CN102549204B - Polyimide fibers and use thereof, and process for production of the polyimide fibers - Google Patents
Polyimide fibers and use thereof, and process for production of the polyimide fibers Download PDFInfo
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- CN102549204B CN102549204B CN201080045560.9A CN201080045560A CN102549204B CN 102549204 B CN102549204 B CN 102549204B CN 201080045560 A CN201080045560 A CN 201080045560A CN 102549204 B CN102549204 B CN 102549204B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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Abstract
Conventional types of polyimide fibers have such disadvantages that the polyimide fibers have poor hydrolysis resistance and have high thermal shrinkage coefficients at higher temperatures. Disclosed are polyimide fibers characterized by having a breaking elongation of 10 to 100% inclusive, a breaking strength of 1.0 to 8.0 cN/dtex inclusive, a fiber fineness of 0.5 to 20 dtex inclusive, a breaking strength retention rate of 80% or more after treated under the conditions of 150 DEG C/100%RH/48 hours, a thermal shrinkage coefficient of 3.0% or less at 300 DEG C, an ellipsoidal cross-sectional view having an ellipticity of 1.1 or more or an array-shaped cross-sectional view. Also disclosed is a process for producing the polyimide fibers. When the polyimide fiber production process is employed, it becomes possible to produce polyimide fibers having excellent hydrolysis resistance and a small thermal shrinkage coefficient at a higher temperature.
Description
Technical field
The present invention relates to the manufacture method of polyimide fiber and utilization thereof and this polyimide fiber.
Background technology
Polyimide fiber is compared with the fiber of general organic polymer resin, and high-temperature stability and chemical proofing are excellent, therefore, and for forming felt or the heat-resisting fabric of taking way of the heat resistance bag hose that pump-down process uses.And then the fiber of excellent heat resistance can be widely used as base cloth or the reinforcing material of the base material purposes of various insulating materials.
As existing polyimide fiber, can use by dry spinning method the polyimide resin of organic solvent solubility is carried out to polyimide fiber that spinning forms (for example,, with reference to patent documentation 1.)。In addition, known have by dry spinning method, make polyimide fiber method (for example, with reference to patent documentation 2), the polyimide fiber made by wet-spinning (for example, with reference to patent documentation 3) and then by cutting the polyimide fiber (for example,, with reference to patent documentation 4) of the method making of polyimide film.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 63-27444 communique (on June 3rd, 1988 is open)
Patent documentation 2: Japanese Patent Publication 42-2936 communique (on February 8th, 1967 is open)
Patent documentation 3: Japanese Patent Publication 59-163416 communique (on September 14th, 1984 is open)
Patent documentation 4: TOHKEMY 2006-176907 communique (on July 6th, 2006 is open)
Summary of the invention
The problem that invention will solve
The polyimide resin of the invention of described patent documentation 1, in order to improve the dissolubility in solvent, has organic group at side chain, has flexible group (Flexible Group) in structure.Therefore, become organic solvent solubility, and thermoplastic polyimide resin.Organic group at side chain can be given the dissolubility in organic solvent, but exists the heat resistance of polyimide resin to reduce, and the low problem of the solvent resistance in organic solvent.In addition, owing to becoming thermoplastic polyimide resin, therefore, for protective clothing purposes in the situation that, at high temperature melting, produces the phenomenon (water droplet phenomenon (drop phenomenon)) be attached to skin etc., therefore, existence can not be widely used in the problem of protective clothing etc.In addition, the cross section of spinning fibre has the odd-shaped cross section different from dumbbell shape, during forming fabric etc., has the problem that causes yield to reduce due to bulky impact.
In the invention of recording at described patent documentation 2, disclose the method for the polyimide fiber being formed by pyromellitic acid anhydride and diaminodiphenyl ether or diaminodiphenyl sulfide by the manufacture of dry spinning method.But, in the manufacture method of this polyimide fiber, obtain like that as described in Example 3 the fiber of the cross sectional shape of circle, different from dumbbell shape of the present invention or elliptical shape.Therefore,, in the situation that polyimide fiber is used for to the dust collect plants such as bag hose, there is the problem that surface area diminishes, dust catching efficiency reduces.In addition, in the manufacture method of the polyimide fiber of patent documentation 2, be included in the operation of the solvent of removing in a large number spinning fibre under oxygen atmosphere and when except desolventizing, have the danger such as blast.That is, the method for patent documentation 2 is suitable for a small amount of production, but has the problem that is difficult to process a large amount of fibers.And then, in the way of shaping polyimide fiber, carry out the impregnation process in water, in air, be dried, therefore, there is the problem that becomes the poor fiber of hydrolytic resistance.In addition, the percent thermal shrinkage that the polyimide fiber of making by the method for patent documentation 2 is deposited at high temperature becomes large problem.
The invention that described patent documentation 3 is recorded is for obtaining the method with the polyimide fiber of same structure of the present invention by wet spinning method, but, in manufacturing process, adopt in water by curing agent and catalyst and carry out the method that fiber that a part of imidizate mixes carries out spinning.But in the method,, owing to carrying out spinning in water, therefore, fail in fact to solve the problem that hydrolytic resistance is low.And then, exist polyimide fiber to be colored as dark brown, only obtain carrying out the problem of the fiber of surperficial hydrolysis.
And then the invention that described patent documentation 4 is recorded is for making the method for making polyimide fiber with coil cutting method after polyimide film.The polyimide fiber obtaining has the physics value same with film, but owing to not carrying out high stretch processing, therefore, has the problem that fibre strength is low.
In order to solve the means of problem
The inventor etc. concentrate on studies in order to solve described problem, found that, by using the polyimide fiber of following formation, can solve described problem points.
1) polyimide fiber, it is characterized in that, the elongation at break of described polyimide fiber is 10%～100%, fracture strength is 1.0cN/dtex～8.0cN/dtex, fiber number is 0.5dtex～20dtex, fracture strength conservation rate after processing under the condition of 150 ℃/100%RH/48 hour is more than 80%, and the percent thermal shrinkage at 300 ℃ is below 3.0%, and the flat ratio with section is more than 1.1 elliptical shape or dumbbell shape.
