are obtained. Obtained. With respect to these airbag fabrics, the following evaluation methods were used to determine the static frictional force between yarns, the residual oil content of the fabric, the residual amount of ester compound (B), the fabric breaking strength, the fabric slip resistance (edge comb) Resistance) was evaluated. The results of the airbag fabric (a) are shown in Tables 4 and 5, and the results of the airbag fabric (b) are shown in Tables 6 and 7.
- T2 / T1 is preferably 2.75 to 3.50.
- the synthetic fiber filaments provided with the synthetic fiber treatment agents for airbags of Examples 1 to 11 have good stretchability during yarn production.
- the air bag base fabrics of Examples 1 to 11 are excellent in the static friction between yarns and yarns in both water jet loom weaving (a) and rapier loom weaving (b). Both fabric breaking strength and base fabric slip resistance are excellent. Therefore, it was possible to achieve both the base fabric breaking strength and the base fabric slip resistance.
- Comparative Examples 1 to 12 treatment agent that does not essentially contain the ester compound (A) and the ester compound (B), and the weight ratio (A / B) of the ester compound (A) to the ester compound (B) is 1
- the stretchability during yarn production is inferior to that of the examples, and the static frictional force between the yarn and yarn is low, and the base fabric breaking strength and base Both cloth slipping resistance is inferior.
- the synthetic fiber treatment agent of the present invention is excellent in extreme pressure properties, lubricity, and heat resistance, and is applied in the fiber manufacturing process and / or processing step. Especially, it is a synthetic material for industrial materials having high strength such as nylon and polyester. Suitable for fiber.
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Abstract
Description
前記合成繊維フィラメントは、ナイロン6,6、ナイロン6またはポリエステルの合成繊維フィラメントであることが好ましい。 The synthetic fiber filament for airbag of the present invention is obtained by adding the above-mentioned synthetic fiber treatment agent for airbag to the synthetic fiber filament.
The synthetic fiber filament is preferably a nylon 6,6, nylon 6, or polyester synthetic fiber filament.
本発明のエステル化合物(A)は、脂肪族多価アルコールと脂肪酸とのエステル(A1)および脂肪族1価アルコールと脂肪族多価カルボン酸とのエステル(A2)から選ばれる少なくとも1種の多価エステルであり、かつ分子量が200~1300である。エステル化合物(A)は、分子内に2個以上のエステル基を有する多価エステルであり、また分子内にポリオキシアルキレン基を有しない化合物である。エステル化合物(A)は1種又は2種以上使用してもよい。
エステル化合物(A)は、後述するエステル化合物(B)による高摩擦を抑え、製糸時と製織時に必要な潤滑性と収束性を与える成分である。さらに、エステル化合物(A)はエアバック基布の滑脱抵抗を下げる作用があるため、エアバック基布製織後の精練またはウォータージェットルーム製織時の水圧で除去されやすい性質(以下、精練性ということがある)が必要である。ポリオキシアルキレン基を含有するエステルは摩擦が高くなるため、好ましくない。 [Ester compound (A)]
The ester compound (A) of the present invention contains at least one polyvalent alcohol selected from an ester (A1) of an aliphatic polyhydric alcohol and a fatty acid and an ester (A2) of an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid. And a molecular weight of 200 to 1300. The ester compound (A) is a polyvalent ester having two or more ester groups in the molecule, and is a compound having no polyoxyalkylene group in the molecule. You may use 1 type (s) or 2 or more types of ester compounds (A).
The ester compound (A) is a component that suppresses high friction due to the ester compound (B) to be described later, and provides lubricity and convergence necessary for yarn production and weaving. Furthermore, since the ester compound (A) has an action of reducing the slip resistance of the airbag base fabric, it is easily removed by scouring after weaving the airbag base fabric or water pressure during weaving the water jet loom (hereinafter referred to as scouring property). Is necessary). Esters containing polyoxyalkylene groups are not preferred because of increased friction.
脂肪族多価アルコールとしては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2-メチル-1,3-プロパンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、シクロヘキサンジオール、シクロヘキサンジメタノール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリグリセリン、テトラグリセリン、ショ糖等が挙げられる。これらの中でも、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ジペンタエリスリトール、ショ糖が好ましく、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタンがより好ましく、グリセリン、トリメチロールプロパンがさらに好ましい。 The aliphatic polyhydric alcohol constituting the ester (A1) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used. The aliphatic polyhydric alcohol is preferably trivalent or more, more preferably 3 to 4 from the viewpoint of further suppressing high friction due to the ester compound (B) and further improving the lubricity and convergence during spinning and weaving. Trivalent is more preferable. In the case of an aliphatic monohydric alcohol, high friction due to the ester compound (B) described later cannot be suppressed, so that the yarn making and weaving passability cannot be satisfied.
Aliphatic polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol, erythritol, Examples include diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, triglycerin, tetraglycerin, and sucrose. Among these, glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose are preferable, and glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan Are more preferable, and glycerin and trimethylolpropane are more preferable.
脂肪族多価カルボン酸としては、クエン酸、イソクエン酸、リンゴ酸、アコニット酸、オキサロ酢酸、オキサロコハク酸、コハク酸、フマル酸、マレイン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等が挙げられる。これらの中でも、アコニット酸、オキサロ酢酸、オキサロコハク酸、コハク酸、フマル酸、マレイン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸が好ましく、コハク酸、フマル酸、マレイン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸がより好ましい。 The aliphatic polyvalent carboxylic acid constituting the ester (A2) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used. The aliphatic polyvalent carboxylic acid used in the present invention does not contain a sulfur-containing polyvalent carboxylic acid such as thiodipropionic acid. The aliphatic polyvalent carboxylic acid is more preferably divalent from the standpoint of further suppressing high friction due to the ester compound (B) and further improving the lubricity and convergence during spinning and weaving. Similarly, it is preferable that no hydroxyl group is contained in the molecule.
