CN103541217A - Fiber based on polyvinyl alcohol structure - Google Patents

Abstract

The invention relates to a fiber based on a polyvinyl alcohol structure. The hot water shrinkage ratio (Wsr) of the fiber is 10% or higher, the strength of the fiber is 4g/d or higher, and the tan delta of the fiber is at least 0.10 at 90 DEG C; the fiber basically has one tan delta peak within a temperature scope of 60-120 DEG C; the breaking elongation of the fiber is at least 10%.

Description

Fiber based on polyvinyl alcohol structures

The present invention relates to high fatigue proof vinylal fibre, and relate to the high endurance impregnated wire that comprises vinylal fibre and the method for producing this impregnated wire.The invention still further relates to the high fatigue-resisting rubber reinforcing material that comprises this impregnated wire.

At present, fiber is widely used for doing the reinforcing material of cement, rubber, resin etc.For example, widely used as rubber reinforcement material is dipping (impregnation) line, and it is to prepare to improve its adherence to rubber by fibre bundle being implemented to special processing with for example RFL (resorcinol formaldehyde latex) finishing agent.Require this kind of impregnated wire not only to there is excellent mechanical properties, and there are other performances such as endurance.Specifically, at impregnated wire, as tire cord, brake hose reinforcing material, when belt reinforcing material and other materials, require them to possess the performances such as highly withstand voltage, endurance, dimensionally stable.

So far, as rubber reinforcement material, generally use polyvinyl alcohol (PVA) series fiber, rayon fiber, polyester fiber, nylon fiber, aramid fibre etc.Yet there is some problem in these fibers.The intensity of rayon fiber is low.For guaranteeing higher enhancing effect, unavoidably to use a large amount of this kind of low-intensity rayon fibers, still, this certainly will cause the increase of production cost and product size excessive., because elastic modelling quantity is low, externally under effect of stress, will there is huge distortion in nylon fiber.Polyester fiber is solid and possess to a certain extent high-modulus, but they are very poor to the adherence of rubber.In addition, in view of they usually shrink after sulfuration, the product size that comprises them will change.Aromatic polyamides is solid and possess high elastic modulus, but they are all very poor to the adherence of rubber and their endurance.On the other hand, PVA series fiber is solid and possess high elastic modulus, and good to the adherence of rubber.In addition, after sulfuration, their size seldom changes.For these reasons, PVA series fiber is widely used as the rubber reinforcement material of flexible pipe, belt and so on.

Strengthening car seat area is to drive comfortable requirement.Yet in contrast, nearest trend is towards automotive small future development, for this reason, engine room and wheel space all will be dwindled.For meeting this requirement, in many situations, brake hose is installed in than in the past narrower space, bends to maximum 30mm, and the very small angles of general preferred maximum 20mm radius of curvature also will repeatedly expand and compress under rigor condition.In addition, for reducing the maintenance cost of automobile and reducing maintenance, brake hose requires to have higher endurance.Similarly, the reinforcing material of tire cord, belt and so on also requires to possess higher endurance.

Under above-mentioned situation, proposed to possess more high strength and elasticity and possessed higher fatigue proof impregnated wire, for example, in saying this patent publication number 207338/1994, suggestion adopts high polymerization degree PVA fiber.This PVA series fiber has higher intensity and the elastic modelling quantity of Geng Gao.For they are configured as to impregnated wire, vinylal fibre is immersed in RFL liquid, reduce it is applied to tension force around here, so that RFL is deeply penetrated into line inside, after so flooding, line is implemented to heat-set treatment, improve its tension force therebetween to reduce its irregular torsion.Yet, in the method, adopted the height-oriented high strength of polymer chain, high elasticity vinal.Therefore, in this case, although the immersion condition of this polyvinyl alcohol anchor line (string) is subject to special control as above, the endurance of impregnated wire still cannot be brought up to satisfied degree.Its endurance still dislikes low under all such rigor condition as mentioned above.

On the other hand, Japanese patent application publication No. 189066/1995 discloses a kind of high endurance impregnated wire, and it adopts the high vinylal fibre that extends.This vinylal fibre is prepared by appropriate restrained stretching ratio, thereby possesses the high extension at break between 6～12%.Japanese patent application publication No. 218221/1996 discloses and has adopted vinylal fibre as the method for rubber reinforcement material and so on.For improving its endurance, wear-resisting and DIMENSIONAL STABILITY, this vinylal fibre is carried out to 1～15%, preferably 2～10% thermal contraction is processed, and makes whereby the orientation disorder of its amorphous segment.Yet, only depend on and increase its elongation at break, be still difficult to improve satisfactorily the endurance of impregnated wire fiber.

Consider the above variety of problems of enumerating, the object of this invention is to provide a kind of vinylal fibre and impregnated wire that possesses the excellent properties such as good endurance, the method for producing the rubber reinforcement material that possesses good fatigue proof impregnated wire and comprise this impregnated wire is also provided.

Fig. 1 is the curve map that schematically represents relation between the tan δ value of vinylal fibre of the present invention (curve A), common dry-spinning vinylal fibre (curve B 1 and curve B 2) and common wet spinning vinylal fibre (curve C) and temperature.

Fig. 2 is the curve map that schematically represents relation between the tan δ value of the vinylal fibre prepared in example and comparative example and temperature.

Preferred embodiment is described below.

The present invention is based on following discovery: specific vinylal fibre, specifically, and this fiber 10% or higher hot water shrinkage (Wsr), and 4g/d or higher intensity, the tan δ that it has at 90 ℃ is at least 0.10; And in 60～120 ℃ of temperature ranges, substantially there is 1 tan δ peak; Its extension at break is at least 10%.At the tan δ of 90 ℃, be at least 0.12, in 60～120 ℃ of intervals, substantially there is 1 tan δ peak, and elongation at break is at least those fibers of 12%, there is good endurance.Owing to being structure so distinguishingly, this vinylal fibre can guarantee to have height endurance, even if such as flexible pipe (as, brake hose, powered flexible pipe and so on), under the rigor condition of the reinforcing material of tire, belt and so on use.

