CN1301350C - Crosslinked polyvinyl alcohol fiber and method for producing the same - Google Patents

Abstract

The present invention relates to crosslinked polyvinyl alcohol raw cord and method for producing the same, and more particularly, to crosslinked polyvinyl alcohol fiber, in which PVA resin having a degree of polymerization of more than 1,000 and a degree of saponification of more than 97.0 mol% is dissolved in dimethyl sulfoxide, the solution is subjected to dry and wet gel spinning using methanol as a coagulation solution, drawn and thermally treated, the resulting polyvinyl alcohol drawn yarn with 500-3,000 deniers is twisted to produce a cabling yarn, the cabling yarn is plied into a 2-ply or 3-ply yarn to produce a raw cord, the raw cord is wound on a bobbin for crosslinking and crosslinked in an aqueous crosslinking solution containing an aromatic aldehyde compound and an acid catalyst.

Description

Polyvinyl alcohol crosslinked fiber and manufacture method thereof

Technical field

The present invention relates to a kind of polyvinyl alcohol crosslinked fiber and manufacture method thereof.In more detail, the polyvinyl alcohol crosslinked fiber that relates to a kind of crosslinking agent adding set and utilize this device to make; The polyvinyl alcohol drawn yarn is twisted, make twisted filament just, described polyvinyl alcohol drawn yarn is to make the degree of polymerization more than or equal to 1,000, saponification degree more than or equal to the PVA resin dissolves of 97.0 moles of % in dimethyl sulfoxide (DMSO) (below be called DMSO), with methyl alcohol as solidifying solvent, through the dry-and wet-type gel spinning, stretching and heat treated 500～3, the polyvinyl alcohol drawn yarn of 000 DENIER, with described just twisted filament Synthetic 2 root or 3 rhizoids, carry out whole sth. made by twisting, make raw cord, and the raw cord of making twisted in cross-linking reaction with after on the bobbin, when the crosslinked aqueous solution that utilization contains aromatic aldehyde compound and acid catalyst carried out cross-linking reaction to twisting in described cross-linking reaction with the raw cord on the bobbin, described crosslinking agent adding set can be induced the cross-linking reaction of the raw cord that batches effectively.

Background technology

Polyvinyl alcohol (below be called PVA) fiber has than polyamide, polyester, more excellent intensity and the spring rate of polyacrylonitrile fibre in the general fiber, particularly because its cementability, water dispersible, alkali resistance and chemical resistance are very excellent, so be often used as various production raw material.

Recently, its purposes variation is used as the reinforcing material of concrete and cement and the reinforcing material of rubber and plastics etc., and in this case, it is in the research and development state as being applied to the big material of possibility of frontier.

Below, introduce the whole bag of tricks of making high strength PVA fiber up to now.

A kind of method of making high strength PVA fiber is disclosed in patent documentation 1, it uses ultra high molecular weight polyethylene as raw material, will be used for the manufacture method of PVA fiber by the gel spinning (patent documentation 2) that powerful stretching process obtains high strength fibre.Gel spinning is a kind of method of common manufacturing high strength fibre, it is made macromolecular compound and solvent after the uniform solution, suitably regulates the state that produces in the spinning process and separates and gelation speed, carry out powerful stretching simultaneously, make high strength fibre thus.

In addition, also once delivered with utilizing described gel spinning and compared, can make the correlation technique of the manufacture method of PVA fiber with better mechanical performance.

A kind of method of the PVA of manufacturing compound silk fiber is disclosed in the patent documentation 3, it is that the ratio (L/D) of the diameter of 0.1～1mm, spinneret orifice length (L) and spinneret orifice is the spinning head of 3～20 spinneret orifice that this method utilization has spinneret orifice diameter (D), carry out the dry-and wet-type spinning, make TENSILE STRENGTH thus more than or equal to the 22g/ DENIER, the initial stage coefficient of elasticity is more than or equal to the 440g/ DENIER, and the coefficient of fineness variation of monofilament (CV) is smaller or equal to 5% PVA compound silk fiber.

But, although utilize the PVA fiber of described method manufacturing to have excellent in mechanical properties, but because the possess hydrophilic property of PVA resin own, in more than or equal to 100 ℃ high-temperature-hot-water, can dissolve, mechanical performance can descend, thereby has limited it greatly and have use in the tire cord etc. of biggest market in fiber in industry.

There is the moisture of minute quantity in inside tires, but under the situation of tire damaged, may have excessive water and flow into, along with galloping, in case tyre temperature rises to about 130 ℃, described moisture becomes hot water, the PVA fiber is sustained damage, thereby jeopardize the safety of automobile.Consequently common PVA fiber can not convenience ground as the reinforcing material of tire.