Aliphatic polycarboxylic acids include citric acid, isocitric acid, malic acid, aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain An acid, sebacic acid, etc. are mentioned. Among these, aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are preferred, and succinic acid, fumaric acid, maleic acid are preferred. Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are more preferable.
分子量が200未満になると、処理剤を付与した合成繊維の極圧性が低く、延伸時に糸条と延伸ローラーとの間で油膜切れを起こし、糸条と延伸ローラーとの摩擦が増大する。その結果、製糸性が低下して合成繊維を高倍率延伸できなくなり、高強度の合成繊維を得ることができなくなる。一方、分子量が1300を越えると、糸条と延伸ローラーなどとの摩擦、すなわち対金属摩擦が高くなり、高倍率延伸によるローラー表面と合成繊維の各単糸との摺動が円滑に行われなくなって、単糸切れが生じやすくなる。
エステル化合物(A)の粘度(25℃)は、エステル化合物(B)による高摩擦を抑え、製糸時と製織時の潤滑性と収束性を向上させる点から、40~90mm2/sが好ましく、50~80mm2/sがより好ましく、60~70mm2/sがさらに好ましい。 The molecular weight of the ester compound (A) is 200 to 1300. As a result, it becomes possible to stabilize the yarn-making property and perform high-strength drawing, and to obtain a high-strength synthetic fiber. The molecular weight is preferably 400 to 1300, more preferably 600 to 1000.
When the molecular weight is less than 200, the extreme pressure property of the synthetic fiber to which the treatment agent is applied is low, and an oil film is cut between the yarn and the drawing roller during drawing, and the friction between the yarn and the drawing roller increases. As a result, the spinning property is lowered and the synthetic fiber cannot be stretched at a high magnification, and a high-strength synthetic fiber cannot be obtained. On the other hand, if the molecular weight exceeds 1300, the friction between the yarn and the drawing roller, that is, the friction against the metal becomes high, and the sliding between the roller surface and each single yarn of the synthetic fiber due to high magnification drawing cannot be performed smoothly. As a result, single yarn breakage is likely to occur.
The viscosity (25 ° C.) of the ester compound (A) is preferably 40 to 90 mm 2 / s from the viewpoint of suppressing high friction due to the ester compound (B) and improving lubricity and convergence during yarn production and weaving. 50 to 80 mm 2 / s is more preferable, and 60 to 70 mm 2 / s is more preferable.
また、エステル化合物は、精練性の点から、分子内に不飽和結合を有することが好ましい。不飽和結合の数については特に限定はないが、同一アルキル鎖中に2つ以上有する場合、酸価により劣化が進行して処理剤が増粘して精練性が損なわれるため、同一アルキル鎖中に1つが好ましい。 The ester compound (A) is preferably one having three or more ester groups in the molecule from the viewpoint of suppressing high friction due to the ester compound (B) and improving lubricity and convergence during yarn production and weaving. Three is more preferable.
Moreover, it is preferable that an ester compound has an unsaturated bond in a molecule | numerator from the point of scourability. The number of unsaturated bonds is not particularly limited, but if there are two or more unsaturated bonds in the same alkyl chain, the deterioration proceeds due to the acid value and the treating agent is thickened to impair the scouring properties. One is preferred.
本発明のエステル化合物(B)は、芳香族カルボン酸とアルコールとのエステル(B1)および芳香族アルコールとカルボン酸とのエステル(B2)から選ばれる少なくとも1種の芳香環を有するエステルであり、かつ分子量が200~2600である。エステル化合物(B)は、分子内に少なくとも1つの芳香環を有するものであり、また分子内にポリオキシアルキレン基を有しない化合物である。エステル化合物(B)は、1種または2種以上を使用してもよい。エステル化合物(B)は、エアバック基布の滑脱抵抗を高める成分であり、エアバック基布製織後の精練またはウォータージェットルーム製織時の水圧で除去され難い性質(以下、残留性ということがある)が必要である。このようなエステル化合物(B)を前述のエステル化合物(A)と併用することにより、製糸時と製織時の潤滑性と収束性を向上させ、さらにエアバック基布の滑脱抵抗を高めることができる。 [Ester compound (B)]
The ester compound (B) of the present invention is an ester having at least one aromatic ring selected from an ester (B1) of an aromatic carboxylic acid and an alcohol and an ester (B2) of an aromatic alcohol and a carboxylic acid, The molecular weight is 200-2600. The ester compound (B) is a compound having at least one aromatic ring in the molecule and having no polyoxyalkylene group in the molecule. 1 type (s) or 2 or more types may be used for an ester compound (B). The ester compound (B) is a component that enhances the slip resistance of the airbag base fabric, and is not easily removed by water pressure during scouring or water jet loom weaving after weaving the airbag base fabric (hereinafter sometimes referred to as persistence). )is required. By using such an ester compound (B) in combination with the above-described ester compound (A), it is possible to improve lubricity and convergence at the time of yarn production and weaving, and to further increase the slip resistance of the airbag base fabric. .
芳香族カルボン酸としては、安息香酸、トルイル酸、ナフトエ酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸、没食子酸、メリト酸、ケイ皮酸、トリメリット酸等が挙げられる。これらの中でも、トリメリット酸、フタル酸、イソフタル酸、テレフタル酸が好ましく、トリメリット酸がさらに好ましい。 The aromatic carboxylic acid constituting the ester (B1) may be a monocarboxylic acid or a polyvalent carboxylic acid. You may use 1 type, or 2 or more types. Aromatic polyvalent carboxylic acids are preferred and aromatic trivalent carboxylic acids are more preferred from the standpoint of slip-off resistance and yarn production.
Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, melittic acid, cinnamic acid, trimellitic acid and the like. Among these, trimellitic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and trimellitic acid is more preferable.
