CN101469509B - Treating agent for synthetic fiber, method for treating synthetic fiber, and synthetic fiber - Google Patents
Treating agent for synthetic fiber, method for treating synthetic fiber, and synthetic fiber Download PDFInfo
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- CN101469509B CN101469509B CN 200810188539 CN200810188539A CN101469509B CN 101469509 B CN101469509 B CN 101469509B CN 200810188539 CN200810188539 CN 200810188539 CN 200810188539 A CN200810188539 A CN 200810188539A CN 101469509 B CN101469509 B CN 101469509B
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- Prior art keywords
- acid
- oil
- compound
- synthetic fiber
- agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 104
- 229920002994 synthetic fiber Polymers 0.000 title claims abstract description 67
- 239000012209 synthetic fiber Substances 0.000 title claims abstract description 66
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- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims abstract description 106
- 150000001875 compounds Chemical class 0.000 claims abstract description 75
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- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims description 77
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- 125000001931 aliphatic group Chemical group 0.000 claims description 27
- 235000019871 vegetable fat Nutrition 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 150000003626 triacylglycerols Chemical class 0.000 claims description 23
- 239000004519 grease Substances 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 21
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 20
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- 150000002170 ethers Chemical group 0.000 claims description 5
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- RJWUMFHQJJBBOD-UHFFFAOYSA-N isooctadecane Natural products CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
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- TVMUIDYDHKXUPI-UHFFFAOYSA-J [C+4].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] Chemical compound [C+4].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] TVMUIDYDHKXUPI-UHFFFAOYSA-J 0.000 claims 3
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- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical class CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical class CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a treating agent which can inhibit generation of fine hair and tar, inhibit fuming and further prevent reduction of operability even when synthetic fibers are subjected to heat treatment under severe high-temperature conditions, a treating method using the treating agent and synthetic fibers prepared by the treating method. As the synthetic fiber treating agent, at least one selected from the following 1) and 2) is used, 1) a compound which performs random transesterification by mixing at least two kinds of oils and fats and heating in the presence of an acidic compound, and 2) a compound which performs random transesterification by mixing oils and fats, an aliphatic monocarboxylic acid, and glycerin and heating in the presence of an acidic compound.
Description
Technical field
The present invention relates to the processing method (hereinafter to be referred as processing method) and the synthetic fiber of a kind of synthetic fibre treating agent (hereinafter to be referred as finishing agent), synthetic fiber.In recent years, in the manufacturing and even manufacturing procedure of synthetic fiber, be accompanied by the propelling of high speed, synthetic fiber at high temperature heat-treated now.Especially; When the industry material that is used for tyre cord (tire cord), band bundle (belt), flexible pipe (hose), safety belt (seatbelt), air bag (airbag) etc. is used synthetic fiber, stretch in order in high speed, to carry out high magnification, just need under harsher high temperature, heat-treat; Thereby easy fine, soft fur (filoplume) and the tar of producing; And be prone to be fuming, the result causes operability to descend, and therefore suppresses the generation of above-mentioned fine, soft fur and tar; And suppress to be fuming, thereby prevent that operability from descending is very important.Therefore, need a kind ofly,, also can suppress the generation of above-mentioned fine, soft fur and tar, and suppress to be fuming, thereby prevent that operability from descending even when this finishing agent is at high temperature heat-treated these synthetic fiber attached to the finishing agent on the synthetic fiber.The synthetic fiber that the present invention relates to a kind of finishing agent that meets above-mentioned requirements, use the processing method of above-mentioned finishing agent and adopt above-mentioned processing method and make.
Background technology
In the prior art, reported the various finishing agents that can suppress fine, soft fur and tar generation etc. when at high temperature heat-treating, wherein reported and used with the example of grease as the trivalent fatty acid ester of representative.Wherein for example known: as 1) to have used the inorganic agent (for example with reference to patent documentation 1) of the alkylene oxide adduct (pay add thing) of two types of hydroxy-containing compounds, specific polyester and base oil; 2) used the inorganic agent (for example with reference to patent documentation 2) of vistanex, smooth agent (level and smooth drug) and emulsifying agent; 3) aromatic ester compound, the alkali metal salt of organic carboxyl acid and the inorganic agent (for example with reference to patent documentation 3) of special antioxidants have been used; 4) used the inorganic agent (for example with reference to patent documentation 4) etc. of polybasic esterification compound, ester compounds, secondary sulfonate (secondary ス Le ホ ネ one ト) compound, organic phosphoric acid salt compound and hindered phenol anti-oxidants with thioether group.
But, if when under the high temperature of harshness, heat-treating in recent years, above-mentioned finishing agent of the prior art in the generation that suppresses fine, soft fur and tar, suppress to be fuming, to prevent to exist aspect the operability decline obviously not enough.
Patent documentation 1: TOHKEMY 2004-353115 communique
Patent documentation 2: TOHKEMY 2006-233379 communique
Patent documentation 3: TOHKEMY 2004-292961 communique
Patent documentation 4: japanese kokai publication hei 8-120563 communique
Summary of the invention
Even problem to be solved by this invention provides a kind of when under the high temperature of harshness, heat-treating in recent years; Generation, the inhibition that also can suppress fine, soft fur and tar are fuming; And prevent the finishing agent that operability descends, the processing method and the resulting synthetic fiber of this processing method of employing of using this finishing agent also are provided.