When using as tire cord, because the high crystalline of PVA fiber has significantly reduced fatigue durability, thereby the also necessary problem that solves the fatigability difference.

Therefore, as the technology of existing raising hot water resistance, fatigue durability, developed PVA spinning with high polymerization degree after, through high magnification hot-stretch and heat treatment, acetalation, utilize the various methods such as cross-linking reaction of acid catalyst.But long fiber (filament) is difficult to enter industrial applications, when using this technology in addition in more than or equal to 130 ℃ hot water, will have problems.

In the particularly previously presented crosslinking technological, before stretching process, crosslinking agent is sneaked in the spinning solution, perhaps extracting the operation or the operation that oils input crosslinking agent.

As the manufacture method of the polyvinyl alcohol fibrid of excellent in resistance to boiling water, proposed to make and contained the precursor of the acetal compound of aliphatic dialdehydes in the patent documentation 4, after its xeothermic stretching, used acid to carry out the method for crosslinking Treatment as crosslinking agent.

As the manufacture method of the polyvinyl alcohol cross filament of excellent in resistance to boiling water, proposed to contain after the xeothermic stretching of precursor of ammonium sulfate as crosslinking agent in the patent documentation 5, carried out the method for crosslinking Treatment.

As mentioned above, the crosslinking technological of Ti Chuing is a mixed cross-linker in stretching process forward direction spinning solution up to now, is perhaps extracting the operation or the operation that oils input crosslinking agent.For described existing cross-linking treatment method, when under more than or equal to 200 ℃ high temperature, carrying out hot-stretch, enter the crosslinking agent generation cross-linking reaction of PVA undrawn yarn inside, draftability is reduced, low-boiling crosslinking agent volatilization reduces cross-linking efficiency, thereby is difficult to have the hot water resistance more than or equal to 130 ℃.

In addition, the bobbin that described cross-linking treatment method just will batch undrawn yarn simply is immersed in crosslinking agent inside, carry out crosslinking Treatment, thereby crosslinking agent can not be soaked in the undrawn yarn that batch the inboard of bobbin, the problem of its existence is that the undrawn yarn that batches in the inboard of bobbin can not carry out crosslinking Treatment fully, and marked difference etc. appears in the outside and the inboard crosslinking Treatment of batching the undrawn yarn on bobbin.

The 4th, 440, No. 711 specifications of [patent documentation 1] United States Patent (USP).

The 4th, 698, No. 194 specifications of [patent documentation 2] United States Patent (USP).

[patent documentation 3] spy opens flat 7-109616 communique.

No. the 210727th, [patent documentation 4] Korea S special permission communique.

[patent documentation 5] Korea S openly speciallys permit communique 96-41438 number

Summary of the invention

Technical task of the present invention is to provide the polyvinyl alcohol crosslinked fiber of a kind of crosslinking agent adding set and this device manufacturing of use, to 500～3, the polyvinyl alcohol drawn yarn twisting of 000 DENIER, make twisted filament just, with described just twisted filament Synthetic 2 root or 3 rhizoids, carry out whole sth. made by twisting, make raw cord, and the raw cord of making twisted in cross-linking reaction with after on the bobbin, the crosslinked aqueous solution that this crosslinking agent adding set utilization contains aromatic aldehyde compound and acid catalyst carries out cross-linking reaction to twisting in described cross-linking reaction with the raw cord on the bobbin, makes cord fabric thread can bring into play good hot water resistance and high-intensity fibrous physical property.

Aforesaidly the invention provides a kind of raw cord that utilizes the crosslinking Treatment that method as described below makes, this method comprises: be 1 by dry-and wet-type or wet type spinning with the degree of polymerization (A), 000～7, after 000 the polyvinyl alcohol spinning, with the undrawn yarn stretching of high magnification with described manufacturing, the operation of heat-treating then; (B) to described polyvinyl alcohol drawn yarn twisting, make twisted filament just, described twisted filament Synthetic 2 root just or 3 rhizoids are carried out whole sth. made by twisting, make the operation of raw cord; (C) described raw cord is impregnated in the crosslinking agent, carries out the treatment process of cross-linking reaction.

In addition, the invention provides a kind of crosslinking agent adding set, described crosslinking agent adding set is characterised in that, it is furnished with bobbin cylindraceous and closed container, wherein said bobbin cylindraceous is formed with mesopore, is formed with a plurality of through holes on periphery, can batch the PVA raw cord; Described closed container is filled with described crosslinking agent, and described cross-linking reaction can be immersed in the described crosslinking agent with bobbin.