脂肪族1価アルコールは、残留性の点から、飽和であることが好ましい。脂肪族1価アルコールは、直鎖状であっても分岐を有していてもよい。脂肪族1価アルコールの炭素数は、製糸性と残留性の両立から、8~24が好ましく、12~24がより好ましく、18~24がさらに好ましい。 The alcohol constituting the ester (B1) may be a monohydric alcohol or a polyhydric alcohol. Moreover, any of aliphatic alcohol, alicyclic alcohol, and aromatic alcohol may be sufficient. You may use 1 type, or 2 or more types. Among these, monohydric alcohols are preferable, and aliphatic monohydric alcohols are more preferable.
The aliphatic monohydric alcohol is preferably saturated from the viewpoint of persistence. The aliphatic monohydric alcohol may be linear or branched. The number of carbon atoms of the aliphatic monohydric alcohol is preferably 8 to 24, more preferably 12 to 24, and still more preferably 18 to 24, from the standpoint of both the spinning property and the persistence.
多価アルコールとしては、エステル(A1)で説明した脂肪族多価アルコールやエステル(B2)で説明する芳香族多価アルコール等を挙げることができる。 Monohydric alcohols include alkylbenzene alcohol, dialkylbenzene alcohol, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol , Elidyl alcohol, bacenyl alcohol, gadrel alcohol, argidinyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetradocosanyl Alcohol, nerbonyl alcohol, serotinyl alcohol, montanyl alcohol, meli Alkenyl alcohol. Among these, alkylbenzene alcohol, dialkylbenzene alcohol, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, Erai Zyl alcohol, bacenyl alcohol, gadryl alcohol, argidinyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetradocosanyl alcohol, Nerbonyl alcohol is preferred, alkylbenzene alcohol, dialkylbenzene Lucol, lauryl alcohol, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, argidinyl alcohol, isoicosanyl alcohol, behenyl alcohol, isodocosanyl alcohol, lignoserinyl alcohol, isotetradocosanyl alcohol Are more preferable, and alkylbenzene alcohol, dialkylbenzene alcohol, stearyl alcohol, isostearyl alcohol, argidinyl alcohol, isoicosanyl alcohol, behenyl alcohol, isodocosanyl alcohol, lignocerinyl alcohol, and isotetradocosanyl alcohol are more preferable.
Examples of the polyhydric alcohol include the aliphatic polyhydric alcohol described in the ester (A1) and the aromatic polyhydric alcohol described in the ester (B2).
芳香族アルコールとしては、アルキルベンゼンアルコール等の芳香族1価アルコール、ジアルキルベンゼンアルコール、ビスフェノールA、ビスフェノールZ、1,3,5-トリヒドロキシメチルベンゼン等の芳香族多価アルコール等が挙げられる。これらの中でもビスフェノールA、ビスフェノールZ、1,3,5-トリヒドロキシメチルベンゼンが好ましく、1,3,5-トリヒドロキシメチルベンゼンがより好ましい。 The aromatic alcohol which comprises ester (B2) may use 1 type (s) or 2 or more types. Aromatic polyhydric alcohols are preferred and aromatic trihydric alcohols are more preferred from the standpoint of slip-off resistance and yarn production.
Examples of the aromatic alcohol include aromatic monohydric alcohols such as alkylbenzene alcohols, aromatic polyhydric alcohols such as dialkylbenzene alcohols, bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene. Among these, bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene are preferable, and 1,3,5-trihydroxymethylbenzene is more preferable.
多価のカルボン酸としては、エステル(A2)で説明した脂肪族多価カルボン酸や、エステル(B1)で説明した芳香族多価カルボン酸等を挙げることができる。 Monovalent carboxylic acids include alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristic acid, Pentadecylic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, Examples include eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetradocosanoic acid, nervonic acid, serotic acid, montanic acid, melicic acid and the like. Among these, alkyl benzene carboxylic acid, dialkyl benzene carboxylic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, pentadecylic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetradoco Sanic acid, nervonic acid and the like are preferable, and alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, isocetylic acid, margaric acid, stearic acid, iso Tealic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, behenic acid, isodocosanoic acid, lignoceric acid, isotetradocosanoic acid, etc. are more preferred, alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, stearic acid, isostearic acid, tuberculosic More preferred are stearic acid, arachidic acid, isoicosanoic acid, behenic acid, isodocosanoic acid, lignoceric acid, isotetradocosanoic acid and the like.
Examples of the polyvalent carboxylic acid include the aliphatic polyvalent carboxylic acid described in the ester (A2) and the aromatic polyvalent carboxylic acid described in the ester (B1).
分子量が200未満になると、完成したエアバッグ用基布を解体した時の経糸、緯糸各々の糸-糸間静摩擦力が低くなり、基布滑脱抵抗力(エッジコームレジスタンス)が小さくなる。また、分子量が2600を越えると、糸条と延伸ローラー等との摩擦、すなわち対金属摩擦が高くなり、高倍率延伸によるローラー表面と合成繊維の各単糸との摺動が円滑に行われなくなって、単糸切れが生じやすくなる。 The molecular weight of the ester compound (B) is 200-2600. This makes it possible to achieve both the stability of the yarn production and the high resistance to slipping out of the fabric (edge comb resistance), and to obtain desirable characteristics as a synthetic fiber for an airbag. The molecular weight is preferably 400 to 2000, and more preferably 600 to 1500.
When the molecular weight is less than 200, the static friction force between the warp and the weft of each warp and weft when the completed airbag base fabric is disassembled becomes low, and the base fabric sliding resistance (edge comb resistance) becomes small. If the molecular weight exceeds 2600, the friction between the yarn and the drawing roller, that is, the friction against the metal becomes high, and the sliding between the roller surface and each single yarn of the synthetic fiber by high magnification drawing cannot be performed smoothly. As a result, single yarn breakage is likely to occur.