2) according to 1) described polyimide fiber, wherein, described polyimide fiber obtains by polyamic acid is carried out to imidizate, and described polyamic acid is to make to be selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4, the dicarboxylic anhydride of more than one in 4 '-benzophenone tetracarboxylic acid dianhydride and be selected from 4,4 '-diaminodiphenyl ether, 3, the diamines of more than one in 4-diaminodiphenyl ether, p-phenylenediamine (PPD) reacts and obtains.
3) polyimide fiber that the manufacture method by polyimide fiber is made, the method is characterised in that,
(a) polyamic acid solution is carried out to dry spinning, obtains the fiber that comprises partial solvent,
(b) by fiber impregnation in water,
(c) under more than 170 ℃ vacuum, be dried and make its imidizate,
(d) and then, the stretching ratio with 1.0 times～2.5 times at the temperature of 200 ℃～600 ℃ stretches, and after stretching, at the temperature of 200 ℃～600 ℃, heats.
4) polyimide fiber, its be by the temperature more than 300 ℃ and with the stretching ratio of 1.0 times～1.2 times by 3) described polyimide fiber heats and makes.
5) polyimides staple fibre, is characterized in that, described polyimides staple fibre comprises 1)～4) in polyimide fiber described in any one, fibre length is 10mm～1500mm, crimp percent is 2～100 curling (crimp)/inch.
6) non-weaving cloth, it comprises 1)～4) in the polyimides staple fibre of polyimide fiber described in any one.
7) heat-resistant filter, it has used 1)～4) in non-weaving cloth described in any one.
8) fabric, it comprises 1)～4) in polyimide fiber described in any one.
9) heat-resistant protective suit, it has used 1)～4) in polyimide fiber described in any one.
10) electric, electronic material, it has used and has comprised 1)～4) in the fabric of polyimide fiber described in any one.
11) manufacture method of polyimide fiber, is characterised in that,
(a) polyamic acid solution is carried out to dry spinning, obtains the fiber that comprises partial solvent,
(b) by fiber impregnation in water,
(c) under more than 170 ℃ vacuum, be dried and make its imidizate,
(d) and then, the stretching ratio with 1.0 times～2.5 times at the temperature of 200 ℃～600 ℃ stretches, and after stretching, at the temperature of 200 ℃～600 ℃, heats.
12) according to 11) manufacture method of described polyimide fiber, it is characterized in that, and then the stretching ratio with 0.9 times～1.2 times heats at more than 300 ℃ temperature.
13) manufacture method of polyimides staple fibre, is characterized in that, finish is coated to 1)～4) in the surface of polyimide fiber described in any one, carry out curling, cutting.
Invention effect
The excellent heat resistance of polyimide fiber of the present invention, have elliptical shape or dumbbell shape, so sense of touch is excellent, specific area is also large, in addition, also can under the condition that needs hydrolytic resistance of the unworkable harshness of polyimide fiber for up to now, use.
Accompanying drawing explanation
Fig. 1 is the key diagram of dry spinning method of the present invention;
Fig. 2 is the key diagram of the flat ratio of polyimide fiber of the present invention.
The specific embodiment
The present invention relates to polyimide fiber, it is characterized in that, the elongation at break with polyimide fiber is 10%～100%, fracture strength is that 1.0cN/dtex～8.0cN/dtex, fiber number are 0.5dtex～20dtex, the fracture strength conservation rate after processing under the condition of 150 ℃/100%RH/48 hour is that percent thermal shrinkage more than 80%, at 300 ℃ is, the flat ratio of section is more than 1.1 elliptical shape or dumbbell shape below 3.0%.
By elongation at break is controlled to 10%～100%, fracture strength is controlled to 1.0cN/dtex～8.0cN/dtex, when being configured as non-weaving cloth or fabric, can not making fibrous fracture and process, therefore preferably.
In addition, by the fiber number of polyimide fiber is controlled to 0.5dtex～20dtex, the yield in the time of can making to be configured as non-weaving cloth or fabric is good, therefore preferably.Particularly, in the situation that fiber number is thin, while being configured as non-weaving cloth, the yield that is woven into base cloth reduces, therefore be preferably above-mentioned scope.
In addition, by the fracture strength conservation rate after processing under the condition at 150 ℃/100%RH/48 hour is controlled at more than 80%, for example, as non-weaving cloth formed thereby and as bag hose in the situation that, in high temperature, super-humid conditions, use, under such condition, can stably use more than 3 years, therefore preferably.In addition, after being configured as fabric, being processed into protective clothing (such as fire-entry suit etc.) and going forward side by side and exercise the used time, even if use than general actual lifespan (5 years) the longer time, also do not find fiber variation, therefore preferably.
In addition, using heat resistant fibre as non-weaving cloth forms and be used as heat-resistant filter in the situation that, for example for the bag hose of the dust-collecting equipment in incinerator, because the temperature in the dust collect plant of incinerator sometimes reaches, approach 300 ℃, therefore, be sometimes exposed to the high temperature of 300 ℃.Now, when the contraction of heat resistant fibre is large, produce in the cage that filter is bonded at fixing bag hose and the problem that cannot take off.Therefore, preferably the percent thermal shrinkage at 300 ℃ is controlled at below 3.0%.
In addition, by thering is the flat ratio of the section of fiber, be more than 1.1 elliptical shape or dumbbell shapes, by polyimide fiber surface colour, be golden, can improve the transporting of fiber, and then, during for heat-resistant filter, can improve dust collecting performance, therefore preferably.
In order to obtain having the polyimide fiber of above-mentioned characteristic, concentrate on studies, result is clear and definite, by optimizing the chemical constitution of polyimide fiber and the manufacture method of polyimide fiber, can obtain having the polyimide fiber of above-mentioned characteristic.
, there is the polyimide fiber of the present invention of above-mentioned characteristic by using polyimide fiber, can realize the various physics values as the feature of polyimide fiber of the present invention, polyimide fiber obtains by polyamic acid is carried out to imidizate, described polyamic acid is to make to be selected from pyromellitic acid anhydride, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic dianhydride, 3, 3 ', 4, the acid dianhydride of more than one in 4 '-benzophenone tetracarboxylic acid dianhydride and be selected from 4, 4 '-diaminodiphenyl ether, 3, 4-diaminodiphenyl ether, the diamines of more than one in p-phenylenediamine (PPD) reacts and obtains.