In addition, the invention provides a kind of raw cord that utilizes the crosslinking Treatment of method manufacturing as described below, this method comprises: (A) with the degree of polymerization 1,000～7,000, saponification degree is dissolved in the dimethyl sulfoxide (DMSO) more than or equal to the polyvinyl alcohol of 97.0 moles of %, after utilizing dry-and wet-type or wet type spinning to carry out spinning, with the stretch undrawn yarn of described manufacturing of high magnification, the operation of heat-treating then; (B) to described polyvinyl alcohol drawn yarn twisting, make twisted filament just,, carry out whole sth. made by twisting, make the operation of raw cord described just twisted filament Synthetic 2 root or 3 rhizoids; (C) in the crosslinked aqueous solution that contains aromatic aldehyde compound and acid catalyst, add alcohol, the operation of utilizing described crosslinked adding set that described raw cord is reacted.

Preferably the alcohol that adds in the crosslinked aqueous solution in described (C) operation is methyl alcohol.

Be 1 weight %～30 weight % to the content of the alcohol of crosslinked aqueous solution adding preferably in described (C) operation.

Calculate with weight ratio, preferably the content that in described (C) operation raw cord is carried out the aromatic aldehyde compound of crosslinking Treatment is 0.1 weight %～5.0 weight %.

Preferably the aromatic aldehyde compound that in described (C) operation raw cord is carried out crosslinking Treatment is terephthalaldehyde (TDA).

In described (C) operation raw cord is carried out crosslinking Treatment when reaction, preferably use acid catalyst.

Acid catalyst in preferably described (C) operation is an acetic acid.

The invention provides a kind of tire cord dipped cord, its raw cord that utilizes adhering liquid (RFL) to handle described crosslinking Treatment is made, and it has following rerum natura:

(1) cut off loading 20.0～50.0kg, (2) fineness 1,000～6,000 DENIER, (3) hot water resistance more than or equal to 130 ℃, (4) endurance more than or equal to 80%.

The invention provides a kind of raw cord that utilizes the crosslinking Treatment of method manufacturing as described below, this method comprises 500～3, the polyvinyl alcohol drawn yarn twisting of 000 DENIER, make twisted filament just, with described just twisted filament Synthetic 2 root or 3 rhizoids, carry out whole sth. made by twisting, make raw cord, the raw cord of making twists in cross-linking reaction with after on the bobbin, in containing the crosslinked aqueous solution of aromatic aldehyde compound and acid catalyst, add alcohol, make to twist in described cross-linking reaction is carried out cross-linking reaction in this solution with the raw cord on the bobbin operation.The raw cord hot water resistance of crosslinking Treatment is good as mentioned above, so be suitable as tire cord.

Description of drawings

Fig. 1 shows the stereogram of cross-linking reaction of the present invention with bobbin.

Fig. 2 shows the user mode figure of cross-linking reaction with the crosslinking agent adding set of bobbin that utilized of the present invention.

Symbol description

10: cross-linking reaction bobbin, 12a, 12b: coiling tubular axis, 13a, 13b: through hole, 30: crosslinking agent feeding pipe, 40: closed container.

The specific embodiment

As the crosslinking agent that the present invention uses, use can be carried out the aldehyde compound of cross-linking reaction with the hydroxyl of PVA, preferably uses the compound with 2 or 2 above aldehyde radicals in order to improve cross-linking efficiency.The aromatic compound that aldehyde compound more preferably only can soak in the fiber amorphous regions.

Have as such aromatic aldehyde compound: terephthalaldehyde (TDA), m-terephthal aldehyde (IDA), naphthalene dicarbaldehyde (NDA) etc., also can mix the aldehyde compound that uses more than 2 kinds or 2 kinds.

Preferred aromatic aldehyde compound is terephthalaldehyde (TDA) among the present invention.

Core technology of the present invention only is to use the aromatic aldehyde that can soak in the amorphous regions of drawn yarn as crosslinking agent.Described aromatic aldehyde mainly only soaks into amorphous regions, thereby can prevent that the intensity of the drawn yarn that crosslinking agent produces from reducing.

Most important characteristic of the present invention is to have the crosslinking Treatment operation.General crosslinking Treatment is soaked into to fibrous inside in order to make crosslinking agent, and use extracting operation crosslinking agent is dissolved in method in the organic solvent, but in more than or equal to 200 ℃ elevated temperature heat stretching process, be in so not that the crosslinking agent of drawing of fiber inside makes the stretched operation reduction, thereby do not have enough hot water resistances and fatigue durability.Extract the crosslinking agent that uses in the operation and cause organic solvent to be difficult to reclaim, it is difficult that whole operation becomes.