The inventor etc. study in order to solve above-mentioned problem, and the result finds, uses the goods that contain the glyceride compounds that from the ester exchange of grease class, obtains just to meet the demands as finishing agent.
That is to say, the present invention relates to a kind of finishing agent, it is characterized in that containing following glyceride compounds.
Glyceride compounds is selected from following 1) and 2) at least a: 1) mix at least two kinds of greases; In the presence of acid compound, heat; Thereby carry out the compound of ester exchange at random; 2) compound lard, aliphatic monocarboxylic acid, glycerine heat in the presence of acid compound, thus the compound that carries out ester exchange at random.
And the invention still further relates to a kind of processing method, it is characterized in that,, adhere to the finishing agent of the invention described above of 0.1～3 quality % supplying synthetic fiber filament yarn bar in heat treatment step.
The invention still further relates to the synthetic fiber that adopt above-mentioned processing method to make in addition.
At first, the finishing agent (hereinafter to be referred as finishing agent of the present invention) that the present invention relates to is described.The glyceride compounds that is used for finishing agent of the present invention is selected from following 1) and 2) at least a.1) mixes at least two kinds of greases; In the presence of acid compound, heat, thus the compound that carries out ester exchange at random, 2) compound lard, aliphatic monocarboxylic acid, glycerine; In the presence of acid compound, heat, thus the compound that carries out ester exchange at random.
The grease that is used for ester exchange can use all animal and plant fats.For example can enumerate out: 1) coconut oil, palm kernel wet goods vegetable fat; This type vegetable fat comprises with the laurate triglycerides of aliphatic acid of the carbon number 6～20 that is main component; 2) linseed oil, olive oil, rice bran oil, sesame oil, safflower oil, soybean oil, tall oil, rapeseed oil, palm oil, sunflower oil, cottonseed oil, peanut wet goods vegetable fat; This type vegetable fat comprises with oleic acid the triglycerides of aliphatic acid of the carbon number 10～24 that is main component; 3) castor oil, rilanit special vegetable fat such as (sclerosis ヒ マ シ oil); This type vegetable fat comprises: the triglycerides of the aliphatic acid of the carbon number 14～20 of hydroxyl aliphatic acid, 4) vegetable fat such as kurrajong (ア オ イ section) seed oil, kapok oil, this type vegetable fat comprises: the triglycerides of aliphatic acid that contains the carbon number 12～20 of ring-type acid; 5) animal fats such as fish oil, whale oil, butter etc., this type animal fat comprises the triglycerides of the aliphatic acid of carbon number 4～24.Wherein, coconut oil, palm-kernel oil, palm oil, olive oil, rapeseed oil, rice bran oil, castor oil, rilanit special, the butter of the preferred carbon number 8～18 of main component of the aliphatic acid of formation grease.
As the glyceride compounds that supplies in finishing agent of the present invention; The carbon number of the preferred fatty acid glyceride compounds more than 4 of being separated by; Said aliphatic acid is the main component of aliphatic acid that is configured for the grease of ester exchange, this glyceride compounds for example: comprise carbon number 6～20 aliphatic acid (is main component with the laurate) triglycerides vegetable fat and comprise the compound that the vegetable fat of triglycerides of the aliphatic acid (is main component with oleic acid) of carbon number 10～24 carries out ester exchange; And comprise carbon number 6～20 aliphatic acid (is main component with the laurate) triglycerides vegetable fat and comprise the compound that the vegetable fat of triglycerides of the aliphatic acid (containing hydroxy fatty acid) of carbon number 14～20 carries out ester exchange.
Specifically; Preferred following compound: the grease and the grease that is selected from following B group that will be selected from the following A group; Mol ratio with the grease that is selected from A group/be selected from the grease of B group is 70/30～30/70 mixed; In the presence of acid compound, heat, thus the compound that carries out ester exchange at random.
A group: coconut oil and palm-kernel oil
B group: palm oil, olive oil, rapeseed oil and rice bran oil
More specifically, can enumerate out:, be 50/50 mixed with coconut oil/palmitic mol ratio 1) with coconut oil and palm oil; Heating in the presence of acid compound, thereby the compound that carries out ester exchange at random, 2) with coconut oil and rapeseed oil; With the mol ratio of coconut oil/rapeseed oil is 50/50 mixed, heating in the presence of acid compound, thereby the compound that carries out ester exchange at random; 3) with palm-kernel oil and palm oil, be 40/60 mixed with palm-kernel oil/palmitic mol ratio, heating in the presence of acid compound; Thereby carry out the compound of ester exchange at random, 4) with palm-kernel oil and rapeseed oil, with the mol ratio of palm-kernel oil/rapeseed oil 60/40 mixed; Heating in the presence of acid compound; Thereby carry out the compound of ester exchange at random, 5) with coconut oil, palm-kernel oil, rapeseed oil and rice bran oil, with the mol ratio of coconut oil/palm-kernel oil/rapeseed oil/rice bran oil 25/25/25/25 mixed; Heating in the presence of acid compound, thereby the compound that carries out ester exchange at random.
