CN103261509B - Processing agent for polyester fiber structure and production method for polyester fiber structure using same - Google Patents

Abstract

The present invention provides an end-capping processing agent of a polyester fiber structure that can exhaust an end-capping agent effectively in a product to be treated, as well as a production method for a polyester fiber structure that is excellent in terms of hydrolysis resistance, using the end-capping processing agent. The present invention is characterized by the processing end blockade by the end-capping processing agent in which a carbodiimide end-capping agent and a carrier containing alkylphthalimide and benzoic ester as essential components are emulsified or dispersed in water or solvent through the use of a surfactant.

Description

The processing agent of polyester fiber works and use the manufacture method of polyester fiber works of this processing agent

Technical field

The manufacture method of the processing agent that the present invention relates to polyester fiber works and the polyester fiber works that uses this processing agent.

Background technology

In recent years, environmental consciousness improves gradually, and in order to reduce plastic refuse, suppress global warming, reducing CO2 emissions is social responsibilities that enterprise should use up.In order to solve these problems, the effective utilization promoting can to expect to utilize enzyme, microorganism carries out the biodegradable plastic decomposed, to advance recirculation, re-use be important.

As the biodegradable plastic made by natural resources, PLA attracts attention especially, and the lactic acid as the raw material of PLA is obtained by plants such as corns, therefore can be described as environment-friendly type plastic.But water-disintegrable very high in the water of room temperature, high temperature of PLA, in addition, also can decompose such character even if having by the moisture in air, thus environment for use, use are restricted.

About hydrolysis, because the proton of releasing from terminal carboxyl group works as self-catalysis agent, thus promote the decomposition of ester, being therefore not only PLA is also the common problem of polyester fiber.

As the polyethylene terephthalate of general purpose polyester compared with PLA, hydrolysis rate is slow, therefore when using as common dress material purposes, there is sufficient hydrolytic resistance, but the uniform in the fields such as medical treatment, nursing, food needs the washing of the hot bath of employing 60 ~ 90 DEG C, the autoclaving process of 120 DEG C ~ 130 DEG C, therefore worries the deterioration being caused cloth and silk by this process.Therefore, present situation is the uniform in medical field, and the ratio of shorter, the disposable product of lifespan is high.

Therefore, by the technology providing the hydrolytic resistance making polyester fiber to improve, thus the use that can realize the biodegradable plastic taking PLA as representative promotes, and require the long lifetime of uniform of washing under high temperature, autoclaving process, can environmental problem be solved.

As the poly-esterolytic means of suppression, method end carboxy concentration being reduced by adding endcapped agent is open in Japanese Unexamined Patent Publication 2001-261797, Japanese Unexamined Patent Publication 2002-30208.But, these methods due to mixing before spinning, add polymeric sheet material, therefore have due to high temperature during spinning, endcapped agent evaporation, decompose and cause and be fuming, produce the problem that stench, toxic gas are such.In addition, therefore must add the such problem of endcapped agent in addition superfluously.In addition spinnability worsens, and productivity also reduces.By using inorganic matter as endcapped agent as disclosed in Japanese Unexamined Patent Publication 2010-189813, although the problem of toxic gas during mixing, spinning can solve, but owing to being the endcapped process of spinning phase, therefore likely the change of silk kind is difficult, or is hydrolyzed in the techniques such as dyeing, aft-loaded airfoil operation.

As other solution, will endcapped agent be made to use dissolution with solvents or the material that utilizes emulsifying agent lo-tionized and obtain directly to contact with treated object, the method closed at the surperficial additional end of treated object discloses in Japanese Unexamined Patent Publication 2009-249450.But in the method, endcapped agent exists only in handled thing near surface, and therefore the administered dose of endcapped agent is insufficient, long-term is insufficient relative to damp and hot hydrolytic resistance.

As making the long-term method improved relative to damp and hot hydrolytic resistance, the surface being desirably in the works of damp and hot direct contact gives endcapped agent with high concentration, and also gives endcapped agent with certain concentration in the inside of works.At the near surface of works with high concentration additional end sealer, and also disclose in Japanese Unexamined Patent Publication 2009-263840 with the method for certain above concentration additional end sealer works is inner.But the exhaustion efficiency of endcapped agent to treated object is low, therefore have working concentration high, the cost of endcapped agent cost uprises such problem.

Although when polyester fiber is processed with the working fluid comprising fiber function imparting agent, the method in this working fluid, carrier being coexisted is open in Japanese Unexamined Patent Publication 2001-98459, but as function processing agent, waterproofing agent, water absorbing agent, fire retardant etc. are only enumerated, bring what kind of effect not record about the carrier recorded in the present invention for endcapped agent, do not study particularly in addition.In addition, use phthalimide compound that polymerization initiator is exhausted in bath and the method for carrying out grafting process discloses in Japanese Unexamined Patent Publication 2000-226765, but bring what kind of effect not record about the phthalimide compound recorded in the present invention for endcapped agent, do not study particularly in addition.

Prior art document

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2001-261797 publication

Patent document 2: Japanese Unexamined Patent Publication 2002-30208 publication

Patent document 3: Japanese Unexamined Patent Publication 2010-189813 publication

Patent document 4: Japanese Unexamined Patent Publication 2009-249450 publication

Patent document 5: Japanese Unexamined Patent Publication 2009-263840 publication

Patent document 6: Japanese Unexamined Patent Publication 2001-98459 publication

Patent document 7: Japanese Unexamined Patent Publication 2000-226765 publication

Summary of the invention

Invent problem to be solved

The present invention, in view of such background in the past, provide and can exhaust the processing agent of the polyester fiber works of carbodiimide compound efficiently relative to treated object and use the manufacture method of polyester fiber works of hydrolytic resistance excellence of this processing agent.

For solving the method for problem

The present invention has following formation to reach above-mentioned purpose.

(1) a kind of processing agent of polyester fiber works, it is characterized in that, be the processing agent making carbodiimide compound and carrier agent emulsification or dispersion in water or solvent, this carrier agent comprises benzoic acid compounds and phthalimide compound as essential component.

(2) processing agent of the polyester fiber works according to above-mentioned (1), is characterized in that, this carbodiimide compound is the compound shown in general formula (I).

General formula (I)

In general formula (I),

R1 represents a kind in the aralkyl of alkyl, the cycloalkyl of carbon number 5 ~ 12, the aryl of carbon number 6 ~ 20, allyl and the carbon number 7 ~ 20 being selected from carbon number 1 ~ 20.

(3) processing agent of the polyester fiber works according to above-mentioned (1) or (2), it is characterized in that, this carbodiimide is for being selected from N, N '-two-2,6-diisopropyl phenyl carbodiimide, N, N '-two-carbodicyclo hexylimide and N, N ' in-DIC at least a kind.

(4) processing agent of the polyester fiber works according to any one of above-mentioned (1) ~ (3), is characterized in that, this carrier agent comprises Ergol and N-butyl phthalimide as essential component.

(5) manufacture method for polyester fiber works, is characterized in that, makes the inside of the exhaustion of the processing agent described in any one to polyester fiber works of above-mentioned (1) ~ (4).

(6) a kind of manufacture method of polyester fiber works, it is characterized in that, giving, to polyester fiber, to there is drying process by the treatment fluid of the processing agent described in any one containing above-mentioned (1) ~ (4), then there is heat treatment step.

(7) a kind of manufacture method of polyester fiber works, it is characterized in that, polyester fiber is dropped into, processing during the circulation of this treatment fluid is bathed in the treatment fluid of the processing agent described in any one containing above-mentioned (1) ~ (4).

(8) manufacture method for polyester fiber works, is characterized in that, gives to polyester fiber, carry out humid heat treatment by the treatment fluid of the processing agent described in any one containing above-mentioned (1) ~ (4).

(9) a kind of polyester fiber works adopting the method described in any one of above-mentioned (5) ~ (8) to obtain, it is characterized in that, in the filament cross section of this polyester fiber, from outer layers towards inner layers, this processing agent concentration diminishes.

The effect of invention

According to the present invention, can, relative to the fiber structure comprising polyester fiber, carbodiimide compound be given efficiently, to fiber structure surface and fiber structure inside, can high hydrolytic resistance be brought.