本発明のエアバッグ用合成繊維処理剤は、必須成分であるエステル化合物(A)とエステル化合物(B)に加えて、チオジプロピオン酸と脂肪族アルコールとのジエステル化合物(C)、含芳香環シリコーン化合物(D)、後述の非イオン界面活性剤(E)および後述の非イオン界面活性剤(F)から選ばれる少なくとも1種を含有することが好ましい。 [Other ingredients]
The synthetic fiber treating agent for an airbag of the present invention includes an ester compound (A) and an ester compound (B) which are essential components, a diester compound (C) of thiodipropionic acid and an aliphatic alcohol, and an aromatic ring. It is preferable to contain at least 1 sort (s) chosen from a silicone compound (D), the below-mentioned nonionic surfactant (E), and the below-mentioned nonionic surfactant (F).
含芳香環シリコーン化合物(D)としては、フェニル変性ジメチルポリシロキサン、ジフェニルポリシロキサン等が用いられる。製糸性と滑脱抵抗の両立から、粘度(25℃)は200~600mm2/sが好ましく、300~500mm2/sがより好ましく、350~450mm2/sがさらに好ましい。ポリシロキサン鎖を構成するメチル基(M)と芳香環を有する基(P)のモル比(M/P)は、10以下が好ましく、5以下がより好ましく、2以下がさらに好ましく、0が特に好ましい。 The aromatic ring-containing silicone compound (D) is a component that increases sliding resistance like the ester compound (B), and is more likely to remain on the airbag base fabric than the ester compound (B). By using the aromatic ring-containing silicone compound (D) in combination, the slip resistance can be further increased. The aromatic ring-containing silicone compound (D) is a group having an aromatic ring such as a phenyl group or a naphthalene group at at least one of both ends, one end, side chain, and both side ends of a polysiloxane such as dimethylpolysiloxane. This refers to a modified silicone modified with One or more aromatic ring-containing silicone compounds (D) may be used.
As the aromatic ring-containing silicone compound (D), phenyl-modified dimethylpolysiloxane, diphenylpolysiloxane and the like are used. From both the spinnability and slippage resistance, viscosity (25 ° C.) is preferably 200 ~ 600mm 2 / s, more preferably 300 ~ 500mm 2 / s, more preferably 350 ~ 450mm 2 / s. The molar ratio (M / P) of the methyl group (M) constituting the polysiloxane chain and the group (P) having an aromatic ring is preferably 10 or less, more preferably 5 or less, further preferably 2 or less, particularly preferably 0. preferable.
ポリオキシアルキレン脂肪族アルコールエーテルとしては、例えば、オクチルアルコール、2-エチルヘキシルアルコール、デシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコールなどの脂肪族アルコールのアルキレンオキサイド付加物が挙げられる。これらの中でも、ラウリルアルコール、トリデシルアルコールのアルキレンオキサイド付加物が好ましく、トリデシルアルコールのアルキレンオキサイド付加物がさらに好ましい。
アルキレンオキサイドの付加モル数としては、2~30モルが好ましく、4~20モルがより好ましく、6~15モルがさらに好ましい。 The polyoxyalkylene aliphatic alcohol ether (E1) is obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to an aliphatic monohydric alcohol. It plays a role of giving uniform adhesion to the raw yarn of the treatment agent. In order to improve the uniform adhesion of the essential component ester compound (A), ester compound (B) (including diester compound (C) and aromatic ring-containing silicone compound (D) in some cases) to the raw yarn surface, The group monohydric alcohol preferably has 11 to 15 carbon atoms. Moreover, what has a branched chain is preferable.
Examples of the polyoxyalkylene aliphatic alcohol ether include alkylene oxides of aliphatic alcohols such as octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. Addenda may be mentioned. Among these, an alkylene oxide adduct of lauryl alcohol and tridecyl alcohol is preferable, and an alkylene oxide adduct of tridecyl alcohol is more preferable.
The number of moles of alkylene oxide added is preferably 2 to 30 moles, more preferably 4 to 20 moles, and even more preferably 6 to 15 moles.
非イオン界面活性剤(E2)に用いられる1価の脂肪族カルボン酸としては、飽和であっても不飽和であってもよい。例えば、ラウリン酸、ミリスチン酸、ミリストレイン酸、ペンタデシル酸、パルミチン酸、パルミトレイン酸、イソセチル酸、マルガリン酸、ステアリン酸、イソステアリン酸、オレイン酸、エライジン酸、バクセン酸、リノール酸、リノレン酸、ツベルクロステアリン酸、アラキジン酸、イソイコサン酸、ガドレイン酸、エイコセン酸、ベヘン酸、イソドコサン酸、エルカ酸、リグノセリン酸、イソテトラドコサン酸、ネルボン酸等が挙げられる。 Examples of the polyhydric alcohol used in the nonionic surfactant (E2) include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose.
The monovalent aliphatic carboxylic acid used for the nonionic surfactant (E2) may be saturated or unsaturated. For example, lauric acid, myristic acid, myristoleic acid, pentadecylic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculosic Examples include stearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetradocosanoic acid, and nervonic acid.
アルキレンオキサイドの付加モル数としては、5~35が好ましく、10~30がより好ましく、15~25がさらに好ましい。
非イオン界面活性剤(E2)の分子量は、1000~3000が好ましく、1200~2800がより好ましく、1500~2500がさらに好ましい。 Among these, as polyhydric alcohol, glycerin, trimethylolpropane, pentaerythritol, erythritol, sorbitan, and monovalent aliphatic carboxylic acid as palmitic acid, palmitoleic acid, isocetylic acid, margaric acid, stearic acid, isostearic acid Oleic acid, elaidic acid, and vaccenic acid are preferable, and as the polyhydric alcohol, glycerin, sorbitan, and monovalent aliphatic carboxylic acid are more preferably stearic acid, isostearic acid, oleic acid, elaidic acid, and vaccenic acid.
The number of added moles of alkylene oxide is preferably 5 to 35, more preferably 10 to 30, and still more preferably 15 to 25.
The molecular weight of the nonionic surfactant (E2) is preferably from 1000 to 3000, more preferably from 1200 to 2800, still more preferably from 1500 to 2500.