Supply to comprise the material that is selected from following compound: grease, aliphatic monocarboxylic acid and glycerine are mixed heating in the presence of acid compound, thereby the compound that carries out ester exchange at random in the glyceride compounds of finishing agent of the present invention.The aliphatic monocarboxylic acid that is used for ester exchange is not had particular restriction here.For example can enumerate out: caproic acid, sad, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, undecanoic acid, dodecoic acid, tridecanoic acid, different tridecanoic acid, tetradecylic acid, pentadecanoic acid, hexadecylic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, mountain Yu acid, erucic acid, 12-kamalolenic acid (Octadecenoic acid), 12-hydroxyl octadecanoid acid (Octadecanoic acid) etc.Wherein preferred: sad, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, dodecoic acid, isostearic acid, oleic acid, 12-kamalolenic acid.
Specifically, can enumerate out:, be 50/150/50 mixed with the mol ratio of coconut oil/oleic acid/glycerine 1) with coconut oil, oleic acid and glycerine; Heating in the presence of acid compound, thereby the compound that carries out ester exchange at random, 2) with coconut oil, oleic acid, isostearic acid and glycerine; With the mol ratio of coconut oil/oleic acid/isostearic acid/glycerine is 50/75/75/50 mixed, heating in the presence of acid compound, thereby the compound that carries out ester exchange at random; 3) with palm-kernel oil, oleic acid, isostearic acid and glycerine, be 50/75/75/50 mixed with the mol ratio of palm-kernel oil/oleic acid/isostearic acid/glycerine, heating in the presence of acid compound; Thereby carry out the compound of ester exchange at random, 4) with rapeseed oil, dodecoic acid and glycerine, with the mol ratio of rapeseed oil/dodecoic acid/glycerine 50/150/50 mixed; Heating in the presence of acid compound; Thereby carry out the compound of ester exchange at random, 5) with rapeseed oil, sad, capric acid, dodecoic acid and glycerine, with the mol ratio of rapeseed oil/caprylic/capric/dodecoic acid/glycerine 50/50/50/50/50 mixed; Heating in the presence of acid compound; Thereby carry out the compound of ester exchange at random, 6) with palm oil, sad, dodecoic acid and glycerine, with the mol ratio of palm oil/sad/dodecoic acid/glycerine 50/75/75/50 mixed; Heating in the presence of acid compound; Thereby carry out the compound of ester exchange at random, 7) with olive oil, capric acid, dodecoic acid and glycerine, with the mol ratio of olive oil/capric acid/dodecoic acid/glycerine 50/75/75/50 mixed; Heating in the presence of acid compound, thereby the compound etc. that carries out ester exchange at random.
For the ester exchange that obtains supplying carrying out, can use known ester-interchange method in the glyceride compounds of finishing agent of the present invention.For example can adopt, mix at least two kinds of greases, in this mixture, add acid compounds such as phosphoric acid, dewater and carry out the reaction of ester exchange while heat; Perhaps fatty acid mixed and glycerine at least a grease add acid compounds such as phosphoric acid again in this mixture, dewater and carry out the reaction of ester exchange while heat.The mixed proportion of at least two kinds of greases is arbitrarily, but when fatty acid mixed and glycerine at least a grease, preferably, with respect to 1 mole of grease, with the mixed of 3 moles of fatty acids and 1 mole of glycerin.
In the finishing agent of the present invention, the glyceride compounds of above-mentioned explanation uses as smooth agent.Finishing agent of the present invention, glyceride compounds also can be brought into play sufficient levelability (flatness) separately, but also can comprise the smooth agent except that glyceride compounds.
When the smooth agent that contains except that glyceride compounds, glyceride compounds is accounted for more than the 65 quality %, more preferably more than the 70 quality % in smooth agent.If because the smooth agent content except that glyceride compounds relatively too much the time, manifests the influence of this smooth agent easily.
Supply the smooth agent except that glyceride compounds, can give an example out: organic esterified compound, mineral oil, polyethers, organo-silicon compound etc., but preferred organic ester compounds in finishing agent of the present invention.Said organic esterified compound; Can give an example out: 1) octyl stearate, lauric acid oil thiazolinyl (oleyl) ester, oleic oil alkenyl esters, 1; Aliphatic ester compounds such as 6-hexylene glycol dicaprate, single oleic acid two laurate trihydroxymethylpropanyl esters (ト リ メ チ ロ one Le プ ロ パ Application モ ノ オ レ one ト ジ ラ ウ レ one ト), adipic acid two lauryls, thio-2 acid two oleyl esters, azelaic acid two oleyl esters, Pentaerythrityl tetraoctanoate; 2) aromatic ester compounds such as stearic acid benzyl ester, bay acid benzyl ester, bisphenol-A dilaurate, M-phthalic acid two isooctadecane esters, trioctyl trimellitate (TOTM), 3) vegetable and animals oils lipid such as coconut oil, palm oil, rapeseed oil, sunflower oil, sesame oil, soybean oil, Linseed oil, castor oil, fish oil, butter etc.