In the present invention, importantly, vinylal fibre is at least 0.12 at the tan δ of 90 ℃, but is at least preferably 0.13, is at least more preferably 0.14.Term as used herein tan δ (loss angle tangent) is a kind of dynamic viscoelastic parameter of sample, shows response when this sample vibrates under assigned frequency and regulation amplitude.Specifically, it points out that sample output waveform is with respect to the tangent of the phase shift δ of its input waveform.Its numerical formula is tan δ=E "/E ', the energy storage elastic modelling quantity of E ' representative sample wherein, E " represents its loss elastic modulus.At 90 ℃, have in the polymer fiber of high tan δ numerical value, the amorphous segment of polymer has height activity and the height free degree.Therefore,, when being subject to external stress, this polymer fiber can absorb well and be relaxed, thereby it has high endurance.

For example, when running car is in conventional environment, the brake hose in automobile will be heated to about 70 ℃, yet apart from decline ramp, continue to travel under such rigor condition along long at automobile, just will be heated to about 90 ℃.Therefore, the accelerated durability test of brake hose carries out the temperature of about 90 ℃ without exception.Vinylal fibre of the present invention has high 90 ℃ of tan δ numerical value, thereby can guarantee good endurance, even if under all that rigor condition as mentioned above.The upper limit of 90 ℃ of tan δ of this vinylal fibre is not subject to specific limited, yet usually, the highest by 0.30, preferably the highest by 0.25.

Important is also, vinylal fibre of the present invention, at 90 ± 30 ℃ (preferably 90 ± 20 ℃), in other words, has 1 tan δ peak that is positioned at 60～120 ℃ of (preferably 70～110 ℃) temperature ranges substantially.Although still imperfectly understand, it is believed that in the polymer fiber that possesses this kind of peak, the amorphous segment of polymer is unrestricted, so they have high-freedom degree.It is believed that this kind of fiber relaxes and to absorb the ability of external stress high, thereby its endurance is also high.

Traditional polyvinyl alcohol series fiber is low at the tan δ numerical value of 90 ℃, and they conventionally do not have 1 and are positioned at 60～120 ℃ of interval tan δ peaks.Their tan δ curve is such: in the curve of dry-spinning vinylal fibre, tan δ increases with the rising of environment temperature, and they have the 1st peak that is positioned at approximately 70 ℃.When temperature is during higher than 70 ℃, tan δ reduces rapidly; And in the time of about 90 ℃, it is reduced to about 0.06 left and right.Along with the further rising of temperature, tan δ increases again, thereby demonstrates the 2nd peak that is positioned at 120～130 ℃.Along with temperature further raises, it reduces again, thereby shows above-mentioned the 2nd peak (seeing curve B 1 and the B2 of Fig. 1).This tan δ curve comes from primary structure and the secondary structure of the polyvinyl alcohol that forms fiber, thereby demonstrates 2 peaks that are positioned at 60～80 ℃ and 110～130 ℃.The secondary structure of common polythene alcohol series fiber is subject to the constraint of hydrogen bond, and the tan δ of whole fiber is very low.

On the other hand, about wet spinning vinylal fibre, the amorphous segment of polyvinyl alcohol is due to below former thereby have the utmost point low degree free degree, and therefore the tan δ of whole fiber is also low.Specifically, in view of the secondary structure of polyvinyl alcohol has low degree-of-freedom, wet spinning vinylal fibre does not have clear and definite 2tan δ peak, and this point is different from dry-spinning vinylal fibre above-mentioned.Therefore, they do not have the large protuberance tan δ peak (seeing Fig. 1 curve C) that is arranged in 60～120 ℃.In this fiber, amorphous segment has than the low free degree of corresponding segment in the present invention fiber.When being subject to external stress (especially at about 90 ℃), these traditional fibre cannot absorb well and be relaxed, so their endurance is very poor.

Contrary with them, in fiber of the present invention, the structure of amorphous segment is by disordering rightly, thereby whole fibre structure is able to homogenizing well.As its result, it is believed that fiber of the present invention has 1 tan δ peak substantially, in addition, the free degree in its amorphous segment is also improved, thereby demonstrates so large tan δ peak (seeing curve A in Fig. 1).

Said 90 ℃ here () tan δ value is that method described in adopting embodiment is below measured.Fiber of the present invention has the protuberance tan δ peak that is positioned at 60～120 ℃ (being preferably placed at 70～110 ℃).

Yet the vinylal fibre with specific tan δ curve can not have high-caliber endurance, also must stipulate clearly the extension at break of vinylal fibre, just can make this fiber possess high endurance.Specifically, the extension at break of vinylal fibre must be at least 12%.Preferably this numerical value is at least 13%, more preferably at least 14%, even more preferably at least 15%, further preferably at least 16%.Possess the extension at break being defined within the scope of this, vinylal fibre just can have the endurance significantly improving.

Although imperfectly understand, but why the endurance that it is believed that vinylal fibre can and improve its extension at break by its tan δ curve of concrete regulation, be improved significantly, due in high extension at break vinylal fibre, polyvinyl alcohol chain may have the certain rich length with respect to fibre length, so fiber can tolerate larger compression and expansion power.In the situation that polyvinyl alcohol chain does not have any affluence, the state of polyvinyl alcohol chain in basic stretching, extension.Therefore, in this case, although polyvinyl alcohol has large tan δ numerical value and their amorphous segment has the large free degree, when they are subject to compressing largely, they still cannot fully relax the external stress being applied thereto.Yet, when polyvinyl alcohol chain is not in full extension state, but still have necessarily when rich, polyvinyl alcohol chain is with respect to the just deformable of rich part of fiber, so this vinylal fibre just can relax the external stress being applied thereto.In addition, in this case, when convenient fiber is subject to expanding, the rich part that forms the polyvinyl alcohol chain of fiber also can further stretch, it is believed that consequently, vinylal fibre can relax the external stress being applied thereto, and therefore its endurance will be improved.Fibrous fracture stretch value is not done to concrete regulation, but generally can be up to 30% left and right.