Detailed description of the invention

According to the present invention, utilize together with the carbodiimide compound of the effect playing endcapped agent, make to comprise phthalimide compound and benzoic acid compounds to process as the treatment fluid of carrier agent emulsification or dispersion in water or solvent of essential component, thus it is inner relative to fiber construct, carbodiimide is exhausted efficiently, with the carboxyl terminal radical reaction formed in the polymer of this fiber construct, end carboxy concentration reduces, and therefore gives hydrolytic resistance.

So-called polyester fiber in the present invention, refers in strand the fiber with ester bond, preferably uses aliphatic polyester, aromatic polyester.

As aliphatic polyester, the polymer in aliphatic polyester aliphatic dicarboxylic acid and aliphatic diol condensation obtained, the copolymer being selected from poly-(D-ALPHA-Hydroxypropionic acid), PLLA, the copolymer of D-ALPHA-Hydroxypropionic acid and Pfansteihl, the copolymer of D-ALPHA-Hydroxypropionic acid and hydroxycarboxylic acid, the copolymer of Pfansteihl and hydroxycarboxylic acid, DL-LACTIC ACID and hydroxycarboxylic acid or their blending body etc. can be enumerated.Wherein, from versatility aspect, preferably use Pfansteihl as the PLA of principal component, the ア ペ Network サ etc. as environment-friendly type polyester that gone on the market by デ ュ ポン society.Here, what is called is using Pfansteihl as principal component, and refer in aliphatic polyester, more than 50 % by weight is Pfansteihl.In addition, about this aliphatic polyester, by adding endcapped agent when spinning, thus can the part of closed end carboxyl.

As the manufacture method of such PLA, known: lactic acid temporarily to be generated lactide as cyclic dimer as raw material, then carries out the lactide method of the two-stage of ring-opening polymerization; Lactic acid is directly carried out in a solvent the direct polymerization method of the one-phase of dehydrating condensation as raw material.The PLA used in the present invention can be obtained by arbitrary method for making.

As aromatic polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate (PBT), PEN, poly-naphthalenedicarboxylic acid propylene glycol ester, PBN etc. can be used.In addition, these aromatic polyesters can comprise other copolymer composition, are not limited to above-mentioned polyester.

As the copolymer composition in polyester, can enumerate and rise to the dimer diols of object, the diol component rising to object by colour rendering, the multifunctional phosphorus compound for the purpose of anti-flammability is given, the sulfoisophthalic acid salt etc. for the purpose of cation dyeable is given by resistance to alkali hydrolysis property, but copolymer composition is not limited thereto.

As above-mentioned dimer diols, specifically, East Asia synthesis (strain) ペ ス processed ポ ー Le HP-1000 (carbon number 36 and the hydrogenation dimer diols of cycloaliphatic type/straight-chain aliphatic type=75/25 (mol%)) etc. can be enumerated.

As above-mentioned diol component, specifically, can enumerate at 1,5-PD, 1, in the compounds such as 6-hexylene glycol, 1,9-nonanediol, neopentyl glycol, bisphenol-A, bisphenol S, addition has the diol compound of ethylene oxide and the copolymer, polyoxyalkylene diols etc. of propylene oxide and ethylene oxide.

As above-mentioned multifunctional phosphorus compound, specifically, preferably phenyl-phosphonic acid dimethyl ester, diphenyl phenylphosphonate etc. are used.As phosphinic acid ester, (2-carboxy ethyl) methyl-phosphinic acid can be enumerated, (2-dion e) methyl-phosphinic acid methyl esters, (2-carboxy ethyl) phenyl phosphinic acid, (2-dion e) phenyl phosphinic acid methyl esters, (4-methoxycarbonyl-phenyl) phenyl phosphinic acid methyl esters, the phosphoric acid esters such as the glycol ester of [2-(beta-hydroxy ethoxy carbonyl) ethyl] methyl-phosphinic acid, (1, 2-dicarboxyethyl) dimethyl phosphine, (2, 3-dicarboxypropyl) dimethyl phosphine, (1, 2-dimethoxy-ethyl-carbonyl) dimethyl phosphine, (2, 3-dimethoxy-ethyl-carbonyl) dimethyl phosphine, [1, 2 two (beta-hydroxy ethoxy carbonyl) ethyl] dimethyl phosphine, [2, 3 two (beta-hydroxy ethoxy carbonyl) ethyl] phosphinoxides such as dimethyl phosphine.

As above-mentioned sulfoisophthalic acid salt, specifically, the alkali metal salt of sulfoisophthalic acid, sulfoisophthalic acid can be enumerated salt and the ester formative derivative derived by it.Specifically, alkali metal salt, the M-phthalic acid 5-sulfonic acid (tetraalkyl) of the sulfoisophthalic acid such as M-phthalic acid 5-sodium sulfonate, M-phthalic acid 5-Sulfonic Lithium can be enumerated with the ester formative derivative etc. derived by it.

The polyester fiber used in the present invention is except common flat yarn, can be the filament yarns such as false-twisted yarn, tight twist yarn, Taslan processing yarn, thickness silk, combined yarn, also can be the fiber of the various forms such as staple fiber, rescutched tow (tow), short fibre yarn or cloth and silk.

The polyester fiber used in the present invention can form alloy (alloy) with other polymer such as polyamide.

In the polyester fiber used in the present invention, natural fabric, regenerated fiber, semisynthetic fibre, synthetic fiber etc. can be used with.As the form of compound, can be any forms such as blending, intertexture, friendship volume.As the form of fiber structure, the fiber structure such as woven fabric, braided fabric, bondedfibre fabric, goods long filament, short fibre yarn can enumerated and obtained by them, but be not limited thereto.

So-called natural fabric, can enumerate cotton, kapok, fiber crops, flax, hemp, ramie, wool, alpaca fibre, goat cashmere, mohair, silk etc.So-called regenerated fiber, can enumerate viscose glue, copper ammonia fibre, polynosic, high wet modulus rayon, solvent spinning fibre cellulose fiber etc.So-called semisynthetic fibre, can enumerate acetic acid esters, diacetate esters, triacetate etc.So-called synthetic fiber, can enumerate polyamide, acrylic fibre, vinylon, polypropylene, polyurethane, polyvinyl chloride, polyethylene, Promix etc.

In the present invention, arbitrary gimmick other fiber mixed in polyester fiber can be adopted, if but the mixed rate of polyester fiber is little.Then effect of the present invention reduces, and therefore the mixed rate of polyester fiber is preferably more than 30 % by weight, and more preferably more than 50 % by weight.

In the present invention, utilize and process polyester fiber works containing the treatment fluid of processing agent, described processing agent is using the endcapped agent of carbodiimide system and comprises phthalimide compound and the benzoic acid compounds carrier as essential component emulsification or dispersion in water or solvent.By this process, make processing agent exhaustion to the inside of fiber structure.

Process the method for polyester fiber as the treatment fluid utilized containing processing agent, preferably use following method: first, in the treatment fluid containing processing agent of the present invention, drop into polyester fiber, the method for processing during treatment fluid circulation is bathed.

Making this treatment fluid circulate while add man-hour in bathing, as the form of treated object, cloth and silk, silk, goods, rescutched tow, cotton etc. can be illustrated, but be not limited to this.As the treating apparatus of processing in bath, the device such as rope dyeing machine, volume dyeing machine, paddle dyeing machine, rotary drum type dyeing machine, liquid-flow dyeing machine, airflow dyeing machine, package dyeing machine, cone dyeing machine, formula dyeing machine difficult to understand can be utilized, but be not limited to this.

Preferably in this treatment fluid, flood cloth and silk, at normal pressure or add pressure, carry out heat treated at 80 ~ 130 DEG C.This heating treatment time is preferably 10 ~ 120 minutes.When aliphatic polyester, more preferably 90 ~ 110 DEG C of process 20 ~ 60 minutes.When aromatic polyester, more preferably 110 ~ 130 DEG C of process 20 ~ 60 minutes.Now, endcapped agent is attached to fiber, exhausts, diffuses to fibrous inside.When the processing time is short, exhaustion from endcapped agent sometimes to fibrous inside, spread insufficient, can not obtain can gratifying hydrolytic resistance.In addition, when the processing time is long, in process, poly-ester hydrolysis carries out.