Finishing agent of the present invention also can contain emulsifying agent.Said emulsifying agent can be enumerated various non-ionic surface active agents.Wherein, For example can enumerate out: the ethers non-ionic surface active agent that 1) contains polyoxy alkylidene in polyoxy alkylidene Octyl Ether, polyoxy alkylidene lauryl ether, polyoxy alkylidene Octyl Ether laurate, polyoxy alkylidene nonylplenyl ether, polyoxy alkylidene oleate, polyoxy alkylidene dodecyl amino ethers, the polyoxy alkylidene laurylamide base ether equimolecular; 2) polyol moiety ester class non-ionic surface active agents such as mono lauric acid dehydration sorbitol ester, three oleic acid sorbitan esters, four oleic acid sorbitol esters, glyceryl monooleate, glyceryl monolaurate, two laurate, two glyceride; 3) polyoxy sub alkyl polylol fatty acid ester non-ionic surface active agents such as polyoxy alkylidene sorbitan monooleate, polyoxy alkylidene sorbitan trioleate, polyoxy alkylidene glyceryl monolaurate, polyoxy alkylidene bisphenol-A dilaurate, polyoxy alkylidene castor oil, polyoxy alkylidene rilanit special, polyoxy alkylidene rilanit special dilaurate, polyoxy alkylidene rilanit special three caprylates; 4) amide-type non-ionic surface active agents such as diethanol amine list lauramide, diethanol amine list oleamide, diethylenetriamines two caprylamides, 5) polyoxy alkylidene fatty acid acyl amine non-ionic surface active agent such as polyoxyethylene diethanol amine list oleamide, polyoxyethylene diethylenetriamines two bay acid amides etc.Wherein, Preferred ethers non-ionic surface active agent, polyol moiety ester class non-ionic surface active agent, polyoxy sub alkyl polylol fatty acid ester non-ionic surface active agent, more preferably polyol moiety ester class non-ionic surface active agent, polyoxy sub alkyl polylol fatty acid ester non-ionic surface active agent.
Finishing agent of the present invention also can further contain antistatic agent.Said antistatic agent can be enumerated out various anion surfactants, cationic surfactant, amphoteric surfactant etc.Preferred anionic surfactant wherein; Said anion surfactant can be enumerated out: 1) organic sulfonates such as tridecyl sodium sulfonate, neopelex; 2) organo-sulfate salt such as polyoxyethylene lauryl sulfate ester sodium; 3) octyl phosphate sodium, polyoxyethylene Tryfac 5573 potassium, oleyl phosphate=triethanolamine, polyoxyethylene Tryfac 5573=organophosphorus ester salt such as polyoxyethylene lauryl amine; 4) organic fatty hydrochlorates such as potassium octanoate, enuatrol, alkenyl succinic acid potassium etc., wherein preferred organic sulfonate, organophosphorus ester salt, organic fatty hydrochlorate etc., more preferably organophosphorus ester salt.
Finishing agent of the present invention preferably contains aforesaid smooth agent 30～85 quality %, emulsifying agent 10～69 quality % and antistatic agent 0.1～10 quality %; The total amount that makes them is 100 quality %, and the glyceride compounds as at least a portion of smooth agent is accounted in smooth agent more than the 65 quality %; More preferably contain smooth agent 40～70 quality %, emulsifying agent 24～59 quality % and antistatic agent 1～8 quality %; The total amount that makes them is 100 quality %, and the glyceride compounds as at least a portion of smooth agent is accounted in smooth agent more than the 70 quality %.
When make finishing agent of the present invention attached to synthetic fiber on the time; Can also be with finishing agent of the present invention and with other composition that conforms with purpose; For example, outward appearance conditioning agent, anti-oxidant, heat-resistant agent (anti-ripe upwards drug), antifoaming agent, preservative agent, rust inhibitor etc., itself and consumption are a small amount of as far as possible.
Next, the processing method (hereinafter to be referred as processing method of the present invention) that the present invention relates to is described.Processing method of the present invention is meant, to supplying the synthetic fiber filament yarn bar in heat treatment step, adheres to the method for the aforesaid finishing agent of the present invention of 0.1～3 quality %, preferred 0.5～1.5 quality %.As making finishing agent of the present invention be attached to the operation on the synthetic fiber, can enumerate out spinning process, stretching process, carry out the operation etc. of spinning and stretching simultaneously.In addition, as making inorganic agent of the present invention be attached to the method on the synthetic fibers, can list: roller (Roller) gives oil process, use the guiding of measuring pump to give oil process, spraying to oil process etc. for oil process (ガ イ De oil supply), dipping.In addition,, can enumerate aqueous liquid (water-based liquid), organic solvent solution, pure substance (ニ one ト) etc. as making finishing agent of the present invention be attached to the form on the synthetic fiber, but preferred aqueous liquid, the more preferably aqueous liquid of 5～30 quality % of finishing agent of the present invention.
Synthetic fiber as processing method applicable object of the present invention can be enumerated out: 1) polyester fibers such as PETG, polytrimethylene terephthalate, poly-lactic acid ester; 2) polyamide-based fiber such as nylon 6, nylon 66; 3) polyacrylic acid, modified acroleic acid polyacrylic acid fibrids such as (モ ダ ア Network リ Le), 4) TPO fiber such as polyethylene, polypropylene, 5) the polyurethanes fiber etc.; To its kind and not restriction of purposes; But in silk producing procedures, when the industry material under being used to be in the harsh conditions that the high temperature height connects pressure (connecing pressure) is used synthetic fiber, demonstrate extraordinary effect; Especially when being used for polyester fiber or polyamide-based fiber, demonstrate extraordinary effect.