From the enhancing ability of fiber, consider preferably, the tensile strength of vinylal fibre of the present invention is at least 5cN/dtex (li newton/dtex), more preferably 6cN/dtex at least.The tensile strength upper limit to fiber is not done concrete regulation.Yet in the situation that fiber tensile strength is too high, fiber cannot have the extension at break of satisfaction.Therefore, preferably, the highest 20cN/dtex of fiber tensile strength, more preferably the highest 10cN/dtex.Generally speaking, thereby can characterize like this through the vinylal fibre that super drawing possesses higher degree oriented crystalline degree, that is, the raising of their tensile strength is that the cost that is reduced to its extension at break brings.Otherwise the vinylal fibre that extension at break is higher will have lower tensile strength.Therefore, vinylal fibre of the present invention will have lower tensile strength conventionally, have higher extension at break simultaneously.Yet the vinylal fibre with the extension at break that this kind improve greatly is but enjoyed the fatigue proof advantage being significantly improved.Therefore, although its tensile strength is lowered to a certain extent, this fiber or good taken as a whole.As what show in embodiment below, vinylal fibre of the present invention can guarantee to have at least 80% under the rigor condition of their actual tests, especially 85～100% endurance.

The method of production vinylal fibre of the present invention is not done to concrete regulation.Yet such vinylal fibre will be difficult to produce by commonsense method.Therefore, vinylal fibre of the present invention is better produced according to method given below.

For producing for polyvinyl alcohol of the present invention, better by the saponification partially or completely of parent polyvinyl acetate.Here the polyvinyl alcohol that used can be to comprise two or more monomers, comprising polyvinyl alcohol, copolymer, or can also be through other copolymers with any other component modification.

Preferably, the polyvinyl alcohol saponification degree that used here, considers it is at least 70mol% from its spinning duration ability to cure, more preferably at least 90%.Heat-resisting from polymer, can spin and mechanical performance considers that further preferably, the saponification degree of polymer is between 99～100mol%.Specifically, the higher vinylal fibre of saponification degree hardly can aggegation (adhesion) together, NAG vinylal fibre can have good endurance.Specifically, improve the saponification degree aggegation that for example can prevent vinylal fibre, in they are immersed in adhesion rubber improver (, RFL etc.) and in the process of heat setting subsequently together.Here said saponification degree represents that hydrolysed ethylene alcohol unit in polyvinyl alcohol is to polyvinyl alcohol parent, that is, and and the ratio of total vinyl acetate unit in polyvinyl acetate or its copolymer.Preferably, the polyvinyl alcohol average degree of polymerization that used is here from spinnability, tensility, extension at break, mechanical performance and the cost consideration of vinal, between 1000～5000 left and right, more preferably the highest by 4000, further preferably the highest by 1500.

Vinylal fibre of the present invention does not always require unique polyvinyl alcohol of planting thus to form, but can comprise additive and any other polymer.For example, they can be the fiber (for example, fiber of sea-island structure and so on) of blend spinning or the fibers of multicomponent spinning of polyvinyl alcohol and any other polymer.Yet, consider its mechanical performance and heat-resisting, preferably at least its 50% (quality), more preferably 80～100% (quality) are polyvinyl alcohol.

Preparation comprises the spinning solution of polyvinyl alcohol as mentioned above.

The solvent that spinning solution is used can be aqueous solvent or organic solvent.Yet, to consider productivity ratio and production cost, and for obtaining the vinylal fibre with 90 ℃ of tan δ of high level, be preferably, spinning solution is the aqueous solution of polyvinyl alcohol.Preferably, the polyvinyl alcohol concentration of spinning solution is between 10～60% (quality), more preferably between 40～55% (quality).The spinning solution with high polyvinyl alcohol concentration is favourable, because like this, the polymer chain that forms vinylal fibre manufactured goods will be difficult to stretch and will take random configuration.Therefore, vinylal fibre just can have higher 90 ℃ of tan δ and can improve endurance.Nature, the impregnated wire of this kind of vinylal fibre also will inevitably have higher endurance.Much less, any other additive also can join in spinning solution.

Then, spinning solution is spun into silk.Serving as reasons, it obtains the vinylal fibre with high 90 ℃ of tan δ, preferably adopts dry spinning.In contrast, wet spinning or dry-wet spinning require the step that spun spinning solution is cured in coagulating bath from spinning head, and for this reason, the polyvinyl alcohol concentration of spinning solution is had to lower.Have this kind relatively polyvinyl alcohol polymer chain in the spinning solution of oligomerisation of ethylene determining alcohol normally stretch.In addition, in wet method or dry wet method, in view of spun spinning solution from spinning head is directly solidified, will there is more regular orientation in the polyvinyl alcohol chain that forms the vinylal fibre that obtains.If so,, vinylal fibre will have low-level 90 ℃ of tan δ.On the other hand, in dry spinning, the polyvinyl alcohol concentration of spinning solution allows higher, so polyvinyl alcohol chain is taked random configuration and do not stretch.In addition, in the method, from the spun spinning solution of spinning head, be dried gradually.Therefore, forming the polyvinyl alcohol chain of the vinylal fibre that obtains can random orientation and have rich length, so this vinylal fibre just can have 90 ℃ of large tan δ.In view of these reasons, this kind of dry spinning,--spinning solution is spun steam atmosphere (being preferably spun in air), then the fiber that obtains directly dry therein--be preferably used for production vinylal fibre of the present invention.

From the spun spinning solution of spinning head, be subject to dry baking temperature, do not do concrete regulation, generally between 100～250 ℃, but preferably between 120～250 ℃ of left and right.Then, dry fiber is accepted stretching under dry heat, to improve its mechanical performance and anti-swelling ability.Preferably, the total drawing ratio during dry heat treatment is at least 9 times of the former length of fiber, preferably at least 10 times, and more preferably at least 11 times.During dry heat treatment higher draw ratio can improve stretch after fiber tensile strength and reduce under the 1.8cN/dtex load that will mention below it in the middle of extend.Yet along with the raising of draw ratio, fiber can reduce at tan δ numerical value and the extension at break of 90 ℃.Therefore, be preferably, the degree of orientation of fiber should be greatly to surpassing the level requiring.Specifically, fiber total drawing ratio is preferably the highest is 30 times of the former length of fiber, more preferably the highest 20 times, further preferably the highest 15 times, further preferably the highest 13 times.The temperature of dry heat treatment is preferably between 180～250 ℃ of left and right, more preferably between 200～250 ℃.