After having carried out in liquid process in the methods described above, carry out dewatering, dry.As long as drying is the condition of moisture drying, be preferably 100 ~ 140 DEG C.The heat treatment of 80 ~ 200 DEG C is preferably carried out in the heat treatment carried out after drying.Its processing time is preferably 15 seconds ~ 8 minutes.When aliphatic polyester, be more preferably and carry out 30 seconds ~ 5 minutes at 90 ~ 140 DEG C.When aromatic polyester, be more preferably and carry out 30 seconds ~ 5 minutes at 130 ~ 190 DEG C.In this treatment fluid, if mixing take DISPERSE DYES as the hydrophobic dye of representative, then can dye while endcapped process, the dehydration in liquid after process, drying, heat treatment can be suitable for carry out in common dyeing process drying, extreme trace setting condition.

As annealing device, stenter, becate (short loop), drying machine (Shrink-Surfer), steamer, drum drier etc. can be utilized, but as long as the device of heat can be given equably to this fiber, be just not limited to this.

In addition, process the method for polyester fiber as the treatment fluid utilized containing processing agent, can enumerate and use the devices such as ironer to give to polyester fiber the treatment fluid containing processing agent, carry out drying, heat-treating methods.

As device polyester fiber being given to the treatment fluid containing processing agent of the present invention, be applicable to using common ironer to give device as liquid, as long as but the device of liquid can be given equably to fiber, not device for limiting.Bubble processing machine, print process, ink-jet, gunite, rubbing method etc. can be adopted to give.

As dry, annealing device, stenter, becate, drying machine, steamer, drum drier etc. can be utilized, as long as but hot device can be given equably to this fiber, be just not limited to this.In containing the treatment fluid of processing agent, flood cloth and silk, after squeezing equably, carry out drying, heat treatment, baking temperature is preferably 80 DEG C ~ 150 DEG C.Its processing time is preferably 15 seconds ~ 5 minutes.When aliphatic polyester, be more preferably and carry out 30 seconds ~ 3 minutes at 90 ~ 110 DEG C.When aromatic polyester, be more preferably and carry out 30 seconds ~ 3 minutes at 100 ~ 140 DEG C.When baking temperature is too high, in drying process, endcapped agent and water react and inactivation sometimes.

Dried heat treatment is preferably 80 ~ 200 DEG C.Its processing time is preferably 15 seconds ~ 8 minutes.When aliphatic polyester, be more preferably and carry out 30 seconds ~ 5 minutes at 90 ~ 140 DEG C.When aromatic polyester, be more preferably and carry out 30 seconds ~ 5 minutes at 130 ~ 190 DEG C.When treatment temperature is too high, polyester melt.This external processing time, when long, in process, poly-ester hydrolysis carried out.

In addition, process the method for polyester fiber as the treatment fluid utilized containing processing agent, also preferably use and the treatment fluid containing processing agent of the present invention is given to polyester fiber, carry out the method for humid heat treatment.When humid heat treatment, compared with carrying out the method for above-mentioned 2 kinds of dry heat treatment, heat transfer is good, and endcapped agent and polyester fiber can be made efficiently to react.

After using ironer etc. to give treatment fluid as described above, carry out humid heat treatment.As humid heat treatment device, normal pressure steamer, autoclave high pressure steamer etc. can be utilized, as long as but hot device can be given equably to this fiber, be just not limited to this.Preferably in the treatment fluid containing endcapped agent, flood cloth and silk, after squeezing equably, carry out the humid heat treatment of 80 ~ 130 DEG C.Its processing time is preferably 15 seconds ~ 8 minutes.When aliphatic polyester, be more preferably and carry out 30 seconds ~ 5 minutes at 90 ~ 105 DEG C.When aromatic polyester, be more preferably and carry out 30 seconds ~ 5 minutes at 105 ~ 130 DEG C.When the processing time is long, in process, poly-ester hydrolysis carries out.

If mixing in the treatment fluid containing endcapped agent with DISPERSE DYES is the hydrophobic dye of representative, then can dye while endcapped process.If endcapped process and dyeing carried out simultaneously, then dyeing concentration uprises.In addition because the number of times by humid heat treatment operation reduces, therefore poly-ester hydrolysis is suppressed.

As hydrophobic dye, reducing dye, bipseudoindoxyl dye, naphthol dye etc. can also be used.

As in the present invention as endcapped agent use carbodiimide compound, as long as have the compound of at least 1 carbodiimide, can use such as, the following compound shown in general formula (I).

In general formula (I), R1 represents a kind in the aralkyl of alkyl, the cycloalkyl of carbon number 5 ~ 12, the aryl of carbon number 6 ~ 20, allyl and the carbon number 7 ~ 20 being selected from carbon number 1 ~ 20.

Specifically, N can be enumerated, N '-two-o-tolyl carbodiimide, N, N '-diphenyl carbodiimide, N, N '-dioctyl decyl carbodiimide, N, N '-two-2,6-3,5-dimethylphenyl carbodiimide, N-tolyl-N '-carbodicyclo hexylimide, N, N '-two-2,6-diisopropyl phenyl carbodiimide, N, N '-two-2,6-bis--tert-butyl-phenyl carbodiimide, N, N '-two-p-nitrophenyl carbodiimide, N, N '-two-p-aminophenyl carbodiimide, N, N '-two-p-hydroxybenzene carbodiimide, N, N '-two-carbodicyclo hexylimide, N, N '-two-p-methylphenyl carbodiimide, to phenylene-bis--two-o-tolyl carbodiimide, to phenylene-bis--dicyclohexylcarbodiimide, hexa-methylene-bis--dicyclohexylcarbodiimide, ethylidene-bis--diphenyl carbodiimide, N, N '-benzyl carbodiimide, N-octadecyl-N '-phenyl carbons diimine, N-benzyl-N '-phenyl carbons diimine, N-octadecyl-N '-tolyl carbodiimide, N-phenyl-N '-tolyl carbodiimide, N-benzyl-N '-tolyl carbodiimide, N, N '-two-adjacent ethylphenyl carbodiimide, N, N '-two-to ethylphenyl carbodiimide, N, N '-two-o-isopropyl phenyl carbodiimide, N, N '-two-p-isopropyl phenyl carbodiimide, N, N '-two-adjacent isobutyl phenenyl carbodiimide, N, N '-two-to isobutyl phenenyl carbodiimide, N, N '-two-2,6-diethyl phenyl carbodiimide, N, N '-two-2-ethyl-6-isopropyl phenyl carbodiimide, N, N '-two-2-isobutyl group-6-isopropyl phenyl carbodiimide, N, N '-two-2,4,6-trimethylphenyl carbodiimide, N, N '-two-2,4,6-triisopropyl phenyl carbodiimide, N, N '-two-2,4,6-triisobutyl phenyl carbons diimine, N, N '-DIC etc.

In addition, can, from these carbodiimide compounds, one kind or two or more compound be at random selected to carry out the carboxyl terminal of closed polyester.

In addition, as the industrial carbodiimide compound that can obtain, can also be applicable to using N, N '-two-2,6-diisopropyl phenyl carbodiimide (TIC), N, N '-two-carbodicyclo hexylimide (DCC), N, N '-DIC (DIC).Be applicable to illustrating " ス タ バ Network ゾ ー Le " I, " ス タ バ Network ゾ ー Le " I LF, " ス タ バ Network ゾ ー Le " P, " ス タ バ Network ゾ ー Le " P-100 of being sold with the trade name of " ス タ バ Network ゾ ー Le " by ラ イ Application ケ ミ ー ジ ャ パ Application Co., Ltd..

The carrier agent used in the present invention is make polyester chain swelling and the object that endcapped agent is exhausted efficiently to fibrous inside is added.The stink of all the time used trichloro-benzenes, methyl naphthalene etc. is also strong, is easy to produce carrier spot, therefore worries the deterioration of operating environment and the stink of end article, quality.Conducting in-depth research to solve such problem, found that, by using phthalimide compound and benzoic acid compounds, endcapped agent can be made efficiently to exhaust to polyester fiber inner.