Thereby among the present invention, in order to improve cross-linking efficiency or in order to prevent the damage of fiber, the PVA raw cord of twisted filament is soaked into after the crosslinking agent, have more than or equal to 130 ℃ hot water resistance with more than or equal to the high strength PVA fiber of 80% high fatigue durability by making it that cross-linking reaction take place, making.

Another core technology of the present invention is, adds alcohol and make raw cord carry out cross-linking reaction in the crosslinked aqueous solution that contains aromatic aldehyde compound and acid catalyst.By in crosslinked fluid, adding alcohol, can prevent to a certain extent that the intensity after the cross-linking reaction from reducing.

Manufacture method to PVA fiber of the present invention specifically describes below.

It is about 1,000～7,000 material that PVA uses the degree of polymerization, the preferred PVA with high polymerization degree of 1,500～4,000 that uses.The degree of polymerization was difficult to form fiber smaller or equal to 1,000 o'clock, and the degree of polymerization is more than or equal to 7,000 o'clock, and viscosity is too high, and the manufacturability of spinning reduces.Need have hot water resistance in industry with the normally used high strength PVA fiber in material field, thereby use the PVA of saponification degree more than or equal to 97.0 moles of %.Can make spent glycol, glycerol and DMSO as organic solvent, the preferred use DMSO best to the dissolubility of PVA.Preferably DMSO being refined to moisture uses after smaller or equal to tens of ppm.

Preferred concentration of regulating PVA stoste so that viscosity 50～4, the scope of 000 pool (poise).In order to obtain good rerum natura, viscosity is that 500～3,000 pool effect is relatively good.If viscosity smaller or equal to 50, form the fiber difficulty, and viscosity then reduces the spinnability of fiber more than or equal to 4,000, so be not preferred.

Can be set at-30～30 ℃ in the temperature of coagulating basin and carry out spinning, but, the temperature of coagulating basin can be set in-10～10 ℃ in order to form even gel.The temperature of coagulating basin is during smaller or equal to-30 ℃, and the PVA spinning solution may freeze sometimes, so be not preferred.The temperature of coagulating basin is during more than or equal to 30 ℃, owing to can not form gel, and reduced spinnability.

The manufacture method of PVA fiber has dry process, damp process and two kinds of dry-and wet-type methods that method is mixed, and for the high strength PVA fiber autofrettage that needs the high magnification stretching process, adopts the dry-and wet-type method effective.When making the PVA silk can be 5～200mm with air-gap setting, but for powerful hot-stretch, the air gap that preferred 5～50mm is narrow; Air gap is during smaller or equal to 5mm, and operability is poor.Opposite air gap is during more than or equal to 200mm, and compare its degree of crystallinity with gelation bigger, can not the high magnification hot-stretch, and in addition owing at nozzle cross-section interfibrous fusion takes place, so can reduce productivity.

In the high strength PVA fiber autofrettage, stretching process is extremely important to improving high strength and hot water resistance.The mode of heating of stretching process has hot blast heating type and roller heating type, and the roller heating type adopts hot blast heating type better effects if because silk contacts with roll surface, and fibrous face is impaired easily so make in the high strength PVA fiber.Heating can be carried out 140～250 ℃ temperature, preferably carries out at 160～230 ℃.Heating-up temperature is during smaller or equal to 140 ℃, because motion fully of strand can not be carried out powerful hot-stretch, and heating-up temperature is during more than or equal to 250 ℃, and PVA decomposes easily, makes rerum natura low.

Secondly, the PVA fiber that is used as tire cord in industry in material need have high strength and fatigue durability, thereby with the twisted filament of PVA drawn yarn, the manufacturing raw cord.When utilizing the twisted filament operation of general synthetic fiber, twisting count increase then intensity reduces, but can improve fatigue durability.So it is very important selecting suitable twisting count according to application target during operation.For example the tire cord that partly uses at carcass is the twisting count with 300～500TPM (twisting count/rice), and 1500d/2p is carried out first twist and eventually twists with the fingers the back and use.

For the hot water resistance and the fatigue durability of the PVA raw cord that improves twisted filament, add crosslinking agent it is reacted.

For crosslinking agent is only soaked in the noncrystalline field of the PVA of high magnification twisted filament fiber, as previously mentioned, use aromatic aldehyde as crosslinking agent.