非イオン界面活性剤(E3)に用いられる脂肪族ヒドロキシ1価カルボン酸としては、リシノール酸、リシネライジン酸、ヒドロキシステアリン酸、セレブロン酸、ヒドロキシリグノセリン酸等が挙げられる。
これらの中でも、多価アルコールとしては、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ソルビタン、脂肪族ヒドロキシ1価カルボン酸としては、リシノール酸、リシネライジン酸、セレブロン酸、が好ましく、多価アルコールとしては、グリセリン、ソルビタン、脂肪族ヒドロキシ1価カルボン酸としては、リシノール酸がさらに好ましい。
アルキレンオキサイドの付加モル数としては、1~50が好ましく、5~35がより好ましく、10~30がさらに好ましく、15~25が特に好ましい。
非イオン界面活性剤(E3)の分子量は、1000~3000が好ましく、1200~2800がより好ましく、1500~2500がさらに好ましい。 Examples of the polyhydric alcohol used in the nonionic surfactant (E3) include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose.
Examples of the aliphatic hydroxy monovalent carboxylic acid used for the nonionic surfactant (E3) include ricinoleic acid, ricineraidic acid, hydroxystearic acid, cerebuloic acid, and hydroxylignoceric acid.
Among these, glycerin, trimethylolpropane, pentaerythritol, erythritol, sorbitan, and aliphatic hydroxy monovalent carboxylic acid are preferable as polyhydric alcohol, and ricinoleic acid, ricinaleic acid, and cerebronic acid are preferable. As glycerin, sorbitan, and aliphatic hydroxy monovalent carboxylic acid, ricinoleic acid is more preferable.
The number of moles of alkylene oxide added is preferably 1 to 50, more preferably 5 to 35, still more preferably 10 to 30, and particularly preferably 15 to 25.
The molecular weight of the nonionic surfactant (E3) is preferably from 1000 to 3000, more preferably from 1200 to 2800, still more preferably from 1500 to 2500.
また、非イオン界面活性剤(F)は、分子中のアルキレンオキサイド全体に対してプロピレンオキサイドを50モル%以上含有することが好ましく、65モル%以上がより好ましく、80モル%以上がさらに好ましい。プロピレンオキサイドの含有量が50モル%未満の場合、完成したエアバッグ用基布を解体した時の経糸、緯糸各々の糸・糸間静摩擦力が小さくなり、基布滑脱抵抗力(エッジコームレジスタンス)が小さくなるため、好ましくない。 The number of moles of alkylene oxide added is preferably 60 to 200, more preferably 80 to 180, and still more preferably 100 to 160.
Moreover, it is preferable that a nonionic surfactant (F) contains 50 mol% or more of propylene oxide with respect to the whole alkylene oxide in a molecule | numerator, 65 mol% or more is more preferable, and 80 mol% or more is further more preferable. When the propylene oxide content is less than 50 mol%, the static friction force between the warp and weft yarns when the finished airbag base fabric is disassembled is reduced, and the fabric slip resistance (edge comb resistance) Is not preferable because it becomes smaller.
エアバッグ用合成繊維処理剤の不揮発分に占める前記エステル化合物(A)の重量割合は、30~80重量%が好ましく、45~80重量%がより好ましく、60~80重量%がさらに好ましい。30重量%未満の場合、糸条と延伸ローラーなどとの摩擦、すなわち対金属摩擦が高くなって、高倍率延伸できず、高強度の合成繊維が得られなくなる場合がある。80重量%超の場合、エアバック基布の滑脱抵抗が低下する場合がある。
処理剤の不揮発分に占める前記エステル化合物(B)の重量割合は、2~30重量%が好ましく、5~20重量%がより好ましく、10~20重量%がさらに好ましい。2重量%未満の場合、エアバック用基布の滑脱抵抗が低下する場合がある。30重量%超の場合、糸条と延伸ローラーなどとの摩擦、すなわち対金属摩擦が高くなって、高倍率延伸できず、高強度の合成繊維が得られなくなる場合がある。
なお、本発明における不揮発分とは、処理剤を105℃で熱処理して溶媒等を除去し、恒量に達した時の絶乾成分をいう。 [Synthetic fiber treatment agent for airbags]
The weight ratio of the ester compound (A) in the nonvolatile content of the synthetic fiber treating agent for airbag is preferably 30 to 80% by weight, more preferably 45 to 80% by weight, and further preferably 60 to 80% by weight. If it is less than 30% by weight, the friction between the yarn and the drawing roller, that is, the friction against the metal becomes high, and high-strength synthetic fibers may not be obtained because high-stretching cannot be performed. If it exceeds 80% by weight, the sliding resistance of the airbag base fabric may be lowered.
The weight ratio of the ester compound (B) in the non-volatile content of the treating agent is preferably 2 to 30% by weight, more preferably 5 to 20% by weight, and even more preferably 10 to 20% by weight. If it is less than 2% by weight, the slip resistance of the airbag fabric may be lowered. If it exceeds 30% by weight, the friction between the yarn and the drawing roller, that is, the friction against the metal becomes high, and high-strength synthetic fibers may not be obtained because high-stretching cannot be performed.
The non-volatile content in the present invention refers to an absolutely dry component when the treatment agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
これらの中でも、均一付着性の理由から、前述の不揮発分を低粘度鉱物油で希釈して給油装置に適切な任意の粘度へ調整したものが好ましい。希釈する鉱物油の粘度(25℃)としては、1~3mm2/sが好ましい。また、鉱物油で希釈したときの不揮発分の濃度は、30~99重量%が好ましい。 The synthetic fiber treatment agent for airbags of the present invention may be composed of the above-mentioned components consisting only of non-volatile components, or may be prepared by diluting the above non-volatile components with a low-viscosity mineral oil, and emulsifies the non-volatile components in water. It may be a water-based emulsion.