Polyamic acid solution in the present invention is described in detail.
Polyamic acid solution in the present invention for making acid dianhydride and diamines react the polyamic acid solution obtaining in organic solvent, preferably the use amount of acid dianhydride is being made as to a mole, the use amount of diamines is made as in the situation of b mole, take mol ratio (a/b) as making it react the hydrolytic resistance that can improve the polyimide fiber finally obtaining more than 0.80 and lower than 1.00 mode, therefore preferably.More preferably take mol ratio as it being reacted more than 0.90 and lower than 1.00 mode.By the mol ratio with such, it is reacted, when carrying out imidizate by polyamic acid solution to polyimides, be difficult for causing the reduction of molecular weight, and then, the hydrolytic resistance of polyimide fiber is improved, therefore preferably.
Particularly, as for polyamic acid solution of the present invention, the fiber of heat resistance, chemical proofing, hydrolytic resistance excellence can be obtained, therefore, the polyamic acid solution of following combination can be preferably used.
1. the polyamic acid solution being formed by pyromellitic acid anhydride and 4,4-diaminodiphenyl ether.
2. the polyamic acid solution being formed by pyromellitic acid anhydride and 4,4-diaminodiphenyl ether, p-phenylenediamine (PPD).
3. by 3,3 ', 4, the polyamic acid solution that 4 '-bibenzene tetracarboxylic dianhydride and p-phenylenediamine (PPD) form.
4. by 3,3 ', 4, the polyamic acid solution that 4 '-bibenzene tetracarboxylic dianhydride and 4,4-diaminodiphenyl ether and p-phenylenediamine (PPD) form.
5. by 3,3 ', 4, the polyamic acid solution that 4 '-bibenzene tetracarboxylic dianhydride, pyromellitic acid anhydride and 4,4-diaminodiphenyl ether and p-phenylenediamine (PPD) form.
6. by 3,3 ', 4, the polyamic acid solution that 4 '-benzophenone tetracarboxylic acid dianhydride and p-phenylenediamine (PPD) form.
7. by 3,3 ', 4, the polyamic acid solution that 4 '-benzophenone tetracarboxylic acid dianhydride and 4,4-diaminodiphenyl ether and p-phenylenediamine (PPD) form.
8. by 3,3 ', 4, the polyamic acid solution that 4 '-benzophenone tetracarboxylic acid dianhydride, pyromellitic acid anhydride and 4,4-diaminodiphenyl ether and p-phenylenediamine (PPD) form.
Wherein, particularly in the present invention, in order to obtain having both the polyimide fiber of various characteristics, preferably use the polyamic acid solution being formed by pyromellitic acid anhydride and 4,4-diaminodiphenyl ether.
In addition, the synthetic organic solvent as for above-mentioned polyamic acid solution, can be used the polar organic acid amides series solvents such as DMF, DMA, METHYLPYRROLIDONE, gamma-butyrolacton; The water-soluble ethers series solvents such as oxolane, diox, dioxolane; The ketone such as acetone, MEK series solvent; The water-soluble nitrile series solvent such as acetonitrile, propionitrile; The non-proton property such as dimethyl sulfoxide (DMSO) polar solvent.These solvents can be used alone, and also can mix two or more uses.
Particularly, in dry spinning method of the present invention, from the viewpoint of baking temperature, consider, can preferably use DMF, DMA, dimethyl sulfoxide (DMSO), dioxolane, acetone.
In addition, as the polymer concentration of polyamic acid solution of the present invention, with solid component concentration, count 1～50 % by weight, be particularly preferably 10～30 % by weight.Solid component concentration in the present invention is the value of being calculated by the calculating formula of solid component concentration=(the diamines weight in the acid dianhydride weight+polyamic acid solution in polyamic acid solution) ÷ (weight of polyamic acid solution) * 100.
In addition, the viscosity for polyamic acid solution in the situation that measuring with Brookfield viscometer, has the viscosity of 100 pool～10000 pools when carrying out spinning at 23 ℃, can stably carry out spinning, therefore preferably.Preferred viscosity is 200 pool～6000 pools, and particularly preferred solution viscosity is 500 pool～4000 pools.Viscosity is controlled within the scope of these and can makes spinning stabilisation, therefore preferably.
In order to control as such viscosity, effectively suitably change above-mentioned acid dianhydride and the mol ratio of diamines.Particularly the polymerization of preferred polyamic acid solution is diamines to be dissolved in the solution of organic solvent in the present invention, adds acid dianhydride and it is reacted take molar ratio computing under the condition below 0.80.Then, limit is stirred the solution limit that acid dianhydride is dissolved in organic solvent and is added to adjust viscosity so that the viscosity of polyamic acid solution, in above-mentioned scope, can be made the polyamic acid solution of suitable viscosity thus.
In addition, as the polymerizing condition of polyamic acid, by under inert gas atmosphere ,-20～60 ℃, preferably it is reacted at 0～50 ℃, polymerizable target polyamic acid solution thus.
And then above-mentioned polyamic acid solution also can be pre-mixed a kind of or two or more various fillers, antioxidant, fire retardant, defoamer, lubricant, colouring agent etc.
In the present invention, find by above-mentioned polyamic acid solution being configured as to fiber shape by following manufacture method, can realize the various physics values as the feature of polyimide fiber of the present invention.
That is, polyimide fiber of the present invention is the polyimide fiber of making by the manufacture method of polyimide fiber, and the method is characterised in that,
(a) polyamic acid solution is carried out to dry spinning, obtains the fiber that comprises a part of solvent,
(b) by fiber impregnation in water,
(c) under more than 170 ℃ vacuum, be dried and make its imidizate,
(d) and then, at the temperature of 200 ℃～600 ℃ and with the stretching ratio of 1.0 times～2.5 times, stretch, after stretching, at the temperature of 200 ℃～600 ℃, heat.
As the dry spinning in the present invention, can use general dry spinning method.Edge graph shows that a routine limit of concrete spinning process describes.