The so-called phthalimide compound used in the present invention, for having the compound of phthalimide-based, the N base being preferably phthalimide has the N substituted phthalimide of aliphatic or aromatic alkyl etc.The alternatively example of base, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, benzyl, naphthyl etc. can be enumerated, but from aspects such as the remaining quantity in fabricated product, stink, security, process operability, be more preferably the N phlhalimide with low molecular weight aliphatic alkyls such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl groups.Wherein, from the excellent compatibility aspect with carbodiimide compound, preferably use N-butyl phthalimide.

The so-called benzoic acid compounds used in the present invention, refers to benzoic acid derivative, but is preferably the benzoic ether obtained by benzoic acid and aliphatic or aromatic alcohols.As the example of benzoic ether, ethyl benzoate, methyl benzoate, propyl benzoate, butyl benzoate, Ergol, phenol benzoate etc. can be enumerated, but from the aspects such as the compatibility of carbodiimide compound, the swelling effect of polyester chain, be more preferably Ergol, phenol benzoate etc.Wherein, preferably use and there is the molecular weight close with the TIC as endcapped agent, and the Ergol that can cheaply obtain.

The blending ratio of phthalimide compound and benzoic acid compounds is, relative to phthalimide compound 50 weight portion, be preferably benzoic acid compounds 10 weight portion ~ 50 weight portion, be more preferably benzoic acid compounds 15 weight portion ~ 40 weight portion, more preferably benzoic acid compounds 20 weight portion ~ 30 weight portion.In addition, phthalimide compound of more than two kinds and benzoic acid compounds of more than two kinds can be used.

As the mixture of N phlhalimide and benzoic ether, to be gone on the market UNIVADINE PB by Ha ンツマン society, can be applicable to using.

The ratio of carbodiimide compound and above-mentioned mixed carrier agent is, relative to carbodiimide compound 25 weight portion, is preferably mixed carrier agent 20 weight portion ~ 35 weight portion, more preferably mixed carrier agent 25 ~ 30 weight portion.

The processing agent of polyester fiber works of the present invention be make above-mentioned carbodiimide compound, comprise benzoic acid compounds, phthalimide compound is as the carrier agent of essential component emulsification or dispersion in water or solvent, as emulsification or dispersant, preferably use at least a kind of surfactant be selected from nonionic system surfactant or anion system surfactant.

About in the present invention as endcapped agent use carbodiimide compound, such as, this endcapped agent and above-mentioned carrier agent and surfactant and organic solvent as required can be mixed, heating, after making uniform fused mass, let cool, obtain the processing agent of liquid self-emulsifying type at normal temperature.Add man-hour at the endcapped carrying out polyester fiber works, if add water in the processing agent of above-mentioned self-emulsifying type, stir, then can obtain the emulsion that decentralized medium is the endcapped agent of water.

On the other hand, if not with an organic solvent, such as, this endcapped agent is mixed with above-mentioned aliphatic hydrocarbon system bulking agent and surfactant, heating, after making uniform fused mass, as uniform fused mass, it is stirred and is added on lentamente in warm water, make its emulsification, let cool, then can obtain the emulsion that decentralized medium is the endcapped agent of water as described above.

In the present invention, when obtaining the emulsion as the carbodiimide compound of endcapped agent, as required, in order to keep the emulsion of gained equably or make the emulsibility of this carbodiimide compound improve, can in the impregnable scope of exhaustion rate of carbodiimide compound, as mentioned above, with an organic solvent.As this organic solvent, can enumerate such as, toluene, dimethylbenzene, Fluhyzon etc. are aromatic hydrocarbon based, the glycolss, two such as the alcohols such as ketone, methyl alcohol, ethanol, ethylene glycol, propylene glycol such as acetone, methyl ethyl ketone the halogenated hydrocarbons such as the sulfoxide type such as amide-type, methyl-sulfoxide, carrene, chloroform such as aklylene glycol alkyl ether, dimethyl formamide such as the ethers such as alkane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol list isobutyl ether.These organic solvents can be used alone, and in addition, can two or more combinationally use as required.

In the present invention, as mentioned above, the endcapped agent making to comprise carbodiimide compound together with carrier agent in water during emulsification, preferably and with at least a kind of surfactant be selected from nonionic system surfactant or anion system surfactant.As above-mentioned nonionic system surfactant, can enumerate such as, the polyol type nonionic system surfactants such as polyoxygenated ene-type nonionic system surfactant, alkyl glycoside, sucrose fatty ester such as higher alcohol alkylen oxide adducts, alkylphenol alkylen oxide adducts, styrenated phenol alkylen oxide adducts, fatty acid oxidation alkene addition product, polyol fat race ester alkylen oxide adducts, senior alkylamines alkylen oxide adducts, fatty acid amide alkylen oxide adducts.These nonionic system surfactants can be used alone, and in addition, can two or more combinationally use as required.

On the other hand, as above-mentioned anion system surfactant, can enumerate such as, the carboxylates such as fatty acid soaps, higher alcohol sulfate salt, senior alkyl polyalkylene glycol ethers sulfuric acid, the sulfuric acid of styrenated phenol alkylen oxide adducts, the sulfuric acid of alkylphenol alkylen oxide adducts, sulfated oil, sulfated fatty acid ester, sulfated fatty acid, the sulfuric acids such as sulphation alkene, alkylbenzenesulfonate, alkylnaphthalene sulfonate, naphthalene sulfonate, the formaline condensates of naphthalene sulfonic acids etc., alpha-alkene sulfonate, paraffin sulfonate, the sulfonate such as sulfosuccinic acid diester salt, high alcohol phosphate salt etc.These anion system surfactants can be used alone, and in addition, can two or more combinationally use as required.

In addition, can as required nonionic system surfactant and anion system surfactant be combined.

The addition of above-mentioned surfactant, relative to carbodiimide compound 25 weight portion, is preferably 0.1 ~ 3.5 weight portion, is more preferably 0.1 ~ 3.0 weight portion, more preferably 0.1 ~ 2.5 weight portion.If surfactant is less than 0.1 weight portion, then carbodiimide compound can not emulsion dispersion fully, if more than 3.5 weight portions, then the exhaustion rate of carbodiimide compound may reduce.

In the present invention, as in order to obtain the equipment that emulsion uses in emulsion dispersion, propeller-type agitator, piston-type high-pressure emulsification machine, homogeneous mixer, ultrasonic type emulsion dispersion machine, pressurized nozzles formula mulser, High Rotation Speed high shear type stirring dispersion machine etc. can be used, their equipment of more than two kinds can also be made to combinationally use.

As long as the amount of the endcapped agent used in the present invention decides according to the amount of the terminal carboxyl group of the polyester fiber as object.

The hydrolytic resistance of the polyester fiber works obtained by the present invention is excellent, preferably as uses such as dress shirt, blouse, pants, skirt, polo shirt, T shirt, sportswear, overcoat, sweater, nightwear, school uniform, Work Clothes, gown of a doctor, clean garment, bathing gown, undershirt, lining, lining cloth.Particularly about material polyethylene terephthalate having been carried out endcapped process, be preferred for the uniform purposes of the medical treatment, nursing, food etc. of the autoclaving process of needs 120 DEG C ~ 130 DEG C.

Embodiment

Below, specifically describe the present invention further by embodiment, but the present invention is not limited to these embodiments.In addition, the physical property in embodiment measures as follows.

(mensuration of various physical property)

(1) end carboxy concentration (equivalent/10 of PLA ³kg): the sample of precision weighing is dissolved in orthoresol (moisture 5%) adjustment liquid, in this solution after appropriate interpolation carrene, utilizes the potassium hydroxide methanol solution of 0.02 equivalent to carry out titration, thus measure.

(2) end carboxy concentration (equivalent/10 of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate (PBT) ³kg): be dissolved in after in benzylalcohol by the sample of precision weighing, after adding chloroform, utilize the potassium hydroxide benzyl alcohol solution of 0.1 equivalent to carry out titration, thus measure.