At last, the synthetic fiber (hereinafter to be referred as synthetic fiber of the present invention) that the present invention relates to are described.Synthetic fiber of the present invention adopt processing method of the present invention and make.Synthetic fiber of the present invention are useful as the industry material that uses in tyre cord, band bundle, flexible pipe, safety belt, the air bag etc. with synthetic fiber.
As stated, among the present invention,, also can reach the generation, the inhibition that suppress fine, soft fur and tar and be fuming, and then prevent the effect that operability descends even be in the following time of harsh conditions that the high temperature height connects pressure with the synthetic fiber that kind at the similar industries material.
The specific embodiment
Below, will enumerate embodiment and wait formation of the present invention and effect further are described particularly, but the present invention does not receive the qualification of these embodiment.Among below the embodiment and comparative example, " part " representative " parts by mass ", " % " representative " quality % ".
Embodiment
Test classification 1 (preparation of finishing agent)
The preparation of embodiment 1{ finishing agent (P-1) }
With 50 parts of following glyceride compounds (K-1); 15 parts of following emulsifying agents (E-1); 20 parts of following emulsifying agents (E-2), 10 parts of following emulsifying agents (E-3), 1 part of following antistatic agent (S-1); 2 parts of following antistatic agents (S-2) and following antistatic agent (S-3) evenly mix for 1 part, the finishing agent (P-1) of preparation embodiment 1.In this finishing agent (P-1), and used 1 part of following using ingredient (T-1).
Glyceride compounds (K-1): mix and wait mole coconut oil and palm oil, add phosphoric acid, the compound that heats and carry out ester exchange at random.
Emulsifying agent (E-1): (paid and added) the ethers non-ionic surface active agent of 7 moles of ethylene oxide (hereinafter to be referred as EO) with respect to 1 mole of laruyl alcohol addition.
Emulsifying agent (E-2): with respect to 1 mole of rilanit special addition the polyol fatty acid ester class non-ionic surface active agent of 20 moles of EO.
Emulsifying agent (E-3): with respect to the addition of 1 mole of single oleic acid sorbitan ester the polyol moiety ester class non-ionic surface active agent of 14 moles of EO.
Antistatic agent (S-1): dodecyl sodium sulfate
Antistatic agent (S-2): oleyl phosphate triethanolamine salt
Antistatic agent (S-3): potassium oleate
Using ingredient (T-1): 1,3,5-trimethyl-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene
The preparation of embodiment 2～42 and comparative example 1～12{ finishing agent (P-2)～(P-42) and finishing agent (R-1)～(R-12) }
Adopt the method identical, preparation finishing agent (P-2)～(P-42) and finishing agent (R-1)～(R-12) with finishing agent P-1.The above employed composition content of each routine finishing agent of preparation shown in table 1～table 5, more than the finishing agent content prepared in each example shown in table 6～table 9.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
In table 6～table 9
Use amount: unit is part
Test classification 2 (each finishing agent adheres to and estimates synthetic fiber)
Each finishing agent is to adhere to (condition 1) of synthetic fiber
When each finishing agent of preparation in the dilution test classification 1, it evenly is diluted to 10% solution with ion exchange water or organic solvent.With conventional method with inherent viscosity be 1.10, carboxyl terminal group amount is 15 equivalents/10
6Behind the chip drying of the PETG of g; Use extruder 295 ℃ of following spinning; The inorganic agent of giving form (paying form) of record in table 10, table 11 and the table 13 or its solution of 10% are attached on the mobile strand behind spinning nozzle ejection and the cooling curing to oil process with the guiding of using measuring pump; Make boundling with guider then; Be 2500m/ minute, 150 ℃ carry-over pinch rolls (draw I and get り ロ one Le) traction again with superficial velocity; Then draw roll, the relax rolls by 245 ℃ is stretched to 2.16 times of full stretching ratios with it, batches with 5400m/ minute up-coiler at last, and the drawn yarn 10kg coiling of 1670 dtexs, 360 long filaments is obtained spinning cake.
Each finishing agent is to adhere to (condition 2) of synthetic fiber
When each finishing agent of preparation in the dilution test classification 1, it evenly is diluted to 10% solution with ion exchange water or organic solvent.Use conventional method with inherent viscosity be 1.10, carboxyl terminal group amount is 15 equivalents/10
6Behind the chip drying of the PETG of g; With extruder 295 ℃ of following spinning; The finishing agent of giving form of record in table 12 and the table 13 or its solution of 10% are attached on the mobile strand behind spinning nozzle ejection and the cooling curing to oil process with the guiding of using measuring pump; Make boundling with guider then, with superficial velocity 550m/ minute, 80 ℃ carry-over pinch rolls traction, draw roll, the relax rolls followed through 200 ℃ are stretched to 5.82 times of full stretching ratios with it again; Batch with 3200m/ minute up-coiler at last, the stretching silk 10kg of 1400 dtexs, 108 long filaments is reeled obtains spinning cake.
Each finishing agent is to adhere to (condition 3) of synthetic fiber
When each finishing agent of preparation in the dilution test classification 1, it evenly is diluted to 10% solution with ion exchange water or organic solvent.Using conventional method is after 3.7 the nylon 6 slice drying with the sulfuric acid relative viscosity; With extruder 280 ℃ of following spinning; The finishing agent of giving form or its solution of 10% of record in table 12 and the table 13 is attached on the mobile strand behind spinning nozzle ejection and the cooling curing to oil process with roller; Make boundling with guider then, use superficial velocity to be 600m/ minute, the traction of the carry-over pinch rolls (draw I and get り ロ one Le) of room temperature again, then draw roll, the relax rolls through 220 ℃ is stretched to 5.25 times of full stretching ratios with it; Batch with 3150m/ minute up-coiler at last, the stretching silk 10kg of 1400 dtexs, 208 long filaments is reeled obtains spinning cake.