Then, make fiber stand thermal contraction and process, to make it to possess tan δ numerical value at 90 ℃ of requirement and there is the extension at break of requirement.Preferably, make fiber stand at least 13% shrinkage factor, more preferably at least 14%, further preferably the thermal contraction of 15%～30% shrinkage factor is processed.As mentioned above, vinylal fibre must possess tan δ numerical value and higher extension at break at higher 90 ℃, can make the fibrous impregnated wire of fiber and bag have the endurance of higher level.Therefore, by thermal contraction, process, wish to improve tan δ value and the extension at break of vinylal fibre at 90 ℃.Preferably, the thermal contraction treatment conditions that comprise shrinkage factor and heating-up temperature are determined according to the polymer of fibre number and formation fiber.Wish, fiber can further stand any other to be processed, as heat setting and so on.In dry spinning vinylal fibre, polyvinyl alcohol chain stretches unlike in wet spinning vinylal fibre, therefore has affluence.So owing to having adopted dry spinning, vinylal fibre can be processed and obtain more effective raising by this kind of thermal contraction at tan δ and the extension at break of 90 ℃.Preferably, the temperature that thermal contraction is processed is between 200～250 ℃, more preferably between 230～250 ℃.Be preferably, the temperature that thermal contraction is processed and the temperature of xeothermic stretch processing are before this in same level.

The method of production vinylal fibre of the present invention requires can be had tan δ value at higher 90 ℃ and have 1 tan δ peak within the scope of set point of temperature can meet a fiber of producing--specified conditions under carry out.Mention above, thousand common method spinning poly PVAL have less tan δ peak and 2 tan δ peaks conventionally.Therefore,, in the method for production vinylal fibre of the present invention, the special treatment that changes the tan δ of institute's producd fibers is absolutely necessary.Can affirm, the vinylal fibre with higher extension at break can be had an endurance improving to some extent.And in having the vinylal fibre of less tan δ, amorphous segment is restricted, its free degree is also very little.Therefore, the vinylal fibre of this type external stress that almost can not relax satisfactorily.

For improving the tan δ at 90 ℃ of vinylal fibres and making fiber there are the means that 1 tan δ peak is taked, do not do concrete regulation, yet it is a kind of method that adds cyclic polyols derivative in vinylal fibre preferably.Although imperfectly understand, but it is believed that, why in vinylal fibre, add cyclic polyols derivative to accomplish the end in view, because this derivative is in connection with to forming on the polyvinyl alcohol of fiber or being penetrated into polyvinyl alcohol structures inside, thereby disturb the structure of polyvinyl alcohol chain, make whereby polyvinyl alcohol structures obtain suitable and uniform disordering, thereby change the tan δ of vinylal fibre.Specifically, cyclic polyols derivative is being joined to high elongation in vinylal fibre, that is, oriented crystalline wherein does not develop in the situation of high level very, this derivative can be penetrated into fibrous inside with comparalive ease, and the fiber that obtains is also just easy to processing.In addition, originally the free degree just the free degree in the very high amorphous segment of vinylal fibre acquisition is further significantly improved, thereby, added the vinylal fibre of this derivative just can there is the high-temperature region tan δ numerical value of further raising.And when cyclic polyols derivative is added in the low elongation vinylal fibre that oriented crystalline developed into high level very, this derivative almost can not be penetrated into fibrous inside, therefore need to could infiltrate wherein for a long time, so the tan δ value of vinylal fibre only can improve seldom after processing.

Specifically, the cyclic polyols derivative that the present invention uses comprises cyclic compound and the derivative thereof with at least 2 oh groups.More particularly, it comprises the aromatic compounds with at least 2 oh groups, and for example benzenediol, naphthalenediol and so on, as catechol, resorcinol etc.; And derivative.Derivative comprises salt, ester, ether and the acetal of this kind of cyclic polyols, and they have low distillation evaporation.In the present invention, can adopt the form of mixtures of multiple cyclic polyols derivative.

In the present invention, especially preferably on phenyl ring, there is the polyhydric phenols of at least 2 oh groups, and derivative.Wherein, consider comprising wherein the impact of any vinylal fibre tan δ more favourable, more preferably bis-phenol and derivative thereof, especially those contained 2 oh groups are in ortho position person.Specifically, the catechol derivatives that comprises catechol and derivative thereof is that the present invention preferably uses.The salt of catechol (especially its sodium salt) more preferably, this be based on it can prevent evaporation from vinylal fibre, it considers the Beneficial Effect of vinylal fibre tan δ, its cost and operability thereof.

Consider the endurance of the vinylal fibre that comprises it, cyclic polyols derivative preferably comprises at least 50% (quality), more preferably at least 80% (quality) catechol and/or its derivative.

Along with the increase of cyclic polyols derivative content in vinylal fibre of the present invention, this vinylal fibre will improve at the tan δ of 90 ℃.Therefore, be preferably, this vinylal fibre comprises, and take fiber quality as benchmark at least 0.1% (quality), more preferably at least 1% (quality) cyclic polyols derivative.Yet, consider fibre property and the vinylal fibre adherence to rubber, for the quantity of the cyclic polyols derivative of fiber, take fiber quality as benchmark preferably the highest by 30% (quality), more preferably the highest by 20% (quality).Even if add greater amount cyclic polyols derivative in fiber, the endurance of fiber also no longer significantly improves.Therefore, consider cost, the cyclic polyols derivative quantity of using in fiber is the highest by 10% (quality), more preferably the highest by 5% (quality) preferably.