(3) molecular weight of PLA: make sample be immersed in chloroform, will only make the lysed chloroformic solution in PLA portion as mensuration solution.Utilize gel permeation chromatography (GPC) to measure it, obtain weight average molecular weight with polystyrene conversion.

(4) intensity (cN/dtex): use Shimadzu Autograph AG-1S, at specimen length 20cm, measure under the condition of draw speed 20cm/ minute.

(5) hydrolysis experiment: adopt 3 kinds of following methods to be hydrolyzed test.

I () uses (strain) Japan to make made constant temperature and moisture test machine THN064PB, 70 DEG C, place sample in the constant temperature and humidity machine of 90%RH, carry out 7 days hydrolysis process.

(ii) use URMINI-COLOR (infrared ray ミ ニ カ ラ ー (development of テ Network サ system skill)), bath raio 1:50,130 DEG C, be hydrolyzed under the condition of 48hr process.

(iii) use URMINI-COLOR (infrared ray ミ ニ カ ラ ー (development of テ Network サ system skill)), bath raio 1:50,130 DEG C, be hydrolyzed under the condition of 16hr process.

(6) strength retention (%): the intensity of the sample after endcapped process is set to A, when the intensity of the sample after the Water Under solution process of above-mentioned (i), (ii) or (iii) is set to B, calculate strength retention by following formula.

Strength retention (%)={ (intensity A after hydrolysis process)/(the intensity B after endcapped process) } × 100

Below the cloth and silk used in the present embodiment is described.

(making of PLA cloth and silk)

The PLLA sheet stock of fusing point 166 DEG C is adopted and is set as the vacuum drier of 105 DEG C dry 12 hours.Sheet stock by drying is fed in melt spinning machine, carries out melt spinning melt temperature 210 DEG C, obtains the undrawn yarn of kind 100dtex-26 long filament with spinning temperature 220 DEG C, spinning speed 4500m/ minute.This undrawn yarn is utilized preheat temperature 100 DEG C, heat-set temperature 130 DEG C doubly stretches with stretching ratio 1.2, obtain the drawn yarn of 84dtex-26 long filament.Adopt the stretching silk weaving taffeta of gained, after concise at 80 DEG C, carry out 1 minute dry heat-setting at 130 DEG C, obtain PLA fabric.

(making of polyethylene terephthalate cloth and silk)

Known method is adopted to obtain the drawn yarn of the polyethylene terephthalate (PET) of 84dtex-26 long filament.Adopt the long filament of gained to knit taffeta processed, after concise 20 minutes at 80 DEG C, carry out 1 minute dry heat-setting at 170 DEG C, obtain PET fabric.

(making of the cloth and silk of PLA/polytrimethylene terephthalate core sheath silk)

Using the poly-L-lactic acid (optical purity 97%L lactic acid) (PLA) of weight average molecular weight 16.5 ten thousand, fusing point 170 DEG C, residual lactide amount 0.085 % by weight as core A, to be that the polytrimethylene terephthalate (PTT) (fusing point 228 DEG C) of titanium oxide 0.3 % by weight of 0.4 μm is as sheath portion containing average 2 particle diameters, separately melting respectively, spinning temperature 250 DEG C within core sheath compound ratio (% by weight) 70:30, spinning speed 3000m/ minute, to obtain the undrawn yarn of core sheath composite construction of 110 dtexs, 36 long filaments.

Then by this undrawn yarn with draw speed 800m/ minute, stretching ratio 1.3 times, draft temperature 90 DEG C, heat-set temperature 130 DEG C stretch, and obtains the drawn yarn of 84 dtexs, 48 long filaments.

Use the drawn yarn of gained, knit taffeta processed, after concise 20 minutes at 80 DEG C, carry out 2 minutes dry heat-settings at 130 DEG C, obtain PLA/PTT fabric.

(making of polybutylene terephthalate (PBT) cloth and silk)

Known method is adopted to obtain the drawn yarn of the polybutylene terephthalate (PBT) (PBT) of 84dtex-24 long filament.Adopt the long filament of gained to knit taffeta processed, after concise 20 minutes at 80 DEG C, carry out 1 minute dry heat-setting at 170 DEG C, obtain PBT fabric.

(making of " ア ペ Network サ "/cotton silks)

Using " the ア ペ Network サ " as environment-friendly type polyester that gone on the market by デ ュ ポン society with cotton adopts known method with 45/55 ratio carry out blending, the short fibre yarn (A/C) of acquisition 45 (131.2dtex).Adopt the short fibre yarn of gained to knit taffeta processed, 100 DEG C of destarch after 30 minutes, 90 DEG C carry out bleaching, refining 30 minutes, carry out 1 minute dry heat-setting at 190 DEG C, thus obtain A/C fabric.

(making of polyethylene terephthalate/cotton silks)

By polyethylene terephthalate (PET) with cotton adopts known method with 40/60 ratio carry out blending, the short fibre yarn A of acquisition 42 (140.6dtex).In addition, PET and the cotton ratio with 65/35 are carried out blending, obtains the short fibre yarn B of 45 (131.2dtex).Using the short fibre yarn A of gained and short fibre yarn B as warp thread, the silk PET silk doubling of the 84dtex-26 long filament adopting known method to obtain obtained, as weft yarn, obtains TWILL CLOTH.By the TWILL CLOTH of gained 100 DEG C of destarch after 30 minutes, 90 DEG C carry out bleaching, refining 30 minutes, carry out 1 minute dry heat-setting at 190 DEG C, thus obtain polyethylene terephthalate/cotton (PET/C) fabric.The mixed rate of PET/C fabric is 63/37.

(making of cation dyeable polyester cloth and silk)

Adopt method disclosed in Japanese Unexamined Patent Publication 2007-169856, use the cationic dyeable polyester fiber formed by the sulfonated aromatic dicarboxylic acids modification polyethylene terephthalate of 84dtex-26 long filament, weave into order and pay 150g/m ², 24 pins circular knit.The knitted fabric of gained is carried out refining 20 minutes at 80 DEG C, carries out 1 minute dry heat-setting at 170 DEG C, obtain cation dyeable polyester (CDP) knitted fabric.

About the preparation method of the endcapped processing agent used in the present embodiment, below illustrate.

(modulation of endcapped processing agent 1)

By two (2,6-diisopropyl phenyl) carbodiimide (ス タ バ ク ゾ ー Le I LF; ラ イ Application ケ ミ ー ジ ャ パ Application Co., Ltd.) 20.0 weight portions, Ergol 5.0 weight portion (Na カ ラ イ テ ス Network Co., Ltd.), N-butyl phthalimide (Na カ ラ イ テ ス Network Co., Ltd.) 10.0 weight portions, sulfated castor oil (sulfonated castor oil; ミ ヨ シ grease Co., Ltd.) 2.0 weight portions mix, and be heated to 60 DEG C and dissolve equably, under stirring with propeller-type agitator, be added on emulsion dispersion in water 50.0 weight portion of 70 DEG C lentamente and let cool, obtaining endcapped processing agent 1.

(modulation of endcapped processing agent 2)

The N-butyl phthalimide of endcapped processing agent 1 is changed to N-butyl phthalimide (Na カ ラ イ テ ス Network Co., Ltd.), in addition, similarly operate, obtain endcapped processing agent 2.

(modulation of endcapped processing agent 3)

The N-butyl phthalimide of endcapped processing agent 1 is changed to N-propyl phthalimide (Na カ ラ イ テ ス Network Co., Ltd.), in addition, similarly operate, obtain endcapped processing agent 3.

(modulation of endcapped processing agent 4)

The N-butyl phthalimide of endcapped processing agent 1 is changed to N-benzylphthalimide (Na カ ラ イ テ ス Network Co., Ltd.), in addition, similarly operate, obtain endcapped processing agent 4.

(modulation of endcapped processing agent 5)

The Ergol of endcapped processing agent 1 is changed to phenol benzoate (Na カ ラ イ テ ス Network Co., Ltd.), in addition, similarly operate, obtain endcapped processing agent 5.