Among these, for the reason of uniform adhesion, those obtained by diluting the aforementioned non-volatile content with a low-viscosity mineral oil and adjusting to an arbitrary viscosity suitable for the oil supply device are preferable. The viscosity (25 ° C.) of the mineral oil to be diluted is preferably 1 to 3 mm 2 / s. The concentration of the non-volatile content when diluted with mineral oil is preferably 30 to 99% by weight.
本発明のエアバック用合成繊維フィラメントは、(原料)合成繊維フィラメントに対して、本発明のエアバック用合成繊維処理剤が付与されたものである。エアバック用合成繊維処理剤の付与量は、(原料)合成繊維フィラメントに対して、0.01~2重量%が好ましく、0.5~1.5重量%がより好ましく、0.75~1.25重量%がさらに好ましい。
(原料)合成繊維フィラメントに本発明のエアバック用合成繊維処理剤を付与する方法としては、特に限定はなく、公知の方法を採用することできる。通常、合成繊維フィラメントの紡糸工程または延伸工程で付与され、(原料)合成繊維フィラメントに対して、不揮発分のみからなる処理剤、不揮発分を低粘度鉱物油で希釈した処理剤、又は水中に不揮発分を乳化した水系エマルジョン処理剤をジェットノズル給油装置やローラー給油装置を用いて付与する方法等が挙げられる。 [Synthetic fiber filament for airbags]
The synthetic fiber filament for airbag of the present invention is obtained by adding the synthetic fiber treating agent for airbag of the present invention to the (raw material) synthetic fiber filament. The amount of the synthetic fiber treating agent for airbag applied is preferably 0.01 to 2% by weight, more preferably 0.5 to 1.5% by weight, and more preferably 0.75 to 1% with respect to the (raw material) synthetic fiber filament. More preferred is .25% by weight.
(Raw material) The method for applying the synthetic fiber treating agent for airbag of the present invention to the synthetic fiber filament is not particularly limited, and a known method can be adopted. Usually given in the spinning process or drawing process of synthetic fiber filaments, (raw material) treatment agent consisting only of non-volatile content, synthetic agent diluted with low-viscosity mineral oil, or non-volatile in water Examples thereof include a method of applying a water-based emulsion treatment agent emulsified with a jet nozzle oiling device or a roller oiling device.
本発明のエアバッグ用基布は、本発明のエアバッグ用合成繊維処理剤が付与されたエアバッグ用合成繊維フィラメントを製織したものである。本発明のエアバッグ用基布を製造する方法は、本発明のエアバッグ用合成繊維処理剤が付与されたエアバッグ用合成繊維フィラメントを製織する製織工程を含むものである。製織工程としては、特に限定はなく、公知の工程・方法を採用できる。例えば、ウォータージェットルームによる製織、レピア製織、エアジェットルーム、スルーザー織機による製織等が挙げられる。 [Base fabric for airbags]
The airbag fabric of the present invention is made by weaving synthetic fiber filaments for airbags to which the synthetic fiber treatment agent for airbags of the present invention is applied. The method for producing the airbag fabric of the present invention includes a weaving step of weaving the synthetic fiber filament for airbag to which the synthetic fiber treatment agent for airbag of the present invention is applied. The weaving process is not particularly limited, and a known process / method can be employed. For example, weaving with a water jet loom, rapier weaving, air jet loom, weaving with a slewer loom and the like can be mentioned.
ウォータージェットルームによって製織するエアバッグ用基布の製造方法では、製織時に水圧により処理剤の大部分が除去されるので、精練工程は省かれる。 In the manufacturing method of airbag fabrics woven by rapier weaving, air jet loom, and slewer loom, a scouring process is usually required to remove spinning oil and weaving oil after weaving synthetic fiber filaments for airbag . There is no limitation in particular as a scouring process, A well-known method is employable. For example, it is carried out by impregnating in a hot water bath containing a scouring agent at 20 to 100 ° C., squeezing with mangle, and then drying at 80 to 150 ° C.
In the method for manufacturing an airbag base fabric woven by a water jet loom, most of the treatment agent is removed by water pressure at the time of weaving, so the scouring process is omitted.
下記表1または表2に記載の成分を混合撹拌して、各実施例・比較例のエアバッグ用合成繊維処理剤の不揮発分を調製した。表1における処理剤成分の各記号の詳細は、表3に示した通りである。これらの処理剤不揮発分と炭素数13のパラフィンオイルを1:1の重量比で混合してエアバッグ用合成繊維処理剤を調製した。
次に、470デシテックス、68フィラメントの丸断面ナイロン6,6フィラメントを溶融紡糸し、調製した処理剤をジェットノズル給油法により、得られた糸条に対して1重量%となるように付与した後、巻き取ることなく210℃で延伸倍率5倍にホットローラーを用いて多段熱延伸して巻き取り、エアバッグ用合成繊維フィラメントを得た。延伸性の評価は下記の方法で行った。その結果を表4及び5に示す。 (Examples 1 to 11, Comparative Examples 1 to 12)
The components listed in Table 1 or 2 below were mixed and stirred to prepare the non-volatile content of the synthetic fiber treating agent for airbags of each Example and Comparative Example. Details of each symbol of the treating agent component in Table 1 are as shown in Table 3. These treatment agent non-volatile components and C13 paraffin oil were mixed at a weight ratio of 1: 1 to prepare a synthetic fiber treatment agent for airbags.
Next, 470 decitex, 68 filament round section nylon 6,6 filament was melt-spun, and the prepared treating agent was applied to the obtained yarn at 1% by weight by the jet nozzle oiling method. Without being wound up, it was wound at 210 ° C. using a hot roller at a draw ratio of 5 times to obtain a synthetic fiber filament for airbag. The stretchability was evaluated by the following method. The results are shown in Tables 4 and 5.