Among the present invention, can enumerate terephthalaldehyde (TDA) as preferred aromatic aldehyde compound.With respect to fiber, the working concentration of cross-linking compounds is 0.1 weight %～5 weight %, is preferably 0.5 weight %～2.0 weight %.The concentration of cross-linking compounds is during smaller or equal to 0.1 weight %, and hot water resistance is inadequate smaller or equal to 130 ℃.The concentration of cross-linking compounds is during more than or equal to 5.0 weight %, and then intensity reduces obviously, is difficult to as high-intensity tire cord.

For the OH base that makes cross-linking compounds and PVA reacts, need acid catalyst in the cross-linking compounds aqueous solution.As acid catalyst, can use acid such as sulfuric acid or acetic acid, but consider the adjusting and the security of reaction speed, preferred acetic acid.The concentration of acid catalyst is preferably the 5 weight %～30 weight % of the cross-linking compounds aqueous solution.The concentration of acid catalyst is during less than 5 weight %, and the speed of carrying out cross-linking reaction is slow excessively, and when surpassing 30 weight %, owing in reaction after washing operation, be difficult to remove acid catalyst, so be not preferred.

Another core technology of the present invention is, by add alcohol in the crosslinked aqueous solution that contains aromatic aldehyde compound and acid catalyst, makes raw cord carry out cross-linking reaction.By in crosslinked fluid, adding alcohol, can prevent to a certain extent that the intensity after the cross-linking reaction from reducing.

Among the present invention, as the alcohols that is added in the crosslinked aqueous solution, particular methanol, ethanol, propyl alcohol and butanols etc., wherein methyl alcohol more preferably.Preferably add alcohol in the scope that is equivalent to the crosslinked aqueous solution 1 weight %～30 weight %.Alcohol is during less than 1 weight %, when carrying out cross-linking reaction, because that intensity reduces is excessive, is difficult to as high-intensity tire cord, and during greater than 30 weight %, and is unfavorable aspect expense, and cross-linking reaction carries out slowly excessively, so be not preferred.

Another core technology of the present invention is, with polyvinyl alcohol drawn yarn Synthetic 2 root or 3 rhizoids, make and batch after cross-linking reaction is with the raw cord on the bobbin, make to twist in described cross-linking reaction and be immersed in the crosslinked fluid, carry out cross-linking reaction with the raw cord on the bobbin.

Soak into for the amorphous regions of the PVA fiber that makes good crystallinity is crosslinked compound, adopt reacting liquid temperature is set at more than or equal to 50 ℃, improve the method for the activity degree of cross-linking compounds, and reaction vessel pressurization back is used.In addition, cross-linking reaction time is different because of cross-linking compounds and condition, but cross-linking reaction time is effective during more than or equal to 30 minutes.But when carrying out cross-linking reaction for a long time, reduce intensity significantly, so not preferred.

For by cleaning and the dry PVA raw cord of crosslinking Treatment and the cementability of rubber of improving, after the PVA of crosslinking Treatment raw cord adheres to REL liquid (below be called dipping), enforcement drying and heat treatment.The dipping operation is described more specifically and is exactly, dipping is to realize by the resin bed that makes fiber surface dipping be known as RFL (resorcinol-formaldehyde-latex), implement dipping and be for improve tire cord with fiber originally with the deficiency of the cementability difference of rubber.

Among the present invention,, can use the material that utilizes following method preparation as the adhering liquid that is used for bonding PVA raw cord and rubber.The embodiment of following record is used for clearly stating more the present invention, and scope of the present invention is not limited thereto.

29.4 resorcinol 45.6 weight portions of weight %

Pure water 255.5 weight portions

37% formalin 20 weight portions

NaOH 3.8 weight portions of 10 weight %

Prepare after the described solution, make its reaction, stir after 5 hours, add following composition while stir at 25 ℃.

VP-latex 300 weight portions of 40 weight %

Pure water 129 weight portions

28% ammoniacal liquor 23.8 weight portions

Add after the described composition, make it 25 ℃ of slakings 20 hours, keeping the concentration of solid constituent is 19.05%.