Dry spinning in the present invention is illustrated in figure 1 after just spinning and in air-flow, emits spinning fibre and by the heat exchange in air-flow and solvent exchange, make the solvent evaporates in spinning fibre, the spinning process that spinning fibre separately can not be merged each other.
More specifically, spinning solution (polyamic acid solution) is supplied to the spinning nozzle 1 that spinning is used, and by the spinneret orifice of opening at spinning nozzle 1 (hole) 2, in air-flow, is sprayed.The diameter of spinneret orifice 2 can suitably be selected by fibre diameter as required.Be preferably the circular hole of diameter 0.01mm～5.00mm.Particularly preferred scope is the scope of diameter 0.05mm～2.00mm.By being made as such scope, can ejection be controlled lowly by pressure during polyamic acid solution, therefore preferably.In addition, more than the hole count of the spinneret orifice of spinning nozzle 1 is preferably 10 holes and below 800 holes.The hole count of spinneret orifice is more, can spinning fibre amount more, but solvent quantitative change in tower is many, therefore, preferably in above-mentioned scope, carries out spinning.
Preferably suitably select spinning solution to the liquor charging amount of spinning nozzle.
The air-flow of air-flow in spinning tower for being produced by air flow-producing device 3, is heated to the internal temperature of spinning cylinder 4 temperature that solvent is volatilized from spinning fibre.More than the internal temperature of the spinning cylinder 4 in the present invention is preferably 100 ℃ and below 300 ℃, more than being particularly preferably 130 ℃ and below 260 ℃.In the situation that the temperature in spinning cylinder 4 is high, the viscosity of the fiber after just spinning and can not maintain fiber shape sometimes, therefore not preferred.On the other hand, in the situation that the temperature in spinning cylinder 4 is low, the volatile quantity of solvent is few and make spinning fibre easily combination each other sometimes, therefore not preferred.For the heating in spinning cylinder 4, by supplying with high temperature air inlet by air flow-producing device 3, also the temperature in spinning cylinder 4 can be heated up, but dispose in the side of spinning tower the heater that becomes thermal source, the structure that employing is heated inner gas from wall is safe, therefore preferably.In addition, the air-flow being produced by air flow-producing device 3 is preferably non-active gas or the dry airs such as argon gas or nitrogen, particularly from the viewpoints such as blast of solvent gas, considers, is preferably the non-active gas such as argon gas or nitrogen.In addition, do not need to be fully full of argon gas or nitrogen, on there is no safety in the scope of problem, so long as can maintain the gas concentration of the state that reduces oxygen amount.
From the polyamic acid solution of spinneret orifice 2 ejections, in spinning cylinder 4, be dried.When the polyamic acid fiber 5 that is dried and is configured as fiber shape is taken out to outside from cylinder unit, use the equilateral twisting of twisting mill 6 limit to reel with bobbin.The spinning fibre 8 of reeling on bobbin by coiler device 7 preferably carries out imidizate.In addition, the remaining solvent ratios in spinning fibre 8 is now preferably more than 1% and below 70%.Particularly preferred scope is more than 15% and below 60%.By control, be the remaining solvent ratios of such polyamic acid fibrous inside, the flat ratio of the section of polyimide fiber can be controlled be more than 1.1 elliptical shape or dumbbell shapes.And then the preferred imidizate of acid imide rate of the polyamic acid fiber of the present application is more than 15%, particularly preferably imidizate is more than 20%.In order to improve the acid imide rate of polyimide fiber, carry out spinning, rate of drying is accelerated thus, and it is more than 1.1 easily flat ratio being controlled, therefore preferably.
Acid imide rate for the present application, for example, by pyromellitic acid anhydride and 4, in the polyamic acid fiber that 4-diaminodiphenyl ether forms and the situation of polyimide fiber, measure respectively the polyimide fiber that carries out imidizate completely and the infrared absorption spectroscopy of measuring the polyamic acid fiber after acid imide rate, by 1780cm
-1absorbance and 1500cm
-1absorbance try to achieve dulling luminosity ratio (1780cm
-1absorbance ÷ 1500cm
-1absorbance), for acid imide rate, by the value that acid imide rate=calculating formula of (dulling luminosity ratio of the polyamic acid fiber after mensuration) ÷ (carrying out the dulling luminosity ratio of the polyimide fiber of imidizate completely) * 100 is calculated, be acid imide rate.
Remaining solvent ratios in so-called the present invention, the spinning fibre 8 obtaining in a sampling part and weigh are also made as Wa (g) by its weight, by this sample in the situation that in the heating furnace of 350 ℃ dry weight after 20 minutes be made as Wb (g), the remaining solvent ratios value that the calculating formula of (Wa-Wb) ÷ Wb * 100 is calculated of serving as reasons.
By remaining solvent ratios is controlled as above-mentioned scope, can improve the flexibility of polyamic acid fiber, when coiling fiber, can avoid the problems such as fluffing, therefore preferably.
In addition, preferably in the manufacturing process of above-mentioned polyamic acid fiber in the present invention with remaining solvent ratios the mode in above-mentioned scope suitably temperature, spinning solution amount, spinning radical, the spinning speed in selected spinning tower, deliver to the throughput in tower.
Then, polyamic acid fiber of the present invention preferably by the polyamic acid fiber impregnation of making by above-mentioned dry spinning method in water, under more than 170 ℃ vacuum, be dried, carry out imidizate.
As the method in water by above-mentioned polyamic acid fiber impregnation, can use and in the water-bath of continous mode, flood the method for polyamic acid fiber or be wound on metal or plastic core is immersed in the method in water with batch (-type); And then, with the state of hank knotting, be immersed in the whole bag of tricks such as method in water.Particularly in the present invention, easily process polyamic acid fiber, therefore, preferably to be wound on metal-cored state, flood.In addition, as water of the present invention, preferably use deionized water or distilled water.In addition, be preferably immersed in the water of 10 ℃ of temperature ranges above and below 100 ℃.By being immersed in water, when the solvent of fibrous inside oozes out in water and in atmosphere dried fibres, can prevent from merging.