紡糸―延伸後、3000m/minで巻き取った10kgのボビン表面を観察し、長さ1mm以上の毛羽の数をもって延伸性とした。
○:毛羽数0以上10未満
△:毛羽数10以上20未満
×:毛羽数20以上 [Extendability during spinning]
After spinning and drawing, the surface of a 10 kg bobbin wound up at 3000 m / min was observed, and the number of fluffs having a length of 1 mm or more was regarded as drawability.
○: Number of fluff 0 or more and less than 10 Δ: Number of fluff 10 or more and less than 20 ×: Number of fluff 20 or more
糸・糸間静摩擦力はエアバック基布を解体して糸(経糸と緯糸)を取り出し、図1のような測定装置を用い、荷重T1(g)の張力下で、撚り数3回、引張り速度3cm/minで引っ張った時の張力T2(g)を測定し、T2/T1の比を糸・糸間静摩擦力とした。T2/T1の数値が大きいほど糸・糸間静摩擦力が高く、数値が小さいほど糸・糸間静摩擦力が低い。エアバック基布の滑脱抵抗と破断強力を両立するためには、T2/T1が2.75~3.50であることが好ましい。 [Thread-to-thread static friction force]
The static friction force between yarns is disassembled from the airbag base fabric and the yarns (warp and weft) are taken out. Using the measuring device as shown in Fig. 1, the yarn is pulled three times under the load T1 (g). The tension T2 (g) when pulled at a speed of 3 cm / min was measured, and the ratio of T2 / T1 was defined as the yarn-to-thread static friction force. The larger the T2 / T1 value, the higher the yarn-to-thread static friction force, and the lower the value, the lower the yarn-to-thread static friction force. In order to achieve both sliding resistance and breaking strength of the airbag base fabric, T2 / T1 is preferably 2.75 to 3.50.
基布試料約300gを採取し、105℃の熱風乾燥機内に90分放置した後の質量(S)を電子天秤で測定し、大型ソックスレー抽出器に入れた。次にシクロヘキサン約2リットルを加えて、約4時間加熱環流した後、シクロヘキサンを回収し、抽出分の絶乾重量(M)を測定し、次式から残留油分量を求めた。 残留油分量(%)=M÷S×100 [Residual oil content of base fabric]
About 300 g of a base fabric sample was collected, and the mass (S) after being left in a hot air dryer at 105 ° C. for 90 minutes was measured with an electronic balance and placed in a large Soxhlet extractor. Next, about 2 liters of cyclohexane was added and heated to reflux for about 4 hours, then cyclohexane was recovered, the absolute dry weight (M) of the extract was measured, and the residual oil content was determined from the following formula. Residual oil content (%) = M ÷ S × 100
抽出された残留油分を溶媒(クロロフォルム90重量部とジエチルエーテル10重量部の混合液)に溶解させ、シリカゲルカラムクロマトグラフィーを通過させた後に溶媒を回収して、エステル化合物(A)とエステル化合物(B)の混合物(チオジプロピオン酸と脂肪族アルコールとのジエステル化合物(C)、含芳香環シリコーン化合物(D)を含む場合はそれらを含む)の重量(X)を得た。次に、この混合物中に含まれるエステル化合物(B)(含芳香環シリコーン化合物(D)を含む場合はそれらの和)の含有率(Y;重量%)をガスクロマトグラフィー/質量分析法により決定し、エステル化合物(B)(含芳香環シリコーン化合物(D)を含む場合はそれらの和)の残留量(%)を次式から求めた。
エステル化合物(B)の残留量(%)=X×Y÷S [Residual amount of ester compound (B)]
The extracted residual oil is dissolved in a solvent (mixed solution of 90 parts by weight of chloroform and 10 parts by weight of diethyl ether), and after passing through silica gel column chromatography, the solvent is recovered and the ester compound (A) and the ester compound ( The weight (X) of the mixture of B) (including a diester compound (C) of thiodipropionic acid and an aliphatic alcohol and an aromatic ring-containing silicone compound (D), if included) was obtained. Next, the content (Y;% by weight) of the ester compound (B) contained in this mixture (or the sum of those containing an aromatic ring-containing silicone compound (D)) is determined by gas chromatography / mass spectrometry. Then, the residual amount (%) of the ester compound (B) (or the sum when the aromatic ring-containing silicone compound (D) is included) was determined from the following formula.
Residual amount of ester compound (B) (%) = X × Y ÷ S
試験法:JIS L1096に基づき、織物幅は3cm、掴み具間距離15cm、引張り速度200mm/minで引っ張った時の破断強力を測定した。
◎:測定値が2250(N)以上
○:測定値が2000(N)以上
△:測定値が1500(N)以上、2000(N)未満
×:測定値が1500(N)未満 [Base fabric breaking strength]
Test method: Based on JIS L1096, the breaking strength was measured when the fabric width was 3 cm, the distance between grips was 15 cm, and the tensile speed was 200 mm / min.
A: The measured value is 2250 (N) or more. ○: The measured value is 2000 (N) or more. Δ: The measured value is 1500 (N) or more and less than 2000 (N). X: The measured value is less than 1500 (N).
試験法::ASTM D6479に基づき、エアバッグ用基布から幅5cm、長さ30cmの大きさのテストピースを切り出し、引張り速度200mm/minで引っ張った時の経糸及び緯糸の滑脱抵抗力を測定した。基布滑脱抵抗力が大きいほど、エアバッグにしたときの気密性が優れていることになる。
◎:測定値が450(N)以上
○:測定値が400(N)以上
△:測定値が300(N)以上、400(N)未満
×:測定値が300(N)未満 [Base fabric slip resistance (edge comb resistance)]
Test method: Based on ASTM D6479, a test piece having a width of 5 cm and a length of 30 cm was cut out from an airbag base fabric, and the slip resistance of warp and weft was measured when pulled at a pulling speed of 200 mm / min. . The greater the resistance to slipping off the base fabric, the better the airtightness when the airbag is made.