The mensuration of finishing agent adhesion amount
As benchmark, the mixed solvent that uses n-hexane/ethanol (50/50 Capacity Ratio) is measured the adhesion amount of finishing agent to synthetic fiber as extracting solvent with JIS-L1073 (synthetic fiber filament test method).The result is shown in table 10～table 13.
The evaluation of operability
In the spinning process of above-mentioned condition 1～condition 3, measure the fracture of wire number of times 10 times of silk per ton, in order to standard down the mean value of measured value is estimated.The result is shown in table 10～table 13 conclusion.
AAA: fracture of wire number of times less than 0.5 time
AA: the fracture of wire number of times is more than 0.5 time～less than 1.0 times
A: the fracture of wire number of times is more than 1.0 times～less than 1.5 times
B: the fracture of wire number of times is more than 1.5 times～less than 2.0 times
C: the fracture of wire number of times is more than 2.0 times
The evaluation of fine, soft fur
In the spinning process of above-mentioned condition 1～condition 3, before silk is wound into spinning cake, measure fine, soft fur number hourly with fine, soft fur counting device (Toray Engineering Co., the DT-105 of Ltd manufactured), estimate in order to following standard.The result is shown in table 10～table 13 conclusion.
AAA: the fine, soft fur number of mensuration is 0
AA: the fine, soft fur of mensuration is counted 1 of less than (but not comprising 0)
A: the fine, soft fur number of mensuration is 1～2
B: the fine, soft fur number of mensuration is 3～9
C: the fine, soft fur number of mensuration is more than 10
The evaluation of tar
Sampling obtains the test silk from the spinning cake that above-mentioned condition 1～condition 3 obtains; Should test silk with initial stage tension force 1kg, silk speed 500m/ minute; The hot-rolling (ホ Star ト ロ one ラ one) that is wrapped in 245 ℃ of surface temperatures (situation of condition 1), 200 ℃ (situation of condition 2) or 220 ℃ (situation of condition 3) is gone up and is moved it; The tar content that hot-rolling produces after detecting by an unaided eye then 12 hours is estimated in order to following standard.The result is shown in the conclusion of table 10～table 13.
AAA: do not find tar
AA: find few tar
A: find a small amount of tar
B: find obvious tar
C: find a large amount of tar
The evaluation of being fuming
Sampling obtains the test silk from the spinning cake that above-mentioned condition 1～condition 3 obtains; Should test silk with initial stage tension force 1kg, silk speed 500m/ minute; Be wrapped on the hot-rolling of 245 ℃ of surface temperatures (situation of condition 1), 200 ℃ (situation of condition 2) or 220 ℃ (situation of condition 3) and move it; The cigarette amount that detects by an unaided eye then and produce on the hot-rolling is estimated in order to standard down.The result is shown in the conclusion of table 10～table 13.
AAA: be not fuming
AA: find seldom to be fuming
A: find to be fuming on a small quantity
B: find obviously to be fuming
C: find to be fuming in a large number
Table 10
Table 11
Table 12
Table 13
In table 10～table 13,
Give the organic solvent fluid on form hurdle: using 40 ℃ viscosity is 2.0 * 10
-6m
2The normal paraffin of/s is as organic solvent.
Claims (18)
1. synthetic fiber are used finishing agent, it is characterized in that: contain following glyceride compounds,
Said glyceride compounds is selected from following 1) and 2) at least a,
1) mix at least two kinds of greases, in the presence of acid compound, heat, thus the compound that carries out ester exchange at random,
2) compound lard, aliphatic monocarboxylic acid, glycerine heat in the presence of acid compound, thus the compound that carries out ester exchange at random,
Said grease is selected from the vegetable fat of triglycerides of aliphatic acid that comprises with the laurate carbon number 6～20 that is main component; The vegetable fat of triglycerides of aliphatic acid that comprises with oleic acid the carbon number 10～24 that is main component; The vegetable fat of triglycerides of aliphatic acid that comprises the carbon number 14～20 of hydroxyl aliphatic acid; Comprise the carbon number 12～20 that contains ring-type acid aliphatic acid triglycerides vegetable fat or comprise the animal fat of triglycerides of the aliphatic acid of carbon number 4～24.
2. synthetic fiber as claimed in claim 1 are used finishing agent; Wherein, contain smooth agent 30～85 quality %, emulsifying agent 10～69 quality % and antistatic agent 0.1～10 quality %, their total content is 100 quality %; And at least a portion as smooth agent contains glyceride compounds; It is accounted in smooth agent more than the 65 quality %, and said glyceride compounds is selected from following 1) and 2) at least a
1) mix at least two kinds of greases, in the presence of acid compound, heat, thus the compound that carries out ester exchange at random,
2) compound lard, aliphatic monocarboxylic acid, glycerine heat in the presence of acid compound, thus the compound that carries out ester exchange at random,
Said grease is selected from the vegetable fat of triglycerides of aliphatic acid that comprises with the laurate carbon number 6～20 that is main component; The vegetable fat of triglycerides of aliphatic acid that comprises with oleic acid the carbon number 10～24 that is main component; The vegetable fat of triglycerides of aliphatic acid that comprises the carbon number 14～20 of hydroxyl aliphatic acid; Comprise the carbon number 12～20 that contains ring-type acid aliphatic acid triglycerides vegetable fat or comprise the animal fat of triglycerides of the aliphatic acid of carbon number 4～24.