In Japanese patent application publication No. 21016/1997,228251/1997 and 291477/1997, it is said that polyalcohol can capture the boronic acid compounds in brake fluid.These documents only say that polyalcohol can capture boronic acid compounds, at all tan δ and the elongation problem of the not mentioned vinylal fibre containing polyalcohol.For example, in the embodiment of the disclosure description, use be 1239 vinylal fibres of Kuraray company.The vinylal fibre using in literary composition has high oriented crystalline degree, thereby its elongation at break is approximately 8%.So, with polyol derivative, process such vinylal fibre and will spend the plenty of time, in addition, with the tan δ that the vinylal fibre that it is processed has, be at most 0.11 left and right.Moreover in view of its extension at break is very low, different from fiber of the present invention, this kind of vinylal fibre can not enjoyed high-level endurance.The data of this point from comparative example 2 described below will see too clearly.

In the present invention, by the method on cyclic polyols derivative paint vinylal fibre, do not do concrete regulation.This derivative can be on paint vinylal fibre during fiber preparation (for example, joined in spinning solution, or joined on as-spun fibre or joined spinning on fiber of being about to batch), or can after fiber is made, be applied up.From the angle of productivity ratio, consider, a kind of preferably rear method, that is, add derivative wherein after vinylal fibre is made.In the present invention, use the not yet full-blown high vinylal fibre that extends of oriented crystalline.Therefore, even if cyclic polyols derivative is joined in the method in fiber after vinylal fibre is made, derivative also can be penetrated into fibrous inside smoothly, and fiber also can be subject to the processing of this derivative efficiently.Cyclic polyols derivative is directly on paint vinylal fibre, but be applied up after also can be in being dissolved into appropriate solvent.

For vinylal fibre of the present invention is configured as to impregnated wire, can adopt any method that twisted fibers is impregnated in cyclic polyols derivative solution and is dried subsequently; Or cyclic polyols derivative is joined in adhesion rubber improver (as RFL liquid, epoxy finishes liquid, rubber slurry etc.), so that fiber is in the processing that stands to stand when adhesion rubber improver is processed derivative.In addition, also can adopt fortifying fibre is knitted into flexible pipe, subsequently derivative is applied on it; Or adopt the surface or the inner method that derivative are added to internal layer tubular rubber or exodermis rubber.Wish any can combining by the mode of any requirement in above-mentioned several different methods.Yet, be to simplify processing step, also, for guaranteeing the good infiltration of cyclic polyols derivative to fiber, be preferably, by derivative join adhesion rubber improver (as, RFL liquid, epoxy finishes liquid, rubber slurry etc.) in.Adhesion rubber improver is applied on fiber and can greatly improves the adherence of obtained vinylal fibre to rubber.Therefore, the method is preferably the method that produces better effects.At cyclic polyols derivative used, be height volatility, and will in the situation that evaporate during the drying steps of handled vinylal fibre, better strengthen the applied amounts of derivative on fiber.Joining the tan δ that cyclic polyols derivative in vinylal fibre and impregnated wire thereof can improve fiber and line, in addition, is also effective with the boronic acid compounds that it is captured in brake fluid.

Therefore the vinylal fibre, obtaining in a manner described can directly be used as reinforcing material.Yet, as rubber reinforcement material, preferably with adhesion rubber improver, process them to make impregnated wire again.

The fiber number that forms the vinylal fibre of this kind of impregnated wire can be stipulated rightly.From their angle of enhancing ability, endurance and productivity ratio, consider, vinylal fibre filament number is preferably between 1～20 dtex (dtex) left and right.Consider productivity ratio and the mechanical performance of impregnated wire, impregnated wire is processed and be configured as to vinylal fibre bundle (the preferably fiber multifilament bundled of twisting).The number of fiber that forms every rhizoid bundle is at least preferably 5, more preferably at least 10.Specifically, processing as follows: by 500～4000 about dtexs, but preferably the multifilament of 1000～2500 dtexs left and right be twisted to 20～120t/m (twist/m) twisting count.Conventionally, the endurance of folded yarn is higher than single twisted yarn; Add the yarn that is twisted to larger twisting count and there is higher endurance.Yet, be not conventionally inclined to and adopt high twisting count, because its procedure of processing is by complicated, also because they are bulky.In the present invention, when even if adhesion rubber improver is applied on the single twisted yarn of vinylal fibre, especially through (specifically, the 100t/m or lower of low twisting count twisting, 60t/m or lower even), the impregnated wire that obtains also can possess good endurance.

For the fiber that forms impregnated wire, vinylal fibre is indispensable, because it has excellent mechanical properties and good anti-expansion.Yet the fiber that forms impregnated wire must not be all always vinylal fibre, but can be by them and any other fiber combinations except vinylal fibre.For guaranteeing effect of the present invention, better at least 60% (quality), more preferably at least 80% (quality), the fiber that further preferably 95～100% (quality) forms impregnated wire is vinylal fibre.

Vinylal fibre bundle stands the processing of adhesion rubber improver.

Adhesion rubber improver is not done to concrete regulation, as long as it can improve the adherence of vinylal fibre to rubber.For example, it comprises RFL (resorcinol formaldehyde latex) liquid, epoxy finishes liquid, rubber slurry, the polyurethane resin aqueous solution etc.Certainly, consider and improve the ability of adhesion rubber and operability, still preferred RFL.More preferably use the aqueous dispersion of RFL, because be conducive to like this evenly applying on fiber.

A kind of method for optimizing of preparing this kind of RFL liquid comprises: by the liquid A of making for 1～10 hour 10～40 ℃ of ageings by resorcinol, formaldehyde and sodium hydrate aqueous solution, mix in the ratio of 5/95～30/70 (quality) with the liquid B (solids content is between 40～60% (quality) left and right) of latex aqueous dispersion, subsequently, institute's mixture that obtains is 10～40 ℃ of ageings about 10～30 hours again.The composition of RFL liquid is not done to concrete regulation, but preferably, make the ratio of latex/resorcinol between 100/1～100/20 left and right, the ratio of latex/formaldehyde is between 100/1～100/20 left and right, and the ratio of latex/NaOH is between 100/0.1～100/3 left and right, and all proportions is mass ratio.The type of latex used should be selected rightly according to the rubber type of preparing combination with it.For example, can adopt the SBR latex etc. of any styrene-butadiene latex (SBR), vinylpyridine-modification.The adhesive capacity (impregnation resin content) (by solid) of RFL on vinylal fibre, from fiber to the adherence of rubber, operability, processing flexibility and the cost consideration of fiber, preferably be up to 20% (quality) of polyvinyl alcohol, more preferably 1～10% of polyvinyl alcohol (quality).By the method on adhesion rubber improver paint fiber, do not do concrete regulation.For example, can adopt any in infusion process, rubbing method, spraying process and so on.