◎: Measurement value is 450 (N) or more ○: Measurement value is 400 (N) or more △: Measurement value is 300 (N) or more and less than 400 (N) ×: Measurement value is less than 300 (N)
一方、比較例1~12(エステル化合物(A)及びエステル化合物(B)を必須に含有しない処理剤や、エステル化合物(A)とエステル化合物(B)との重量比(A/B)が1/1~40/1を満足しない処理剤を用いた場合)では、実施例と比べ、製糸時の延伸性が劣るものがあり、また糸・糸間静摩擦力が低く、基布破断強力及び基布滑脱抵抗力ともに劣っている。 As can be seen from Tables 4 and 5, the synthetic fiber filaments provided with the synthetic fiber treatment agents for airbags of Examples 1 to 11 have good stretchability during yarn production. As can be seen from Tables 4 to 7, the air bag base fabrics of Examples 1 to 11 are excellent in the static friction between yarns and yarns in both water jet loom weaving (a) and rapier loom weaving (b). Both fabric breaking strength and base fabric slip resistance are excellent. Therefore, it was possible to achieve both the base fabric breaking strength and the base fabric slip resistance.
On the other hand, Comparative Examples 1 to 12 (treatment agent that does not essentially contain the ester compound (A) and the ester compound (B), and the weight ratio (A / B) of the ester compound (A) to the ester compound (B) is 1 In the case of using a treatment agent that does not satisfy / 1 to 40/1), the stretchability during yarn production is inferior to that of the examples, and the static frictional force between the yarn and yarn is low, and the base fabric breaking strength and base Both cloth slipping resistance is inferior.
Claims (10)
- 脂肪族多価アルコールと脂肪酸とのエステルおよび脂肪族1価アルコールと脂肪族多価カルボン酸とのエステルから選ばれる少なくとも1種の多価エステルであり、かつ分子量が200~1300であるエステル化合物(A)と、
芳香族カルボン酸とアルコールとのエステルおよび芳香族アルコールとカルボン酸とのエステルから選ばれる少なくとも1種の芳香環を有するエステルであり、かつ分子量が200~2600であるエステル化合物(B)とを必須に含有し、
前記エステル化合物(A)と前記エステル化合物(B)の重量比(A/B)が1/1~40/1である、エアバック用合成繊維処理剤。 An ester compound having at least one polyvalent ester selected from an ester of an aliphatic polyhydric alcohol and a fatty acid and an ester of an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid, and having a molecular weight of 200 to 1300 ( A) and
An ester compound (B) having at least one aromatic ring selected from esters of aromatic carboxylic acids and alcohols and esters of aromatic alcohols and carboxylic acids and having a molecular weight of 200 to 2600 is essential. Contained in
A synthetic fiber treating agent for airbag, wherein the weight ratio (A / B) of the ester compound (A) to the ester compound (B) is 1/1 to 40/1. - 前記エステル化合物(A)が、不飽和結合を有する化合物である、請求項1に記載の処理剤。 The processing agent according to claim 1, wherein the ester compound (A) is a compound having an unsaturated bond.
- 前記エステル化合物(A)が、分子内に3個以上のエステル基を有する化合物である、請求項1または2に記載の処理剤。 The treatment agent according to claim 1 or 2, wherein the ester compound (A) is a compound having 3 or more ester groups in the molecule.
- 前記エステル化合物(A)が、3価以上の脂肪族多価アルコールと炭素数8~24の不飽和脂肪酸とのエステルである、請求項1~3のいずれかに記載の処理剤。 The treating agent according to any one of claims 1 to 3, wherein the ester compound (A) is an ester of a trihydric or higher aliphatic polyhydric alcohol and an unsaturated fatty acid having 8 to 24 carbon atoms.
- 前記エステル化合物(B)が、分子内に2個以上のエステル基を有する化合物である、請求項1~4のいずれかに記載の処理剤。 The treatment agent according to any one of claims 1 to 4, wherein the ester compound (B) is a compound having two or more ester groups in the molecule.
- 前記エステル化合物(B)が、芳香族カルボン酸と炭素数8~24の脂肪族アルコールとのエステルである、請求項1~5のいずれかに記載の処理剤。 The treatment agent according to any one of claims 1 to 5, wherein the ester compound (B) is an ester of an aromatic carboxylic acid and an aliphatic alcohol having 8 to 24 carbon atoms.
- 処理剤の不揮発分に占める、前記エステル化合物(A)の重量割合が30~80重量%であり、前記エステル化合物(B)の重量割合が2~30重量%である、請求項1~6のいずれかに記載の処理剤。 The weight ratio of the ester compound (A) in the nonvolatile content of the treating agent is 30 to 80% by weight, and the weight ratio of the ester compound (B) is 2 to 30% by weight. The processing agent in any one.
- 合成繊維フィラメントに対して、請求項1~7のいずれかに記載の処理剤が付与された、エアバック用合成繊維フィラメント。 A synthetic fiber filament for airbag, wherein the treatment agent according to any one of claims 1 to 7 is applied to the synthetic fiber filament.
- 前記合成繊維フィラメントが、ナイロン6,6、ナイロン6またはポリエステルの合成繊維フィラメントである、請求項8に記載のエアバック用合成繊維フィラメント。 The synthetic fiber filament for airbag according to claim 8, wherein the synthetic fiber filament is a synthetic fiber filament of nylon 6, 6, nylon 6, or polyester.
- 請求項8または9に記載の合成繊維フィラメントを製織した、エアバッグ用基布。 A base fabric for an air bag in which the synthetic fiber filament according to claim 8 or 9 is woven.
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WO2014123090A1 (en) * | 2013-02-06 | 2014-08-14 | 旭化成せんい株式会社 | Fabric for airbag and fabric roll |
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Also Published As
Publication number | Publication date |
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CN102947501A (en) | 2013-02-27 |
CN102947501B (en) | 2014-11-26 |
JP4940382B2 (en) | 2012-05-30 |
JPWO2011162073A1 (en) | 2013-08-19 |
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