(modulation of endcapped processing agent 6)

The Ergol of endcapped processing agent 2 is changed to phenol benzoate, in addition, similarly operates, obtain endcapped processing agent 6.

(modulation of endcapped processing agent 7)

The Ergol of endcapped processing agent 3 is changed to phenol benzoate, in addition, similarly operates, obtain endcapped processing agent 7.

(modulation of endcapped processing agent 8)

The Ergol of endcapped processing agent 4 is changed to phenol benzoate, in addition, similarly operates, obtain endcapped processing agent 8.

(modulation of endcapped processing agent 9)

The Ergol of endcapped processing agent 1 is changed to butyl benzoate (Na カ ラ イ テ ス Network Co., Ltd.), in addition, similarly operate, obtain endcapped processing agent 9.

(modulation of endcapped processing agent 10)

The Ergol of endcapped processing agent 2 is changed to butyl benzoate, in addition, similarly operates, obtain endcapped processing agent 10.

(modulation of endcapped processing agent 11)

The Ergol of endcapped processing agent 3 is changed to butyl benzoate, in addition, similarly operates, obtain endcapped processing agent 11.

(modulation of endcapped processing agent 12)

The Ergol of endcapped processing agent 4 is changed to butyl benzoate, in addition, similarly operates, obtain endcapped processing agent 12.

(modulation of endcapped processing agent 13)

Two (2,6-diisopropyl phenyl) carbodiimides of endcapped processing agent 1 are changed to DIC (Tokyo HuaCheng Industry Co., Ltd), in addition, similarly operates, obtain endcapped processing agent 13.

(modulation of endcapped processing agent 14)

Two (2,6-diisopropyl phenyl) carbodiimides of endcapped processing agent 1 are changed to dicyclohexylcarbodiimide (Tokyo HuaCheng Industry Co., Ltd), in addition, similarly operates, obtain endcapped processing agent 14.

(modulation of endcapped processing agent 15)

Use two (2,6-diisopropyl phenyl) carbodiimide 20.0 weight portion, trichloro-benzenes 15.0 weight portion (Na カ ラ イ テ ス Network Co., Ltd.), sulfated castor oil 2.0 weight portion, water 20.0 weight portion, adopt the step same with endcapped processing agent 1 to obtain endcapped 15.

(modulation of endcapped processing agent 16)

The trichloro-benzenes of endcapped processing agent 15 is changed to methyl naphthalene, in addition, similarly operates, obtain endcapped processing agent 16.

(modulation of endcapped processing agent 17)

The trichloro-benzenes of endcapped processing agent 15 is changed to Ergol, in addition, similarly operates, obtain endcapped processing agent 17.

(modulation of endcapped processing agent 18)

The trichloro-benzenes of endcapped processing agent 15 is changed to phenol benzoate, in addition, similarly operates, obtain endcapped processing agent 18.

(modulation of endcapped processing agent 19)

The trichloro-benzenes of endcapped processing agent 15 is changed to butyl benzoate, in addition, similarly operates, obtain endcapped processing agent 19.

(modulation of endcapped processing agent 20)

The trichloro-benzenes of endcapped processing agent 15 is changed to N-butyl phthalimide, in addition, similarly operates, obtain endcapped processing agent 20.

(modulation of endcapped processing agent 21)

The trichloro-benzenes of endcapped processing agent 15 is changed to N-ethyl phthalimide, in addition, similarly operates, obtain endcapped processing agent 21.

(modulation of endcapped processing agent 22)

The trichloro-benzenes of endcapped processing agent 15 is changed to N-propyl phthalimide, in addition, similarly operates, obtain endcapped processing agent 22.

(modulation of endcapped processing agent 23)

The trichloro-benzenes of endcapped processing agent 15 is changed to N-benzylphthalimide, in addition, similarly operates, obtain endcapped processing agent 23.

(modulation of endcapped processing agent 24)

The addition of the Ergol of endcapped processing agent 1 is changed to 1.0 weight portions, and the addition of N-butyl phthalimide changes to 14 weight portions, in addition, similarly operates, and obtains endcapped processing agent 24.

(modulation of endcapped processing agent 25)

The addition of the Ergol of endcapped processing agent 1 is changed to 9.0 weight portions, and the addition of N-butyl phthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 25.

(modulation of endcapped processing agent 26)

The addition of the phenol benzoate of endcapped processing agent 5 is changed to 1.0 weight portions, and the addition of N-butyl phthalimide changes to 14 weight portions, in addition, similarly operates, and obtains endcapped processing agent 26.

(modulation of endcapped processing agent 27)

The addition of the phenol benzoate of endcapped processing agent 5 is changed to 9.0 weight portions, and the addition of N-butyl phthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 27.

(modulation of endcapped processing agent 28)

The addition of the Ergol of endcapped processing agent 4 is changed to 1.0 weight portions, and the addition of N-benzylphthalimide changes to 14 weight portions, in addition, similarly operates, and obtains endcapped processing agent 28.

(modulation of endcapped processing agent 29)

The addition of the Ergol of endcapped processing agent 4 is changed to 9.0 weight portions, and the addition of N-benzylphthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 29.

(modulation of endcapped processing agent 30)

The addition of the phenol benzoate of endcapped processing agent 8 is changed to 1.0 weight portions, and the addition of N-benzylphthalimide changes to 14 weight portions, in addition, similarly operates, and obtains endcapped processing agent 30.

(modulation of endcapped processing agent 31)

The addition of the phenol benzoate of endcapped processing agent 8 is changed to 9.0 weight portions, and the addition of N-benzylphthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 31.

(modulation of endcapped processing agent 32)

The addition of the Ergol of endcapped processing agent 1 is changed to 11 weight portions, and the addition of N-butyl phthalimide changes to 22 weight portions, in addition, similarly operates, and obtains endcapped processing agent 32.

(modulation of endcapped processing agent 33)

The addition of the Ergol of endcapped processing agent 1 is changed to 3.0 weight portions, and the addition of N-butyl phthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 33.

(modulation of endcapped processing agent 34)

The addition of the phenol benzoate of endcapped processing agent 5 is changed to 11 weight portions, and the addition of N-butyl phthalimide changes to 22 weight portions, in addition, similarly operates, and obtains endcapped processing agent 34.

(modulation of endcapped processing agent 35)

The addition of the phenol benzoate of endcapped processing agent 5 is changed to 3.0 weight portions, and the addition of N-butyl phthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 35.

(modulation of endcapped processing agent 36)

The addition of the Ergol of endcapped processing agent 4 is changed to 11 weight portions, and the addition of N-benzylphthalimide changes to 22 weight portions, in addition, similarly operates, and obtains endcapped processing agent 36.

(modulation of endcapped processing agent 37)

The addition of the Ergol of endcapped processing agent 4 is changed to 3.0 weight portions, and the addition of N-benzylphthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 37.

(modulation of endcapped processing agent 38)

The addition of the phenol benzoate of endcapped processing agent 8 is changed to 11 weight portions, and the addition of N-benzylphthalimide changes to 22 weight portions, in addition, similarly operates, and obtains endcapped processing agent 38.

(modulation of endcapped processing agent 39)

The addition of the phenol benzoate of endcapped processing agent 8 is changed to 3.0 weight portions, and the addition of N-benzylphthalimide changes to 6.0 weight portions, in addition, similarly operates, and obtains endcapped processing agent 38.

(modulation of endcapped processing agent 40)

By two (2,6-diisopropyl phenyl) carbodiimide (ス タ バ ク ゾ ー Le I LF; ラ イ Application ケ ミ ー ジ ャ パ Application Co., Ltd.) 20.0 weight portions, to mix using Ergol, N-butyl phthalimide, sulfated castor oil as polyester carrier agent (Ha ンツマン society UNIVADINE PB) 20.0 weight portions of principal component, be heated to 60 DEG C and dissolve equably, under stirring with propeller-type agitator, be added into emulsion dispersion in water 40.0 weight portion of 70 DEG C lentamente and let cool, obtaining endcapped processing agent 40.

By as follows for the example of the processing employing the endcapped processing agent obtained by said method.