After processing with this kind of adhesion rubber improver, better fiber is implemented to dry and heat treatment, to improver is fixed on fiber.Preferably, baking temperature is between 100～130 ℃.

For improving the tan δ of impregnated wire, to improve its anti-expansion and reduce its elongation under 1.8cN/dtex load, and even improve its tensile strength, thereby improve its enhancing ability, better make impregnated wire heat-treat after dry, treatment temperature is between 100～200 ℃ (preferably between 150～190 ℃) and in 0.10cN/dtex at least, preferably at least under the tension force of 0.13cN/dtex.Conventionally, the heat treatment under tension force can improve the mechanical performance of processed fiber, but usually can reduce its extension at break and its endurance is worsened.Yet, by controlling heat treatment temperature, the temperature stretching before making it lower than fiber treatment, and lower than they were once subject to before this thermal contraction treatment temperature, after processing, the reduction of the extension at break of fiber just can significantly alleviate, thereby can obtain impregnated wire flexible, that endurance is good.From productivity ratio angle, consider, heat treated tension force is better up to 1cN/dtex, more preferably the highest 0.5cN/dtex.

In the present invention, impregnated wire must have at least 0.12, but preferably at least 0.13, more preferably at least 0.14 90 ℃ of tan δ.As for the upper limit of its 90 ℃ of tan δ, do not do concrete regulation, however preferably the highest by 0.30, more preferably the highest by 0.25, to make impregnated wire there is excellent mechanical properties.Such impregnated wire for example can be produced by the vinylal fibre with high 90 ℃ of tan δ.In the situation that they heat-treat in the manner described above under high-tension condition, its 90 ℃ of tan δ can significantly improve.Although still imperfectly understand, but it is believed that, why heat treatment can improve line after the processing tan δ at 90 ℃ greatly, because the vinylal fibre through setting, formation line can stand heating and crystallization does not occur, whereby, the polyvinyl alcohol chain originally tangling is each other unclamped, and becomes the polyvinyl alcohol chain with rich length.As a result, the free degree of the amorphous segment in polyvinyl alcohol chain improves greatly, and the tan δ of the line after so processing also will be improved.

For further improving its endurance, be preferably, impregnated wire has between 60～120 ℃, the more preferably tan δ peak of 70～110 ℃, and also the peak (number) in 0～200 ℃ of temperature range is 1 substantially.It is the same that its reason is mentioned when relating to vinylal fibre above.Impregnated wire, in the upper limit of the tan δ of 90 ℃, is not done concrete regulation, but generally can be the highest by 0.30, preferably the highest by 0.25, to guarantee the mechanical performance of impregnated wire.

From endurance, consider, the extension at break of impregnated wire is at least preferably 10%, more preferably at least 11%, more preferably at least 12%, further preferably at least 13%.Had so specific extension at break, the polyvinyl alcohol segments that forms impregnated wire just can have certain affluence, so the endurance of impregnated wire just can significantly improve.After like this structure, impregnated wire just can have at least 80%, and preferred 85～100% endurance degree, even if under the such harsh condition standing such as embodiment sample actual tests.

From its fatigue proof angle, consider, impregnated wire preferably has higher extension at break.Yet, from its productivity ratio and DIMENSIONAL STABILITY (anti-expansion) angle, consider, be preferably, the extension at break of impregnated wire is the highest is 20%, more preferably the highest by 17%.Its extension at break will reduce after the heat treatment under overtension at impregnated wire.Therefore,, as the vinylal fibre for the production of impregnated wire, preferably use extension at break to extend vinylal fibre higher than the height of impregnated wire extension at break required value.Be preferably, impregnated wire process is under tension force after heat treatment, and its extension at break reduction amplitude is no more than 5%, more preferably between 0～4%.

From its enhancing ability and DIMENSIONAL STABILITY (anti-swelling) angle, consider, the tensile strength of impregnated wire is at least preferably 5cN/dtex, more preferably 6cN/dtex at least.The tensile strength upper limit of impregnated wire, does not do concrete regulation, but considers productivity ratio and the cost of line, preferably the highest 20cN/dtex.Yet, from its extension at break between balanced consideration, be more preferably, the tensile strength of impregnated wire is up to 10cN/dtex.The tensile strength of impregnated wire can improve by the vinylal fibre tensile strength improving for the production of impregnated wire.

Through pressing the heat treatment under tension force as mentioned above, the tensile strength of impregnated wire, compares with untreatment fiber tensile strength, can improve at least 0.2cN/dtex, preferably 0.5～2cN/dtex left and right.In view of impregnated wire tensile strength can improve by the heat treatment under tension force, therefore even if there is the lower tenacity fibers of lower tensile strength, also can be made into the impregnated wire with required tensile strength.In the situation that improving heat treatment tension force and temperature, the tensile strength of impregnated wire can further improve.

From its DIMENSIONAL STABILITY and anti-expansion angle, consider, be preferably, impregnated wire extends and is up to 4% in the middle of 1.8cN/dtex load place, more preferably the highest by 3%, more preferably the highest by 2.5%, further preferably the highest by 2%.For example, in the situation that impregnated wire is used for brake hose reinforcing material, brake hose will be easily because brake fluid flowing pressure expands, if the middle elongation excessive words of impregnated wire reinforcing material used under 1.8cN/dtex load.And if so, when touching on the brake pedal, Pressure Drop will be very large, result, the automobile travelling just can not be braked well.Yet, for making impregnated wire enjoy higher endurance, wish that again it is at least 1% that impregnated wire extends in the middle of 1.8cN/dtex load place.In view of through by after heat treatment, extending and will reduce in the middle of impregnated wire under load as mentioned above, can adopt its middle vinylal fibre extending in the middle of the target that is greater than impregnated wire that extends to produce impregnated wire.For example, can adopt the middle vinylal fibre extending between 1～6% left and right.The middle of vinylal fibre extends, and the shrinkage factor in the time of can processing by the draw ratio during the xeothermic stretching of raising fiber or by reduction filament contraction, reduces.