Particularly in the present invention, preferably in being immersed in the water of low temperature after, be immersed in the water of high temperature.More than being particularly preferably immersed in 10 ℃ and in 70 ℃ of following water, make water retting to fibre bundle inside, more than being immersed in 70 ℃ and in 100 ℃ of following water.By aforesaid operations, when vacuumize polyamic acid fiber, can remove efficiently the contained moisture of polyamic acid fibrous inside in the short time, therefore preferably.In addition, by carrying out so two stage temperature, control, the hydrolytic resistance of the polyimide fiber that finally obtains is improved, therefore preferably.
Metal-cored preferred use aluminium core or the stainless steel core of dipping polyamic acid fiber.
The dip time of polyamic acid fiber of the present invention in water is preferably suitably selected so that water spreads all over to fibre bundle inner.The hole of particularly preferably seizing loud, high-pitched sound water flowing for the easy infiltration of the water capacity is extremely inner is opened in above-mentioned core.
In the present invention, preferably under more than 170 ℃ vacuum, be dried and be immersed in the fiber in water.The inventor finds to be dried under the vacuum by the temperature more than 170 ℃, can, at the dry contained water of polyamic acid fibrous inside of short time, can remove the contained solvent of polyamic acid fibrous inside in the short time.And then, also find owing to being dried in the short time, therefore can prevent efficiently that the polyamic acid fiber that the solvent because oozing out causes from merging each other.
And then the present invention is preferably polyimide fiber by carrying out continuously continuous heating after dehydration by polyamic acid fiber imidizate.By carry out like this imidizate under vacuum, can suppress the hydrolysis that causes because of residual moisture, it is more than 80% can making the fracture strength conservation rate after the polyimide fiber that finally obtains is processed under the condition of 150 ℃/100%RH/48 hour.Above-mentioned heating-up temperature can be for processing identical temperature with vacuum dehydration, also can process above temperature for vacuum dehydration, even identical with dehydration treatment equipment, also can temporarily from dehydration treatment equipment, take out polyamic acid fiber and heat other device.Above-mentioned heat time heating time and heating-up temperature are preferably suitably selected according to the kind of polyamic acid, at polyamic acid fiber, be by pyromellitic acid anhydride and 4, in the situation of the polyamic acid fiber that 4 '-diaminodiphenyl ether forms, polyamic acid fiber preferably heats more than 3 hours in the vacuum drying oven of 170 ℃, preferably in the stove of 200 ℃, heat more than 2 hours, in when more than 250 ℃, heat more than 1 hour.In addition, under vacuum, the device of dry polyamic acid fiber can be used public device.In above-mentioned operation, by heating polyamic acid fiber, carry out imidizate, can improve fibre strength, in the stretching process next carrying out, show sufficient fibre strength, therefore preferably.And then, under airtight vacuum, process, therefore, can avoid operating safely with contacting of solvent, therefore preferably.
In addition, clear and definite in patent documentation 2, owing in air, the moisture of fiber being dewatered, therefore carry out the hydrolysis of polyamic acid fiber, hydrolytic resistance reduces.That is, the inventor finds, by dewatering, can improve the hydrolytic resistance of the polyimide fiber finally obtaining first under vacuum.
Then, in the present invention, by being stretching under above-mentioned vacuum at the temperature at 200 ℃～600 ℃ and with the stretching ratio of 1.0 times～2.5 times, be dried, the fiber of imidizate, after stretching, at the temperature of 200 ℃～600 ℃, heat, can obtain polyimide fiber of the present invention.
Inventor concentrates on studies, found that when vacuum drying polyamic acid fiber has been carried out in stretching, by stretching in the temperature range at 200 ℃～600 ℃, can not can make fiber heat stretch deterioratedly, the elongation at break of the polyimide fiber finally obtaining can be controlled to 10%～100%, fracture strength be controlled in the scope of 1.0cN/dtex～8.0cN/dtex.The draft temperature of the polyamic acid fiber while particularly preferably stretching is preferably 200 ℃～600 ℃, more preferably 250 ℃～580 ℃, is particularly preferably 300 ℃～550 ℃ and stretches.By temperature being controlled in above-mentioned scope, the painted and degree of stretching that can suppress fiber reduces.
In the present invention, temperature during in the situation that stretch is higher than 600 ℃, sometimes polyamic acid fiber variation and be colored as dark brown, the elongation of polyimide fiber is reduced to below 10%, in the situation that the temperature while stretching is lower than 200 ℃, polyamic acid fiber during stretching is fully not softening, therefore, when stretching, sometimes cause fibrous fracture, therefore not preferred.
Heating means during as above-mentioned stretch processing, use the device for the stretch processing of fiber, for example, can use: use have the radiant heater that is controlled at the far infrared within the scope of said temperature or the heating furnace that utilizes hot blast, use has the heating furnace of microwave or warm-up mill or the heating plate that use has heating wire or load coil.Particularly, owing to easily conducting heat until fibre bundle is inner, therefore, preferably use: use the warm-up mill or the heating plate that have heating wire or load coil.
And then preferably the sour fiber of the preferred stretching ratio drawing polyamide with 1.0 times～2.5 times within the scope of said temperature, stretches particularly preferably in 1.3 times～2.3 times.By the stretching ratio with such, stretch, the elongation at break of the polyimide fiber finally obtaining can be controlled to 10%～100%, fracture strength is controlled in the scope of 1.0cN/dtex～8.0cN/dtex, therefore preferably.In addition, at stretching ratio, lower than 1.0 in the situation that, the fracture strength of fiber diminishes sometimes, and when being configured as non-weaving cloth or fabric, the weakened of cloth sometimes, therefore not preferred.And then, while stretching to be greater than the stretching ratio of 2.5 times, although can make the fracture strength of the polyimide fiber that finally obtains also stronger than 8.0cN/dtex, but elongation at break is lower than 10% sometimes, and then the hydrolytic resistance of polyimide fiber reduces sometimes, therefore not preferred.In brief, in order to show the physical property of polyimide fiber of the present invention, preferably with above-mentioned stretching ratio, stretch.
Then, preferably, in the manufacture method of polyimide fiber of the present invention, after stretching, at the temperature of 200 ℃～600 ℃, heat.