RFL liquid is impregnated into inside dearly when adhering to RFL liquid, when adhering to RFL liquid, makes it carry out 0.5%～3% elongation, and the adhesive rate (hereinafter referred to as DPU) of perhaps controlling RFL liquid is 3.0 weight %～9.0 weight %.Elongation was smaller or equal to 0.5% o'clock, and DPU is more than or equal to 9 weight %, and it is excessive to form, and is impregnated into filamentary inside dearly, and fatigue durability is reduced.In addition, when elongation more than or equal to 3% the time, raw cord produces excessive tension force, causes raw cord impaired.Heat treatment must be carried out at 170～230 ℃, carries out particularly preferably in best 200～220 ℃ of the motion of the PVA molecule of noncrystalline part.At this moment, the tension force minimum that fiber is subjected to allows molecular motion to greatest extent, and makes heat treated effect best, can make high-intensity PVA dipped cord thus.In the heat treatment step that after raw cord is immersed in the maceration extract, carries out, importantly percentage elongation is set at 0～-5%.Percentage elongation was more than or equal to 0% o'clock in the heat treatment, and the elongation of dipped cord is low, thereby when being used for requirement and having tire cord more than or equal to 60% high fatigue durability, cord fabric thread took place cut off or break-off.Opposite percentage elongation was smaller or equal to-5% o'clock, because the molecule overexercise producing recrystallization with fiber axis in vertical direction, reduces intensity.When the crosslinking agent that does not have in the crosslinking Treatment operation in advance to clean remains in the inside of fiber, residual crosslinking agent becomes the impurity of PVA fibre, it can be by heat-treating more than or equal to 200 ℃ temperature, residual cross-linker is reacted or volatilize, with the crosslinked effectiveness of further raising.

At this, the cross-linking reaction of using when described crosslinking Treatment is described simply is with bobbin and user mode thereof.

Fig. 1 shows the stereogram of cross-linking reaction of the present invention with bobbin, and Fig. 2 shows the user mode figure of cross-linking reaction of the present invention with bobbin.

When carrying out described crosslinking Treatment, be provided with cross-linking reaction bobbin 10, described cross-linking reaction is provided with bobbin 10 and forms the 2nd bobbin 10b that cross-linking reaction is used the opposite side of bobbin 10 with the 1st bobbin 10a and the formation cross-linking reaction of a side of bobbin 10, and described the 2nd bobbin 10b can combine discretely with described the 1st bobbin 10a; Described the 1st, the 2nd bobbin 10a, 10b are respectively equipped with coiling tubular axis 12a, the 12b of the drum that batches PVA raw cord 1, described coiling tubular axis 12a, 12b form mesopore 16a, 16b respectively, form a plurality of through hole 13a, 13b at periphery, be formed with at the medial end of described the 1st, the 2nd bobbin 10a, 10b and be used for corresponding in conjunction with described the 1st bobbin 10a and described the 2nd bobbin 10b in conjunction with jaw 18a and engagement groove 18b.

Wherein, described the 1st bobbin tooth 14a that configuration combines with described the 1st bobbin 10a, make in conjunction with after the side of the mesopore 16a that forms with bobbin 10 of described cross-linking reaction airtight, described the 2nd bobbin tooth 14b that combines with described the 2nd bobbin 10b is provided with the crosslinking agent feeding pipe 30 of supplying with described crosslinking agent 2, utilization is with the feedway of the described crosslinking agent 2 of specific pressure feed, mesopore 16a to the formation in described cross-linking reaction usefulness bobbin 10 of described crosslinking agent 2,16b pressurization or decompression drop into crosslinking agent 2 to batching in described cross-linking reaction with the inboard of the PVA raw cord 1 on the bobbin 10.

The described cross-linking reaction bobbin 10 of PVA raw cord 1 is batched in setting, make the state that is in the described crosslinking agent 2 of dipping in its closed container 40 that when crosslinking Treatment, is being filled with crosslinking agent 2, to described crosslinking agent 2 pressurizations or decompression, supply with crosslinking agent 2 with specific pressure by described crosslinking agent feeding pipe 30, the described crosslinking agent of supplying with 2 is by respectively the wind the line tubular axis 12a of described cross-linking reaction with bobbin 10, a plurality of through hole 13a of the last formation of 12b, 13b, move laterally from the inboard of the PVA raw cord 1 that batches, perhaps, can make like this and batch in the inside and outside cross-linking reaction of carrying out equably of described cross-linking reaction with the PVA raw cord 1 on the bobbin 10 from the lateral medial movement of PVA raw cord 1.

Embodiment

Enumerate specific embodiment and comparative example below, formation of the present invention and effect are described in further detail, these embodiment are used for understanding more clearly the present invention, and scope of the present invention is not limited thereto.Profit is estimated its physical property in the following method in embodiment and the comparative example.

(a) PVA cord fabric thread intensity (kgf)

Under 107 ℃, dry 2 hours, utilize the low-speed tensile type cupping machine of Instron (ィ Application ス ト ロ Application) company then, at twisting 80TPM (80 twisting count/rice) afterwards, be 300 meters/minute with draw speed and measure that sample is long to be 250mm.