Vinylal fibre of the present invention can be used in any form.For example, they can be processed into cut staple, filament yarn, bundle yarn, short fiber spinning yarn, cloth (woven, knit goods and non-weaving cloth), strand etc.They can merge with any other fiber.About its Application Areas, this vinylal fibre can be widely used as reinforcing material and the coating material of rubber, resin, hydraulic pressure material etc., and this is because it has good endurance.

Impregnated wire of the present invention can be used in any form.For example, the form that they can (twist) line is for multiple fields, also can be made into knotwork, woven and knitted fabric and so on.They can merge with any other material or be laminated.About Application Areas, impregnated wire is preferred for tire cord and rubber reinforcement material as belt (conveyer belt, odontoid belt, vee-belt), and for flexible pipe (water brake flexible pipe, steam heater hose, fire hose), to bring into play its superior mechanical intensity, endurance and other properties.Specifically, owing to having high endurance, impregnated wire is especially preferably used as brake hose reinforcing material.As the reinforcing material of brake hose, preferably they are knitted into desired structure.

The present invention will specifically describe by the following examples, yet the embodiment providing does not intend forming limitation of the scope of the invention.

The sample of preparing in embodiment is analyzed by the following method and is tested.

The applied amounts (percentage to polyvinyl alcohol dry mass) of cyclic polyols derivative on polyvinyl alcohol:

The sample of 2g fortifying fibre or impregnated wire, on it, applied cyclic polyols derivative, pour into together with 100mL distilled water in 300mL Erlenmeyer flask, make it in bottle, under room temperature, place 24 hours, make whereby cyclic polyols derivative extract from sample.By HPLC method, adopt ultraviolet detector to analyze this liquid, thereby determine cyclic polyols derivative content in sample.In the following embodiments, cyclic polyols derivative used is catechol sodium.At this, measure in the HPLC (high efficiency liquid chromatography) of use, the post of use is anti-phase ODS post, and movement is water/methyl alcohol=1/1 mutually.

tanδ：

The FT Rheo spect rer DVE-V4 that adopts Rheology company, the sample of vinylal fibre or impregnated wire, is heated to 250 ℃ with the rates of heat addition of 3 ℃/min from-50 ℃.Frequency is 10Hz, and amplitude is 5 μ m.Read the tan δ data of various different temperatures.

The composition of RFL:

Liquid A: 11 parts of 24 parts of sodium hydrate aqueous solutions of 11 parts of formaldehyde of 300 parts of resorcinols of water (37% (quality)) (10% (quality))

This liquid A was 25 ℃ of ageings 6 hours.

Liquid B: 260 parts, 130 parts of water of 130 parts of vinylpyridine-modification SBR latex of SBR latex

Liquid B is mixed with the liquid A of ageing, then 25 ℃ of ageings 16 hours again, thereby is prepared into RFL.

Tensile strength, cN/dtex; Extension at break, %; Middle elongation, %;

Vinylal fibre or impregnated wire are dried at least 2 hours at 105 ℃, thereby make the sample that moisture is the highest by 1% (quality) of polyvinyl alcohol.According to JIS L1013, tensile strength and the extension at break of " artificial filament's test method " working sample.Draw the load elongation chart of sample, therefrom read sample and extend in the middle of 1.8cN/dtex load place.

In the actual production of flexible pipe, material heats at least 150 ℃ of temperature during vulcanization of rubber step, and the moisture that therefore strengthens the vinylal fibre of use should be maximum 1% (quality) of polyvinyl alcohol.Therefore,, when the curve of the fiber of check brake hose reinforcing material, importantly, fiber moisture content should be up to 1% of polyvinyl alcohol.In the situation that sample (untreatment fiber or the fiber of processing with adhesion rubber improver) has absorbed 1% (quality) that water and its moisture surpass polyvinyl alcohol from air, its elongation measurement value will be greater than the respective value of the sample that do not absorb water.

Endurance, %:

Vinylal fibre endurance appraisal procedure is as follows: fiber is twisted to 90t/m becomes twisted yarn, then with RFL, processes RFL content and equals 3% (quality).The yarn of processing carries out disk fatigue test (Goodrich method) according to JIS L1017.Extensibility and compression ratio that inside is added with the rubbery sample of yarn are 1%; Disc rotary speed is 2500rpm; Temperature, 90 ℃; Disk corotation turns 1000,000 times.Fiber tensile strength before test represents with A; After test, with B, represent.The endurance of sample represents with (B/A) x100.

Impregnated wire endurance appraisal procedure is as follows: vinylal fibre is processed into double twisting strand by the twisting count of the twisting count of first twist 300t/m and retwist 300t/m by double twisting, then with RFL process to RFL content be 8% (quality).The strand of processing carries out disk fatigue test according to JIS L1017.Extensibility and compression ratio that inside is added with the rubbery sample of strand are 2%; Disc rotary speed is 2500rpm; Temperature, 90 ℃; Disk corotation turns 300,000 times.Strand tensile strength before test represents with A; After test, with B, represent.The endurance of sample represents with (B/A) x100.

Example 1:

The polyvinyl alcohol water solution of the degree of polymerization 1750, saponification degree 99.9mol% (polyvinyl alcohol concentration of solution is 45% (quality)) is spun in air and is dried by 200 hole spinning plate (every hole aperture 0.8mm).Fiber carries out xeothermic stretching at 243 ℃, and total drawing ratio is 12 times of the former length of fiber, then under same temperature, shrinks 16% shrinkage factor, thereby makes polyvinyl alcohol multifilament (1333dtex/200f) (1333 dtex/200 monofilament).Using this silk as raw material long filament.Material polyethylene alcohol multifilament is 0.057 at the tan δ numerical value of 90 ℃; Its tensile strength is 6.3cN/dtex; Its extension at break is 17.4%; In the middle of it, extending is 4.4%; Its endurance is 61% (referring to curve B in Fig. 1 1).