After stretching, at the temperature of 200 ℃～600 ℃, heat, imidizate is carried out at the polyamic acid position that can make to remain on the fiber after stretching, can improve hydrolytic resistance, the intensity of polyimide fiber is improved, therefore preferably.
Heating means after stretching of the present invention can be used the heating means of using when above-mentioned stretching.And then, as the mode in when heating, such as the fiber limit that can use limit to extract out to stretch, at the temperature of 200 ℃～600 ℃, carry and the method for reeling or be wound on metal bobbin and the method heating at the temperature of 200 ℃～600 ℃ etc.
Preferably suitably select according to the structure of polyimide fiber heating-up temperature, heat time heating time.For example in the situation that the polyamic acid fiber consisting of pyromellitic acid anhydride and diaminodiphenyl ether is carried out to imidizate and the polyimide fiber that obtains, by maximum sintering temperature being made as to 450 ℃, burn till, can obtain polyimide fiber.Narrate an example, in the situation that being provided with 3 heating furnaces, in the time of 350 ℃, 400 ℃, 410 ℃, heat, for example, while changing according to 60 minutes, 10 minutes, 1 minute chien shih its by each stove, burn till, then carry out cooling and reel, can obtain the polyimide fiber of hydrolytic resistance excellence.
Polyimide fiber of the present invention also can be for after burning till, then through the polyimide fiber of the operation that heats with the stretching ratio of 0.9 times～1.2 times at more than 300 ℃ temperature.By like this polyimide fiber being added to hot-stretch, the percent thermal shrinkage at 300 ℃ can be controlled is below 3%.For the percent thermal shrinkage at 300 ℃ is controlled, be particularly below 3%, preferably at the temperature of 310 ℃～550 ℃, heat, further preferably at the temperature of 320 ℃～500 ℃, heat, particularly preferably in 350 ℃～450 ℃ of temperature, heat.
By heating, can further dwindle percent thermal shrinkage within the scope of said temperature.And then the stretching ratio that stretching ratio is preferably 0.9 times～1.2 times, particularly, by stretching in the scope at 0.9 times～1.1 times, can be controlled at the percent thermal shrinkage at 300 ℃ below 3%, therefore preferably.
For static is removed the polyimide fiber obtaining, preferably limit extracts with other device the finish that limit consists of surfactants such as anionic property, both sexes, cationic at surface-coated out again, and preferably suitably selected finish is coated with.
In the present invention, polyimide fiber preferably carry out curling processing and cutting process be configured as fibre length be 10mm～1500mm, crimp percent be 2～100 curling (crimp)/inch polyimides staple fibre.Being particularly preferably the particularly length of fiber is 25mm～100mm, and crimp percent is 2～30 curling (crimp)/inch.By being configured as such staple fibre, being easily configured as non-weaving cloth or being configured as and twist thread, therefore preferably.Polyimide fiber obtained above is carried out to curling processing with false-twisting device, can obtain the staple fibre of polyimide fiber.As curling treating apparatus, can use public methods such as clogging box or gear mode.And then the polyimide fiber after curling processing can use public apparatus for cutting fiber, be configured as the staple fibre of 25mm～100mm.
Above-mentioned polyimides staple fibre can be processed into public device twists thread or non-weaving cloth is used.Polyimide fiber of the present invention has the feature that percent thermal shrinkage is little, uses above-mentioned polyimides staple fibre and the percent thermal shrinkage of the non-weaving cloth made is little, can be preferred for bag hose etc. and be exposed to the heat-resistant filter in high temperature.And then in the filametntary situation of using with the base cloth that acts on non-weaving cloth, the size changing rate because heat resistance, hydrolytic resistance are excellent, during high temperature is little, therefore, can use for a long time under high temperature, how wet environment.For heat-resistant filter in the situation that, the mesh of filter with low uncertainty, can maintain strainability steadily in the long term, therefore preferably.
In addition, under ore furnace Work Clothes or fire-entry suit etc. are exposed to the temperature atmosphere of high temperature, be exposed in the Work Clothes of high temperature and also can preferably using the little polyimide fiber of the present invention of shrinkage factor under high temperature.Polyimide fiber is except heat resistance, and anti-flammability is also excellent, also has self-extinguishment, even if also cause at short notice the in the situation that of having just in case catch fire on clothes from putting out, the impact on human body is suppressed for minimal effect.And then, such as being also preferred for training clothes etc., be exposed to the high heat-resistant protective suit purposes of possibility in fire.
In addition, polyimide fiber of the present invention is except heat resistance, and electrical insulating property is also excellent, therefore, also can be preferred for needing the heat-resisting clothes etc. of the arc welding operation use of the tracing property of resistance to electric arc.
Polyimide fiber of the present invention is that the flat ratio with section is the fiber of more than 1.1 elliptical shapes, and skin sense of touch is also good, in the situation that for the fiber of industry goods, materials and equipments purposes, also can be preferred for the purposes with skin contact.For example, twisting thread of consisting of the mixed cotton with cotton can be widely used in various fibres.And then, by flat ratio, be that more than 1.1 self shows gloss fiber, with the fabric that polyimide fiber is made, can show gloss, therefore preferably.And then, by flat ratio being more than 1.1 polyimide fiber coating finishes, the excellences such as the line transporting while making fabric thus, the contact friction of the fiber of processing during fabric can be greatly reduced, therefore, fluffing that the friction because of line causes etc. can be suppressed, the goods that improve fabric are worth, therefore preferably.
And then, use heat resistance, flexibility, the electrical insulation reliability of the fabric that has polyimide fiber of the present invention excellent, therefore, can be preferably used as electric, electronic material.More specifically, can be preferred in fabric the lining material on the surfaces such as the electric wiring substrate made containing thermosetting resins such as epoxy resin dipping or bimaleimide resins or electric wire.
Embodiment
Below, by embodiment, the present invention will be described, but the present invention is not limited to these embodiment.
< fiber number >
Mensuration is cut to the tow of the polyimide fiber consisting of Sa root the weight (Sbg) of the fiber of 10cm, by following calculating formula, calculates fiber number.