3. synthetic fiber as claimed in claim 1 are used finishing agent; Wherein, contain smooth agent 40～70 quality %, emulsifying agent 24～59 quality % and antistatic agent 1～8 quality %, their total content is 100 quality %; And at least a portion as smooth agent contains glyceride compounds; It is accounted in smooth agent more than the 70 quality %, and said glyceride compounds is selected from following 1) and 2) at least a
1) mix at least two kinds of greases, in the presence of acid compound, heat, thus the compound that carries out ester exchange at random,
2) compound lard, aliphatic monocarboxylic acid, glycerine heat in the presence of acid compound, thus the compound that carries out ester exchange at random,
Said grease is selected from the vegetable fat of triglycerides of aliphatic acid that comprises with the laurate carbon number 6～20 that is main component; The vegetable fat of triglycerides of aliphatic acid that comprises with oleic acid the carbon number 10～24 that is main component; The vegetable fat of triglycerides of aliphatic acid that comprises the carbon number 14～20 of hydroxyl aliphatic acid; Comprise the carbon number 12～20 that contains ring-type acid aliphatic acid triglycerides vegetable fat or comprise the animal fat of triglycerides of the aliphatic acid of carbon number 4～24.
4. synthetic fiber as claimed in claim 3 are used finishing agent, and wherein, glyceride compounds is selected from following compound:
Mix being selected from least two kinds of greases in coconut oil, palm-kernel oil, palm oil, olive oil, rapeseed oil, rice bran oil, castor oil, rilanit special and the butter, in the presence of acid compound, heat, thus the compound that carries out ester exchange at random.
5. synthetic fiber as claimed in claim 3 are used finishing agent, and wherein, glyceride compounds is selected from following compound,
With grease that is selected from the following A group and the grease that is selected from following B group, be 70/30～30/70 mixed with the mol ratio of the grease that is selected from the A group/be selected from the grease of B group, in the presence of acid compound, heat, thus the compound that carries out ester exchange at random,
A group: coconut oil and palm-kernel oil;
B group: palm oil, olive oil, rapeseed oil and rice bran oil.
6. synthetic fiber as claimed in claim 3 are used finishing agent, and wherein, glyceride compounds is selected from: mixed grease, aliphatic monocarboxylic acid, glycerine, in the presence of acid compound, heated, thus the compound that carries out ester exchange at random.
7. synthetic fiber as claimed in claim 6 are used finishing agent, and wherein, that aliphatic monocarboxylic acid is selected from is sad, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, dodecoic acid, isostearic acid, oleic acid and 12-kamalolenic acid.
8. synthetic fiber as claimed in claim 5 are used finishing agent, and wherein, the smooth agent except that glyceride compounds is selected from aliphatic ester compound, aromatic ester compound and animal and plant fat,
Said aliphatic ester compound is selected from octyl stearate, lauric acid oil alkenyl esters, oleic oil alkenyl esters, 1; 6-hexylene glycol dicaprate, single oleic acid two laurate trihydroxymethylpropanyl esters, adipic acid two lauryls, thio-2 acid two oleyl esters, azelaic acid two oleyl ester or Pentaerythrityl tetraoctanoates
Said aromatic ester compound is selected from stearic acid benzyl ester, bay acid benzyl ester, bisphenol-A dilaurate, M-phthalic acid two isooctadecane ester or trioctyl trimellitate (TOTM)s,
Said animal and plant fat is selected from coconut oil, palm oil, rapeseed oil, sunflower oil, sesame oil, soybean oil, Linseed oil, castor oil, fish oil or butter.
9. synthetic fiber as claimed in claim 7 are used finishing agent, and wherein, the smooth agent except that glyceride compounds is selected from aliphatic ester compound, aromatic ester compound and animal and plant fat,
Said aliphatic ester compound is selected from octyl stearate, lauric acid oil alkenyl esters, oleic oil alkenyl esters, 1; 6-hexylene glycol dicaprate, single oleic acid two laurate trihydroxymethylpropanyl esters, adipic acid two lauryls, thio-2 acid two oleyl esters, azelaic acid two oleyl ester or Pentaerythrityl tetraoctanoates
Said aromatic ester compound is selected from stearic acid benzyl ester, bay acid benzyl ester, bisphenol-A dilaurate, M-phthalic acid two isooctadecane ester or trioctyl trimellitate (TOTM)s,
Said animal and plant fat is selected from coconut oil, palm oil, rapeseed oil, sunflower oil, sesame oil, soybean oil, Linseed oil, castor oil, fish oil or butter.
10. synthetic fiber as claimed in claim 8 are used finishing agent; Wherein, emulsifying agent is selected from ethers non-ionic surface active agent, polyol moiety ester class non-ionic surface active agent and the polyoxy sub alkyl polylol fatty acid ester non-ionic surface active agent that has polyoxy alkylidene in the molecule.