(b) hot water resistance (WTb, ℃)

Select the raw cord of 3,000 DENIER in the raw cord of twisted filament, it is long to be cut into 4cm, and making terminal loading afterwards is the 3g/ branch.It is deposited on the pressurization that is filled with water with in the glass container, its speed with 2 ℃/minute is rapidly heated, the temperature when measuring fiber simultaneously and being cut off.

(c) endurance

Utilize normally used Goodrich disc type fatigue tester (Goodrich Disc Fatigue Tester) in the fatigue test of tire cord, carry out fatigue test, measure residual intensity, relatively endurance.The condition of fatigue test is 120 ℃, 2500RPM, compression 10% and 18%, and after the fatigue test, dipping is 24 hours in tetrachloro-ethylene liquid, make rubber swelling after, rubber is separated the mensuration residual intensity with cord fabric thread.Mensuration to residual intensity is as follows.In 107 ℃ of dryings 2 hours, utilize common instron then, measure according to described (a) method.

Embodiment 1

PVA uses the saponification degree and the degree of polymerization to be respectively the powdered substance of 99.9 moles of % and 2,000, and methyl alcohol and DMSO use the refining solvent of moisture more than or equal to 100ppm.With DMSO and methanol mixed, make mixed solvent, making the methanol content in the solvent is 5 volume %, with the PVA dissolving, make its relatively and the PVA spinning solution be 22 weight %.Then by having utilized the dry-and wet-type spin processes dissolving PVA fiber of gel spinning.At this moment the number of nozzle and diameter are respectively 500 and 0.5mm, and use L/D is 5 round nozzle, and air gap is 50mm, and the solvent in the coagulating bath uses methyl alcohol.At this moment the condition that keeps coagulating bath is that the mixed proportion of solvent/methyl alcohol is 20/80, and temperature is 0 ℃.After the extraction groove, in the PVA fiber DMSO solvent can not be arranged.If residual solvent in silk in the elevated temperature heat stretching process variable color takes place, this is the major reason that causes the rerum natura of filum terminale to reduce.2 sections hot blast heating types are used in hot-stretch, and in the hot blast heating-up temperature, the 1st section is 200 ℃, and the 2nd section is 220 ℃, and adjusting total stretching ratio is 13.5 times.Finally produce the high strength PVA fiber of intensity 13.0g/d, elongation 7.0%.To such drawn yarn twisting, first twist and whole the sth. made by twisting are respectively 300/300TPM, make the curtain filament.The intensity of the raw cord of making is 34kgf.The crosslinking agent adding set of cross-linking reaction can be effectively induced in utilization, makes to batch in cross-linking reaction is immersed in terephthalaldehyde (TDA) as aromatic aldehyde with the raw cord on the bobbin, carries out crosslinking Treatment.The process of crosslinking Treatment is as follows.With the acetate dissolution of the terephthalaldehyde of 2 weight % and 10 weight % in water, make after the crosslinked aqueous solution, in the described crosslinked aqueous solution, add the methyl alcohol of 10 weight %, make then be in batch cross-linking reaction with bobbin on the raw cord of state flooded therein 1 hour in 70 ℃, wash after the reaction.The intensity of the raw cord after crosslinked is 33.6kgf, floods with RFL liquid, makes the PVA dipped cord.Evaluation of physical property the results are shown in table 1.

Embodiment 2 and 3

With the ratio that the ratio shown in the table 1 is regulated terephthalaldehyde, acetic acid, methyl alcohol, compare intensity and endurance after the crosslinking Treatment.

Comparative example 1 and 2

Comparative example 1 is the situation of not carrying out crosslinking Treatment, and the result is as shown in table 1.Comparative example 2 is the fibrous physical properties when not using methyl alcohol in the aqueous solution, and the result is as shown in table 1.

Comparative example 3 and 4

Comparative example 3 is situations of implementing cross-linking reaction after 6 hours, and the result is as shown in table 1.Relatively 4 is situations of 30 ℃ that reaction temperature is set in, and the result is as shown in table 1.