Fiber number (dt ex)=Sb ÷ Sa * 100000
< elongation at break and fracture strength >
Use Co., Ltd.'s A & D company テ Application processed シ omnipotent experimental rig of ロ Application (RTC-1210A) and measure according to JIS-L1015.
< fracture strength conservation rate >
By said method, carry out the mensuration of the initial stage fracture strength Ha (cN/dtex) of polyimide fiber, polyimide fiber is carried out the decomposition accelerated test of 20 hours under 150 ℃, the saturated steam of 100%RH, 4 air pressure.After accelerated test, measure the fracture strength Hb (cN/dtex) of fiber and calculate fracture strength conservation rate by the calculating formula of Hb/Ha * 100.In addition, in the present invention, fracture strength conservation rate means that more greatly hydrolytic resistance is better.
< flat ratio >
Use the schematic cross-section (Fig. 2) of polyimide fiber to describe the flat ratio of polyimide fiber.With electron microscope (NEC デYiタム Co., Ltd. system, JSM-6380LA), measure the cross sectional shape of polyimide fiber, about 10 fibers wherein, as shown in Figure 2 the diameter of section of the major axis of polyimide fiber is made as to La, when the diameter of section of the vertical direction of the middle position of major axis is made as to Lb, calculate La/Lb, using the mean value of 10 fibers as flat ratio.
Percent thermal shrinkage > at <300 ℃
Try to achieve as follows the percent thermal shrinkage of polyimide fiber.Make the bundle of 1200 of the polyimide fibers of 500mm, at upper and lower 100mm, sentence the interval additional marking of 300mm, be dropped in the stove that is heated to 300 ℃ 30 minutes.Next, measure the length of the fiber of the additional marking after dropping into.Length by the fibre bundle after measuring is also calculated percent thermal shrinkage by the calculating formula of percent thermal shrinkage={ 300-(length of the fibre bundle after mensuration) } ÷ 300 * 100.
The acid imide rate > of < polyamic acid fiber
Try to achieve as follows the acid imide rate of polyamic acid fiber.Obtain the polyamic acid fiber that has carried out dry spinning, the manufacture method of the polyimide fiber by the present application, obtains completely by the polyimide fiber of imidizate.With micro-ATR-FTIR absorption spectromtry device (Paragon 1000 Perkin E1mer company systems), measure completely by the infrared absorption spectroscopy of the polyimide fiber of imidizate and polyamic acid fiber respectively, try to achieve 1780cm
-1absorbance and 1500cm
-1absorbance.By its absorbance, try to achieve dulling luminosity ratio (1780cm
-1absorbance ÷ 1500cm
-1absorbance), by the calculating formula of acid imide rate=(dulling luminosity ratio of the polyamic acid fiber after mensuration) ÷ (having carried out the dulling luminosity ratio of the polyimide fiber of imidizate completely) * 100, calculate.
(synthesis example 1)
In the reaction unit of 200L that has carried out nitrogen replacement, in the reaction unit of installation for the agitator arm of agitating solution, react.In reaction unit, drop into DMF 31.44k g, drop into 4,4 '-diaminodiphenyl ether 4.41 this, dissolve completely.
In this solution, drop into pyromellitic acid anhydride 4.32 this and uniform stirring 20 minutes.In this solution, add bit by bit that this is dissolved in N by pyromellitic acid anhydride 0.48, the solution forming in dinethylformamide 9.1kg, under the condition of 23 ℃, with Brookfield viscometer, measure in the viscosity situation of spinning solution, in the moment that becomes 2300 pools, finish to add.Become after uniform viscosity, continue uniform stirring 1 hour, obtain the polyamic acid solution that spinning is used.The solid component concentration of polyamic acid solution is 18.5%.
(embodiment 1～5)
Use the polyamic acid solution (being spinning solution below) obtaining in synthesis example 1 to carry out spinning experiment.Use the device same with Fig. 1 to carry out dry spinning.The hole count of the spinneret orifice of spinning nozzle 12 is made as to 200 holes tests.The circular spinning nozzle that the diameter that uses spinneret orifice is 0.20mm.Atmosphere temperature in spinning tower is adjusted into 210 ℃～220 ℃ and carries out spinning, confirm that the degree that can not merge each other with polyamic acid fiber in the bottom of spinning tower is dried, and is wound on bobbin.The winding speed of take was reeled as 700m/ minute.
The spray volume of spinning solution of take is adjusted as the mode of 250g/ minute, obtains polyamic acid fiber.The intrastitial remaining solvent ratios of polyamic acid is now 35%, and acid imide rate is 34%.Respectively obtain 6 these polyamic acid fibers, be processed into the tow shape of 1200.
Each 500g of tow of the polyamic acid fiber of obtaining like this is wound on the metal bobbin of stainless steel.
In the distilled water of 25 ℃, dipping was wound on fibre bundle on metal bobbin after 45 minutes, flooded 15 minutes boiling to the distilled water of 90 ℃, after dipping, at 2 minutes, with interior, put in the vacuum drying oven that is heated to 200 ℃, started decompression and heating.In vacuum drying oven, heat drying is 6 hours, obtains by the polyamic acid fiber of imidizate.
Draw speed, the stretching ratio of limit to record in table 1, the polyamic acid fiber limit after stretching imidizate stretches.
Fiber after stretching is heated under the state being wound on metal bobbin and with heating condition and the time of table 1, carry out imidizate.The polyimide fiber obtaining is processed with heating condition and the stretching ratio recorded in table 1, obtains polyimide fiber.
The result of the percent thermal shrinkage at the fracture strength conservation rate after processing under the condition of the fiber number of the polyimide fiber that mensuration is obtained, fracture strength, elongation at break, 150 ℃/100%RH/48 hour, the flat ratio of section, 300 ℃ is recorded in table 1.
(comparative example 1)
About the goods of the trade name P84 (average fineness 2.2dtex) of イ Application ス ペ Star Network Off ア イ バYi company system, the table 2 that the results are summarized in of fracture strength, elongation at break, fracture strength conservation rate will be evaluated.
Can be clear and definite, to compare with the polyimide fiber obtaining in embodiment, fracture strength conservation rate reduces greatly, and hydrolytic resistance is low.