(embodiment 1) is for PET fabric, use high pressure dyeing testing machine, use the endcapped processing agent 1 that the solid constituent of endcapped agent is 2%owf, flood in the treatment fluid of bath raio 1:20, use URMINI-COLOR (infrared ray ミ ニ カ ラ ー (development of テ Network サ system skill)), under the condition of 130 DEG C, 30 minutes, make treatment fluid circulate process.In addition, utilize nonionic system surfactant グ ラ Application ア ッ プ US-20 (Sanyo Chemical Industries, Ltd.) 0.5g/L, the sodium hydrate aqueous solution 1.0g/L of concentration 30%, bisulfites 2.0g/L, bath raio 1:20, under the condition of 80 DEG C, 20 minutes, carry out reduction washing.After centrifugal dehydration, be set as carrying out drying in the pin stenter of 130 DEG C.In addition, be set as carrying out 1 minute dry heat-setting with permanent fabric width in the pin stenter of 170 DEG C.After setting, use URMINI-COLOR, bath raio 1:50,130 DEG C, be hydrolyzed under the condition of 48hr process.

In (embodiment 2) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 2, carries out same process.

In (embodiment 3) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 3, carries out same process.

In (embodiment 4) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 4, carries out same process.

In (embodiment 5) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 5, carries out same process.

In (embodiment 6) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 6, carries out same process.

In (embodiment 7) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 7, carries out same process.

In (embodiment 8) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 8, carries out same process.

In (embodiment 9) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 9, carries out same process.

In (embodiment 10) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 10, carries out same process.

In (embodiment 11) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 11, carries out same process.

In (embodiment 12) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 12, carries out same process.

In (embodiment 13) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 13, carries out same process.

In (embodiment 14) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 14, carries out same process.

In (comparative example 1) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 15, carries out same process.

In (comparative example 2) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 16, carries out same process.

In (comparative example 3) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 17, carries out same process.

In (comparative example 4) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 18, carries out same process.

In (comparative example 5) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 19, carries out same process.

In (comparative example 6) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 20, carries out same process.

In (comparative example 7) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 21, carries out same process.

In (comparative example 8) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 22, carries out same process.

In (comparative example 9) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 23, carries out same process.

In (comparative example 10) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 24, carries out same process.

In (comparative example 11) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 25, carries out same process.

In (comparative example 12) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 26, carries out same process.

In (comparative example 13) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 27, carries out same process.

In (comparative example 14) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 28, carries out same process.

In (comparative example 15) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 29, carries out same process.

In (comparative example 16) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 30, carries out same process.

In (comparative example 17) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 31, carries out same process.

In (comparative example 18) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 32, carries out same process.

In (comparative example 19) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 33, carries out same process.

In (comparative example 20) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 34, carries out same process.

In (comparative example 21) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 35, carries out same process.

In (comparative example 22) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 36, carries out same process.

In (comparative example 23) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 37, carries out same process.

In (comparative example 24) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 38, carries out same process.

In (comparative example 25) embodiment 1, endcapped processing agent 1 is changed to endcapped processing agent 39, carries out same process.

In (reference example 1) embodiment 1, do not add endcapped processing agent, carry out same process.

Demonstrate, as shown in reference example 1, when not carrying out endcapped process, the strength of the cloth and silk after hydrolysis experiment reduces, reach the degree that can not measure intensity, on the other hand, as shown in embodiment 1 ~ 14, if processed with comprising N phlhalimide and the benzoic ether endcapped processing agent as essential component, then can give good wet heat durability (table 1).

Demonstrate on the other hand, as shown in comparative example 1 ~ 9, when individually using trichloro-benzenes, methyl naphthalene, N phlhalimide, benzoic ether, although wet heat durability to a certain degree can be given, but wet heat durability when not reaching and use N phlhalimide and benzoic ether, by also showing excellent effect (table 2) with N phlhalimide and benzoic ether.

In addition demonstrate, as shown in comparative example 10 ~ 25, endcapped agent and N phlhalimide and benzoic ether containing ratio in certain scope, the effect (table 3) that performance is excellent especially.

(embodiment 15) is for PLA fabric, use high pressure dyeing testing machine, use the endcapped processing agent 1 that the solid constituent of endcapped agent is 2%owf, be immersed in the treatment fluid of bath raio 1:20, use URMINI-COLOR (infrared ray ミ ニ カ ラ ー (development of テ Network サ system skill)), under the condition of 110 DEG C, 30 minutes, make treatment fluid circulate process.In addition, utilize nonionic system surfactant グ ラ Application ア ッ プ US-20 (Sanyo Chemical Industries, Ltd.) 0.5g/L, soda ash 1.5g/L, bisulfites 2.0g/L, bath raio 1:20, under the condition of 60 DEG C, 20 minutes, carry out reduction washing.After centrifugal dehydration, be set as carrying out drying in the pin stenter of 110 DEG C.In addition, be set as carrying out 1 minute dry heat-setting with permanent fabric width in the pin stenter of 130 DEG C.After setting, use (strain) Japan to make made constant temperature and moisture test machine THN064PB, 70 DEG C, place sample in the constant temperature and humidity machine of 90%RH, carry out 7 days hydrolysis process.

In (embodiment 16) embodiment 15, process cloth and silk is changed to PLA/PTT fabric from PLA fabric, and the temperature of endcapped process was changed to 130 DEG C, 30 minutes from 110 DEG C, 30 minutes, carry out same process.

In (embodiment 17) embodiment 1, process cloth and silk is changed to PBT fabric from PET fabric, carries out same process.

In (embodiment 18) embodiment 1, process cloth and silk is changed to PET/C fabric from PET fabric, carries out same process.Be hydrolyzed after process, from fabric pull-out weft yarn, measure the TENSILE STRENGTH of weft yarn, calculate strength retention.

In (embodiment 19) embodiment 1, process cloth and silk is changed to CDP knitted fabric from PET fabric, under condition similarly to Example 1, carries out endcapped process and setting.After setting, use URMINI-COLOR, bath raio 1:50,130 DEG C, be hydrolyzed under the condition of 16hr process.

(embodiment 20) is for A/C fabric, use high pressure dyeing testing machine, use the endcapped processing agent 1 that the solid constituent of endcapped agent is 2%owf, be immersed in the treatment fluid of bath raio 1:20, use URMINI-COLOR (infrared ray ミ ニ カ ラ ー (development of テ Network サ system skill)), under the condition of 100 DEG C, 30 minutes, make treatment fluid circulate process.In addition, utilize nonionic system surfactant グ ラ Application ア ッ プ US-20 (Sanyo Chemical Industries, Ltd.) 0.5g/L, soda ash 1.5g/L, bisulfites 2.0g/L, bath raio 1:20, under the condition of 60 DEG C, 20 minutes, carry out reduction washing.After centrifugal dehydration, be set as carrying out drying in the pin stenter of 110 DEG C.After drying, use (strain) Japan to make made constant temperature and moisture test machine THN064PB, 70 DEG C, place sample in the constant temperature and humidity machine of 90%RH, carry out 7 days hydrolysis process.

In (comparative example 26) embodiment 15, endcapped processing agent 1 is changed to endcapped processing agent 16, carries out same process.

In (comparative example 27) embodiment 16, endcapped processing agent 1 is changed to endcapped processing agent 16, carries out same process.

In (comparative example 28) embodiment 17, endcapped processing agent 1 is changed to endcapped processing agent 16, carries out same process.

In (comparative example 29) embodiment 20, endcapped processing agent 1 is changed to endcapped processing agent 16, carries out same process.

In (reference example 2) embodiment 15, do not add endcapped processing agent, carry out same process.

In (reference example 3) embodiment 16, do not add endcapped processing agent, carry out same process.

In (reference example 4) embodiment 17, do not add endcapped processing agent, carry out same process.

In (reference example 5) embodiment 18, do not add endcapped processing agent, carry out same process.

In (reference example 6) embodiment 19, do not add endcapped processing agent, carry out same process.

In (reference example 7) embodiment 20, do not add endcapped processing agent, carry out same process.

Demonstrate, as shown in reference example 2 ~ 7, when not carrying out endcapped process, in hydrolysis experiment, the intensity of cloth and silk significantly reduces, but as shown in embodiment 15 ~ 20, by carrying out endcapped process, good wet heat durability (table 4) can be given.