This raw material long filament passes the cyclic polyols derivative aqueous solution under 0.09cN/dtex tension force, Negotiation speed is 40m/min, then 40% (quality) that to drain to content liquid be polyvinyl alcohol, subsequently through 90℃ heated air drying district, thereby is dried.The long filament of so processing has the extension at break of raising and 90 ℃ of tan δ numerical value of raising, and has 1 tan δ peak in 60～120 ℃ of temperature ranges.Its endurance is good.Data are loaded in table 1 and Fig. 2.Here the cyclic polyols derivative that used is catechol sodium, by 10 weight portion catechols and 2 weight portion NaOH, is prepared from.

Then, fibre bundle floods in RFL, then heat treatment, thereby makes dipping strand.In heat treatment, the tension force applying is 0.15cN/dtex (measuring with the tensometer of gamut 4.9N); Translational speed is 40m/min; Baking temperature is 120 ℃; Curing temperature is 185 ℃.The carried interest line of dipping contains the cyclic polyols derivative that its amount is the RFL of 3% (quality) of polyvinyl alcohol and 2% (quality) of polyvinyl alcohol.This dipping strand has the extension at break of raising and 90 ℃ of tan δ numerical value of raising, and has 1 tan δ peak in 60～120 ℃ of temperature ranges.Its endurance is good.In addition, the elongation of dipping strand under 1.8cN/dtex load is very little, and its intensity is very high.Therefore, this dipping strand has good DIMENSIONAL STABILITY and anti-expansion, so be preferred rubber reinforcement material, is particularly useful for brake hose.

Example 2:

According to the method preparation dipping strand identical with example 1.Yet in this example, the catechol derivatives aqueous solution is joined in RFL, to use the processing of cyclic polyols derivative and with the processing of adhesion rubber improver simultaneously.In this is processed, cyclic polyols derivative catechol sodium effectively paint on long filament.The ratio of catechol sodium/RFL is 4.5/2.5 (quality), and the vinylal fibre of preparation here contains the cyclic polyols derivative that its amount is the FRL of 3% (quality) of polyvinyl alcohol and 2% (quality) of polyvinyl alcohol.Here obtain dipping strand and there are the extension at break of raising and 90 ℃ of tan δ numerical value of raising, and its endurance is good.In addition, the elongation of dipping strand under 1.8cN/dtex load is very little, and its intensity is very high.Therefore, this dipping strand has good DIMENSIONAL STABILITY and anti-expansion, so be preferred brake hose reinforcing material.

Comparative example 1:

Repeat the process of example 1.Yet in this example, on long filament, do not apply cyclic polyols derivative.The long filament that this example obtains and the tan δ numerical value of dipping strand at 90 ℃ are all little, and have 2 peaks in 0～200 ℃ of temperature range.The endurance of the long filament obtaining in this example and dipping strand is inferior in example 1.Data are loaded in table 1 and Fig. 2.

Comparative example 2:

Repeat the process of example 1.Yet the dry spinning polyvinyl alcohol filament yarn of ，Yi Kuraray company (Kuralon, the trade mark-1239:1332dtex/200f) is as raw material long filament in this example.This raw material long filament is 0.040 at the tan δ numerical value of 90 ℃; Tensile strength is 8.3cN/dtex; Its extension at break is 8.0%; In the middle of it, extending is 1.9; Its endurance is 26% (referring to curve B in Fig. 1 2).

And 90 ℃ of tan δ numerical value and the extension at break of the long filament of processing with cyclic polyols derivative obtaining in this example and dipping strand are all little and low, and its endurance is poor.Data are loaded in table 1 and Fig. 2.

Comparative example 3:

Repeat the process of example 1.Yet the dry spinning polyvinyl alcohol filament yarn of ，Yi Kuraray company (Kuralon, the trade mark-5506:1332dtex/600f) is as raw material long filament in this example.This raw material long filament is 0.028 at the tan δ numerical value of 90 ℃; Tensile strength is 9.5cN/dtex; Its extension at break is 8.0%; In the middle of it, extending is 1.7; Its endurance is 20% (referring to curve C in Fig. 1).

And 90 ℃ of tan δ numerical value and the extension at break of the long filament of processing with cyclic polyols derivative obtaining in this example and dipping strand are all little and low, and its endurance is poor.Data are loaded in table 1 and Fig. 2.

Although the present invention is described in conjunction with specific embodiments, it will be apparent to those skilled in the art that under the condition that does not depart from spirit and scope of the invention and also can make various change and modification.

Claims (9)

1. a vinylal fibre, this fiber 10% or higher hot water shrinkage (Wsr), and 4g/d or higher intensity, the tan δ that it has at 90 ℃ is at least 0.10; And in 60～120 ℃ of temperature ranges, substantially there is 1 tan δ peak; Its extension at break is at least 10%.

2. the vinylal fibre of claim 1, it comprises cyclic polyols derivative.

3. the vinylal fibre of claim 2, wherein cyclic polyols derivative is catechol derivatives.

4. the impregnated wire containing vinylal fibre bundle of processing with adhesion rubber improver, the tan δ that it has at 90 ℃ is at least 0.12; And in 60～120 ℃ of temperature ranges, substantially there is 1 tan δ peak; Its extension at break is at least 10%.

5. the impregnated wire of claim 4, it comprises cyclic polyols derivative.

6. the impregnated wire of claim 5, wherein cyclic polyols derivative is catechol derivatives.

One kind manufacture 90 ℃ at tan δ at least 0.12 and substantially have the method for the impregnated wire of 1 tan δ peak and extension at break at least 10% in 60～120 ℃ of temperature ranges, the method comprises: by the vinylal fibre of adhesion rubber improver paint extension at break at least 12%, then by this fiber drying, then in the temperature between 110～200 ℃ and at least under 0.1cN/dtex tension force, it is heat-treated.

8. the impregnated wire production method of claim 7, the method also comprises: by cyclic polyols derivative paint vinylal fibre, this can be during by the step on adhesion rubber improver paint fiber or before carry out.

9. the rubber reinforcement material that comprises the impregnated wire of any one in claim 4～6.