(comparative example 2)
Use the polyamic acid solution of synthesis example 1 to make the polyamic acid fiber identical with embodiment 1～5.Limit is extracted this polyamic acid fiber limit out and in the pure water of 75 ℃, is flooded 1 minute, stretches therebetween with the stretching ratio of 1.5 times.Fiber roll after stretching is around on metal-cored.Fiber after the hot air apparatus inner dryings of 100 ℃ are reeled 4 hours.By dry fiber roll under the state of bobbin, in the stove of 275 ℃, drop into 25 minutes, in the stove of 400 ℃, drop within 25 minutes, heat, imidizate, although the surperficial fiber of result polyimide fiber is scalable, be wound with the fiber fusion of the bobbin part of fiber.Under such state, be difficult to make in large quantities polyimide fiber.And then the physics value of the polyimide fiber that mensuration can be extracted out, is recorded in table 2 by result.
Result by table 2 can be clear and definite, and the fracture strength conservation rate of polyimide fiber reduces, and hydrolytic resistance reduces.The percent thermal shrinkage of in addition, defining polyimide fiber also becomes large.
Table 1
[table 2]
| Unit | Comparative example 1 | |
| Fiber number | dtex | 2.2 |
| Fracture strength | cN/dtex | 4.5 |
| Elongation at break | ％ | 27 |
| Fracture strength conservation rate | ％ | 40 |
[table 3]
Description of reference numerals
The spinning nozzle that 1 spinning is used
2 spinneret orifices (hole)
3 air flow-producing devices
4 spinning cylinders
5 polyamic acid fibers
6 twisting mills (twisting apparatus)
7 coiler devices
8 spinning fibres
The diameter of section of the major axis of La polyimide fiber
The diameter of section of the vertical direction of the middle position of Lb major axis
Claims (10)
1. polyimide fiber, it is characterized in that, described polyimide fiber obtains by polyamic acid is carried out to imidizate, described polyamic acid is to make to be selected from pyromellitic acid anhydride, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic dianhydride, 3, 3 ', 4, the dicarboxylic anhydride of more than one in 4 '-benzophenone tetracarboxylic acid dianhydride and be selected from 4, 4 '-diaminodiphenyl ether, 3, 4-diaminodiphenyl ether, the diamines of more than one in p-phenylenediamine (PPD) reacts and obtains, the elongation at break of described polyimide fiber is 10%～100%, fracture strength is 1.0cN/dtex～8.0cN/dtex, fiber number is 0.5dtex～20dtex, fracture strength conservation rate after processing under the condition of 150 ℃/100%RH/48 hour is more than 80%, percent thermal shrinkage at 300 ℃ is below 3.0%, and having flat ratio is more than 1.1 elliptical shapes, or the section of dumbbell shape.
2. polyimide fiber according to claim 1, its manufacture method manufacture by polyimide fiber forms, and the method is characterised in that,
(a) polyamic acid solution is carried out to dry spinning, obtaining remaining solvent ratios is the fiber more than 15% and below 60%,
(b) by fiber impregnation in water,
(c) under more than 170 ℃ vacuum, be dried and make its imidizate,
(d) and then, the stretching ratio with 1.0 times～2.5 times at the temperature of 200 ℃～600 ℃ stretches, after stretching, at the temperature of 200 ℃～600 ℃, heat,
(e) after burning till, then heat by the stretching ratio with 0.9 times～1.2 times at the temperature at 310 ℃～550 ℃.
3. polyimides staple fibre, is characterized in that, described polyimides staple fibre comprises the polyimide fiber described in claim 1 or 2, and fibre length is 10mm～1500mm, and crimp percent is 2～100 curling/inches.
4. non-weaving cloth, the polyimides staple fibre that it comprises the polyimide fiber described in claim 1 or 2.
5. heat-resistant filter, it has used the polyimide fiber described in claim 1 or 2.
6. fabric, it comprises the polyimide fiber described in claim 1 or 2.
7. heat-resistant protective suit, it has used the polyimide fiber described in claim 1 or 2.
8. electric, electronic material, it has used the fabric that comprises the polyimide fiber described in claim 1 or 2.
9. the manufacture method of polyimide fiber claimed in claim 1, is characterized in that,
(a) polyamic acid solution is carried out to dry spinning, obtaining remaining solvent ratios is the fiber more than 15% and below 60%,
(b) by fiber impregnation in water,
(c) under more than 170 ℃ vacuum, be dried and make its imidizate,
(d) and then, the stretching ratio with 1.0 times～2.5 times at the temperature of 200 ℃～600 ℃ stretches, after stretching, at the temperature of 200 ℃～600 ℃, heat,
(e) after burning till, then the stretching ratio with 0.9 times～1.2 times heats at the temperature of 310 ℃～550 ℃.
10. the manufacture method of polyimides staple fibre, is characterized in that, finish is coated to the surface of the polyimide fiber described in claim 1 or 2, carries out curling, cutting.
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| PCT/JP2010/005015 WO2011018893A1 (en) | 2009-08-11 | 2010-08-10 | Polyimide fibers and use thereof, and process for production of the polyimide fibers |
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| CN103255491B (en) * | 2013-05-31 | 2015-05-20 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| JP6289014B2 (en) * | 2013-10-11 | 2018-03-07 | ソマール株式会社 | Polyimide fibers and assemblies |
| KR102431539B1 (en) * | 2017-07-19 | 2022-08-10 | 토라따니 가부시키가이샤 | clothing |
| CN109440206B (en) * | 2019-01-08 | 2021-07-09 | 长乐力恒锦纶科技有限公司 | Production process of novel FDY (fully drawn yarn) dull polyamide-6 with flat section |
| US20220186440A1 (en) * | 2019-02-19 | 2022-06-16 | Du Pont-Toray Co., Ltd. | Polyimide fiber paper using non-thermoplastic polymer |
| CN113604899A (en) * | 2021-09-08 | 2021-11-05 | 许绝电工股份有限公司 | Continuous production method of polyimide fibers |
| CN114632433B (en) * | 2022-04-18 | 2023-05-09 | 南昌大学共青城光氢储技术研究院 | Preparation method of flexible three-dimensional self-supporting noble metal-carbon fiber network material |
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