Table 1

Classification		Embodiment	1	Embodiment 2	Embodiment 3	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
										Crosslinked condition	Terephthaldehyde's aldehyde concentration (the weight %/aqueous solution)	2	2	2	-	5	2	2
Acetate concentration (the weight %/aqueous solution)	10	10	15	-	10	10	10
								Methanol concentration (the weight %/aqueous solution)	10		5	10		-	10	10
Reaction temperature (℃)	70	70	70	-	70	70	30
								Reaction time (branch)	60		60	60	-	60	360	60
Fiber characteristics	The TENSILE STRENGTH of drawn yarn (g/d)	13.5	13.5	13.5	13.5	13.5	13.5										13.5
								The intensity of raw cord (kgf)	34	34	34	34	34	34	34
	The intensity of crosslinked raw cord (kgf)	33.6	32.8	32.1	-	21.2	28.2									33.4
								The intensity of dipped cord (kgf)	37.9	37.2	36.5	38	26.4	31.5	38.2
	Fatigue durability (%)	99	95	97	62	98	98									98
								Hot water resistance (℃)	172	167	172	107	170	171	108

Claims (10)

1, a kind of adding set of crosslinking agent is characterized in that, it is provided with cross-linking reaction bobbin, the 1st bobbin tooth, the 2nd bobbin tooth and closed container, wherein,

Cross-linking reaction is made of the 1st bobbin and the 2nd bobbin with bobbin, and described the 1st bobbin has a plurality of through holes that are used to batch the polyvinyl alcohol raw cord and form on periphery, and the coiling tubular axis that is formed with in conjunction with the mesopore tubular of jaw by the bottom constitutes; Described the 2nd bobbin has a plurality of through holes that are used to batch the polyvinyl alcohol raw cord and form on periphery, and is made of the coiling tubular axis that top is formed with the mesopore tubular of engagement groove, described engagement groove and described the 1st bobbin combine the jaw combination;

Described the 1st bobbin tooth is combined in the top of the mesopore of described the 1st bobbin, breaks away from the polyvinyl alcohol raw cord that prevents to be batched, and seals the mesopore of described cross-linking reaction with bobbin;

Described the 2nd bobbin tooth is combined in the bottom of the mesopore of described the 2nd bobbin, break away from the polyvinyl alcohol raw cord that prevents to be batched, and being combined with the crosslinking agent feeding pipe, described crosslinking agent feeding pipe is supplied with crosslinking agent to described cross-linking reaction with the inboard of the mesopore of bobbin by pressurization or decompression;

Described closed container is used to hold described crosslinking agent, cross-linking reaction bobbin, the 1st bobbin tooth and the 2nd bobbin tooth.

2, a kind of raw cord through crosslinking Treatment, it is to utilize the method that comprises following operation to make, (A) be 1 by dry-and wet-type or wet type spinning with the degree of polymerization, 000～7, after 000 the polyvinyl alcohol spinning, with the not stretch spinning stretching of high magnification with described manufacturing, the operation of heat-treating then; (B) make twisted filament just to described through heat treated polyvinyl alcohol drawn yarn twisting, described twisted filament Synthetic 2 root just or 3 rhizoids are carried out whole sth. made by twisting, make the operation of raw cord; (C) in the crosslinked aqueous solution that contains the aromatic aldehyde compound, add alcohol, utilize the adding set of the described crosslinking agent of claim 1 to make described raw cord carry out the operation of cross-linking reaction.

3, the raw cord through crosslinking Treatment as claimed in claim 2 is characterized in that, in described (A) operation, the saponification degree of polyvinyl alcohol is more than or equal to 97.0 moles of %, and is dissolved in the dimethyl sulfoxide (DMSO).

4, the raw cord through crosslinking Treatment as claimed in claim 2 is characterized in that, the alcohol that adds in the crosslinked aqueous solution in described (C) operation is methyl alcohol.

5, the raw cord through crosslinking Treatment as claimed in claim 2 is characterized in that, the content that adds the alcohol of the crosslinked aqueous solution in described (C) operation is 1 weight %～30 weight %.

6, the raw cord through crosslinking Treatment as claimed in claim 2 is characterized in that, in weight ratio, the content that in described (C) operation raw cord is carried out the aromatic aldehyde compound of crosslinking Treatment is 0.1 weight %～5.0 weight %.

7, the raw cord through crosslinking Treatment as claimed in claim 2 is characterized in that, the aromatic aldehyde compound that in described (C) operation raw cord is carried out crosslinking Treatment is for to benzene two acetals.

8, the raw cord through crosslinking Treatment as claimed in claim 2 is characterized in that, in described (C) operation, the crosslinked aqueous solution also comprises acid catalyst.

9, the raw cord through crosslinking Treatment as claimed in claim 8 is characterized in that, the acid catalyst in described (C) operation is an acetic acid.

10, tire cord dipped cord, it is that the RFL processing raw cord through crosslinking Treatment as claimed in claim 2 that is used as adhering liquid is made, it has following rerum natura:

(1) cut off loading 20.0～50.0kg, (2) fineness 1,000～6,000 DENIER, (3) hot water resistance more than or equal to 130 ℃, (4) endurance more than or equal to 80%.

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