Known on the other hand, as shown in comparative example 26 ~ 29, when using methyl naphthalene as carrier agent, although wet heat durability also improves, the synergy (table 4) of too late Ergol and N-butyl phthalimide.

Demonstrated by above result, the present invention is also effective for the polyester beyond PET.

(embodiment 21) makes PET cloth and silk impregnated in following treatment fluid, (pick-up rate: 82%) after adopting ironer to squeeze unnecessary treatment fluid, utilize and be set as the stenter of 130 DEG C dry 2 minutes, then utilize the stenter heat treatment 3 minutes being set as 170 DEG C.By the PET cloth and silk after heat treatment, the hot water of 60 DEG C being added with nonionic system surfactant グ ラ Application ア ッ プ US-20 (Sanyo Chemical Industries, Ltd.) 0.5g/L is utilized to carry out washing in 10 minutes.PET cloth and silk after washing is utilized and is set as the stenter of 130 DEG C dry 2 minutes.After drying, the method similarly to Example 1 of employing is hydrolyzed test.

(treatment fluid) endcapped agent: 25g/L

Ergol: 5.2g/L

N-butyl phthalimide: 10.5g/L

Sulfated castor oil: 2.5g/L

In (embodiment 22) embodiment 21, PET cloth and silk is changed to PLA cloth and silk, baking temperature is changed to 110 DEG C from 130 DEG C, dry heat treatment temperature is changed to 130 DEG C from 170 DEG C.In addition, hydrolysis experiment adopts method similarly to Example 15 to carry out.

In (embodiment 23) embodiment 22, PLA cloth and silk is changed to PLA/PTT cloth and silk, carries out same process.

In (embodiment 24) embodiment 21, PET cloth and silk is changed to PBT cloth and silk, carries out same process.

In (embodiment 25) embodiment 21, PET cloth and silk is changed to PET/C cloth and silk, carries out same process.

In (embodiment 26) embodiment 22, PLA cloth and silk is changed to A/C cloth and silk, carries out same process.

In (embodiment 27) embodiment 21, heat treatment method is changed to the individual composition undertaken by the saturated vapour of 102 DEG C from dry heat treatment, carry out same process.

In (embodiment 28) embodiment 22, heat treatment method is changed to the individual composition undertaken by the saturated vapour of 102 DEG C from dry heat treatment, carry out same process.

In (embodiment 29) embodiment 23, heat treatment method is changed to the individual composition undertaken by the saturated vapour of 102 DEG C from dry heat treatment, carry out same process.

In (embodiment 30) embodiment 24, heat treatment method is changed to the individual composition undertaken by the saturated vapour of 102 DEG C from dry heat treatment, carry out same process.

In (embodiment 31) embodiment 25, heat treatment method is changed to the individual composition undertaken by the saturated vapour of 102 DEG C from dry heat treatment, carry out same process.

In (embodiment 32) embodiment 26, heat treatment method is changed to the individual composition undertaken by the saturated vapour of 102 DEG C from dry heat treatment, carry out same process.

Demonstrate, as shown in embodiment 21 ~ 26, even if also good wet heat durability can be given by dry heat treatment.In addition, as shown in embodiment 27 ~ 32, even if good wet heat durability (table 5) also can be given by humid heat treatment.

In (embodiment 33) embodiment 1, except endcapped processing agent 1, add Dianix Tuxedo black F concentrate 8.0%owf, carry out same process.

In (embodiment 34) embodiment 15, except endcapped processing agent 1, add the black GS 4.5%owf of DENAPLA, carry out same process.

In (embodiment 35) embodiment 16, except endcapped processing agent 1, add the black GS 4.5%owf of DENAPLA, carry out same process.

In (embodiment 36) embodiment 17, except endcapped processing agent 1, add Dianix Tuxedo black F concentrate 8.0%owf, carry out same process.

(embodiment 37) is for PET fabric, use liquid-flow dyeing machine, use the endcapped processing agent 1 that the solid constituent of endcapped agent is 2%owf, then black for Dianix Tuxedo F concentrate 8.0%owf is fed in the treatment fluid of bath raio 1:25, under the condition of 130 DEG C, 30 minutes, makes treatment fluid circulate process.With the input length of grey cloth be 30m, grey cloth speed processes for 42m/ minute.In addition, utilize nonionic system surfactant グ ラ Application ア ッ プ US-20 (Sanyo Chemical Industries, Ltd.) 0.5g/L, the sodium hydrate aqueous solution 1.0g/L of concentration 30%, bisulfites 2.0g/L, bath raio 1:20, under the condition of 80 DEG C, 20 minutes, carry out reduction washing.After centrifugal dehydration, be set as carrying out drying in the pin stenter of 130 DEG C.In addition, be set as carrying out 1 minute dry heat-setting with permanent fabric width in the pin stenter of 170 DEG C.After setting, use URMINI-COLOR, bath raio 1:50,130 DEG C, be hydrolyzed under the condition of 48hr process.

Demonstrate, as shown in embodiment 33 ~ 36, in bath, drop into dyestuff, even if to carry out dyeing and endcapped process with bath, good wet heat durability (table 6) also can be given.

In addition, as shown in embodiment 37, utilize liquid-flow dyeing machine to carry out growing processing, results verification has good wet heat durability, confirms less than problems (table 6) such as depth limit, two ends aberration.

In (embodiment 38) embodiment 33, endcapped processing agent 1 is changed to endcapped processing agent 40, carries out same process.

In (embodiment 39) embodiment 34, endcapped processing agent 1 is changed to endcapped processing agent 40, carries out same process.

In (embodiment 40) embodiment 35, endcapped processing agent 1 is changed to endcapped processing agent 40, carries out same process.

In (embodiment 41) embodiment 36, endcapped processing agent 1 is changed to endcapped processing agent 40, carries out same process.

In (embodiment 42) embodiment 37, endcapped processing agent 1 is changed to endcapped processing agent 40, carries out same process.

As shown in embodiment 38 ~ 42, by processing with endcapped processing agent 40, thus confirm that there is good wet heat durability (table 7).

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

Claims (9)

1. the processing agent of a polyester fiber works, it is characterized in that, be the processing agent making carbodiimide compound and carrier agent emulsification or dispersion in water or solvent, this carrier agent comprises benzoic acid compounds and phthalimide compound as essential component.

2. the processing agent of polyester fiber works according to claim 1, is characterized in that, this carbodiimide compound is the compound shown in general formula (I),

General formula (I)

In general formula (I),

R1 represents a kind in the aralkyl of alkyl, the cycloalkyl of carbon number 5 ~ 12, the aryl of carbon number 6 ~ 20, allyl and the carbon number 7 ~ 20 being selected from carbon number 1 ~ 20.

3. the processing agent of polyester fiber works according to claim 1, is characterized in that, this carbodiimide is for being selected from N, N '-two-2,6-diisopropyl phenyl carbodiimide, N, N '-two-carbodicyclo hexylimide and N, N ' in-DIC at least a kind.

4. the processing agent of polyester fiber works according to claim 1, is characterized in that, this carrier agent comprises Ergol and N-butyl phthalimide as essential component.

5. a manufacture method for polyester fiber works, is characterized in that, makes the inside of the exhaustion of the processing agent described in any one to polyester fiber works of Claims 1 to 4.

6. a manufacture method for polyester fiber works, is characterized in that, giving, to polyester fiber, to have drying process by the treatment fluid of the processing agent described in any one containing Claims 1 to 4, then has heat treatment step.

7. a manufacture method for polyester fiber works, is characterized in that, in the treatment fluid of the processing agent described in any one containing Claims 1 to 4, drop into polyester fiber, processing during the circulation of this treatment fluid is bathed.

8. a manufacture method for polyester fiber works, is characterized in that, gives to polyester fiber, carry out humid heat treatment by the treatment fluid of the processing agent described in any one containing Claims 1 to 4.

9. adopt the polyester fiber works that method according to claim 5 obtains, it is characterized in that, in the filament cross section of this polyester fiber, from outer layers towards inner layers, this processing agent concentration diminishes.