11. synthetic fiber as claimed in claim 9 are used finishing agent; Wherein, emulsifying agent is selected from ethers non-ionic surface active agent, polyol moiety ester class non-ionic surface active agent and the polyoxy sub alkyl polylol fatty acid ester non-ionic surface active agent that has polyoxy alkylidene in the molecule.
12. synthetic fiber as claimed in claim 10 are used finishing agent, wherein, antistatic agent is selected from organic sulfonate, organophosphorus ester salt and organic fatty hydrochlorate.
13. synthetic fiber as claimed in claim 11 are used finishing agent, wherein, antistatic agent is selected from organic sulfonate, organophosphorus ester salt and organic fatty hydrochlorate.
14. the processing method of synthetic fiber is characterized in that:, adhere in the claim 1～13 of 0.1～3 quality % each described synthetic fiber and use finishing agent to supplying synthetic fiber filament yarn bar in heat treatment step.
15. the processing method of synthetic fiber as claimed in claim 14; Wherein, Synthetic fiber are mixed with the aqueous liquid of 5～30 quality % with finishing agent, adhere to this aqueous liquid to supplying in the synthetic fiber filament yarn bar of heat treatment step, making synthetic fiber use the adhesion amount of finishing agent is 0.1～3 quality %.
16. the processing method of synthetic fiber as claimed in claim 15, wherein, synthetic fiber are that the industry material is used synthetic fiber.
17. the processing method of synthetic fiber as claimed in claim 16, wherein, the industry material is polyester fiber or polyamide-based fiber with synthetic fiber.
18. synthetic fiber, its processing method through synthetic fiber as claimed in claim 16 obtains.
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| JP2007-335936 | 2007-12-27 | ||
| JP2007335936 | 2007-12-27 | ||
| JP2007335936A JP4947798B2 (en) | 2007-12-27 | 2007-12-27 | Synthetic fiber treatment agent, synthetic fiber treatment method and synthetic fiber |
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| CN101469509A CN101469509A (en) | 2009-07-01 |
| CN101469509B true CN101469509B (en) | 2012-12-12 |
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| JP4940382B2 (en) * | 2010-06-24 | 2012-05-30 | 松本油脂製薬株式会社 | Synthetic fiber treatment agent for airbag, synthetic fiber filament for airbag, and base fabric for airbag |
| WO2014024647A1 (en) * | 2012-08-07 | 2014-02-13 | 松本油脂製薬株式会社 | Processing agent for synthetic fibers and use thereof |
| JP6351569B2 (en) * | 2013-03-29 | 2018-07-04 | 松本油脂製薬株式会社 | Treatment agent for synthetic fibers and use thereof |
| JP5500745B1 (en) * | 2013-08-19 | 2014-05-21 | 竹本油脂株式会社 | Synthetic fiber treatment agent, synthetic fiber treatment method and synthetic fiber |
| WO2015068671A1 (en) * | 2013-11-09 | 2015-05-14 | 松本油脂製薬株式会社 | Synthetic fiber treatment agent and use for same |
| JP5903450B2 (en) * | 2014-02-04 | 2016-04-13 | 松本油脂製薬株式会社 | Treatment agent for synthetic fibers and use thereof |
| JP6482945B2 (en) * | 2015-05-07 | 2019-03-13 | 松本油脂製薬株式会社 | Treatment agent for synthetic fibers and use thereof |
| JP5960885B1 (en) * | 2015-06-30 | 2016-08-02 | 松本油脂製薬株式会社 | Treatment agent for synthetic fibers and use thereof |
| JP5967852B1 (en) * | 2015-07-27 | 2016-08-10 | 竹本油脂株式会社 | Synthetic fiber treatment agent aqueous liquid, synthetic fiber treatment agent emulsion, and synthetic fiber treatment method |
| US10463699B2 (en) * | 2016-04-04 | 2019-11-05 | Omeza LLC | Fish oil topical composition |
| KR101928865B1 (en) | 2017-01-19 | 2018-12-14 | 효성첨단소재 주식회사 | Eco-friendly addititives containing lyocell dipped cord improved fatigue properties |
| JP6310168B1 (en) * | 2018-01-09 | 2018-04-11 | 竹本油脂株式会社 | Synthetic fiber treatment agent and synthetic fiber |
| JP6480052B1 (en) * | 2018-03-13 | 2019-03-06 | 竹本油脂株式会社 | Diluted solution for treating agent for synthetic fiber and method for producing synthetic fiber |
| KR102355502B1 (en) * | 2018-04-16 | 2022-02-08 | 다케모토 유시 가부시키 가이샤 | Treatment agent for synthetic fibers and synthetic fibers |
| CN112482027B (en) * | 2020-11-20 | 2022-10-25 | 南京玻璃纤维研究设计院有限公司 | Carbon fiber surface treating agent and treating method |
| CN113980723A (en) * | 2021-10-08 | 2022-01-28 | 江苏悦孚油品有限公司 | Antistatic reagent for hot box of elasticizer and preparation method thereof |
| JP7098210B1 (en) * | 2022-04-15 | 2022-07-11 | 竹本油脂株式会社 | Treatment agents for carbon fiber precursors and carbon fiber precursors |
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| JP4947798B2 (en) | 2012-06-06 |
| CN101469509A (en) | 2009-07-01 |
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