CN1776035A - PVA fiber and its non-woven fabric preparing method - Google Patents
PVA fiber and its non-woven fabric preparing method Download PDFInfo
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- CN1776035A CN1776035A CN 200510016460 CN200510016460A CN1776035A CN 1776035 A CN1776035 A CN 1776035A CN 200510016460 CN200510016460 CN 200510016460 CN 200510016460 A CN200510016460 A CN 200510016460A CN 1776035 A CN1776035 A CN 1776035A
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Abstract
A method for making PVA fiber and non-woven fabrics, whose formula (by weight) is PVA 5-15 %, 20-85 % of inorganic metal oxide micropowder. 0-5 % of dispersant, 0-5 % of anti precipitant and the others are water. Said PVA has 1700-2000 of degree of polymerization, said inorganic metal oxide micropowder is any one kind of ZnO, Al2O3, TiO2, SiO2 or ceramic powder with 0.5-60 micrometer of grain size, said dispersant is one kind of polyethylene, Tween or polyacrylic acid, said anti precipitant is one kind of cane sugar, glucose, Arabic gum, polyacrylamide, soluble starch or beeswax. Said method can adopts improved traditional two-stage method or new one-stage method, the prepared non-woven fabrics has both of original and new performance.
Description
Technical field
The present invention relates to a kind of chemical fibre and manufacture method thereof and goods technology, be specially a kind of manufacture method technology that contains the PVA fiber and the nonwoven fabric thereof of inorganic matter micropowder, international monopoly Main classification number plan is Int.CL
7D01F 6/14.
Background technology
Polyvinyl alcohol (PVA) is the widely used chemical fibre of a class, owing to have hydroxyl in its molecular structure, makes PVA fiber and nonwoven fabric product thereof have excellent moisture pick-up properties, thereby is widely used in medical treatment, health and field such as civilian.The PVA fiber generally adopts the solvent spinning process to obtain, and is about to PVA and is dissolved in certain solvent, adopts wet method or dry process to carry out spinning, passes through operations such as drawing-off, HEAT SETTING again, the PVA fiber that just can obtain having certain intensity.In inventor's range of search, the PVA fiber that adopts the solvent spinning process to obtain is at present all made by one matter PVA, does not promptly contain other solid constituents.The deficiency of this one matter PVA fiber is the fiber strand silk smooth surface, the clothing that is suitable for being made into, and be difficult to as Wiping material.On the other hand, the PVA fiber is commonly used to make the nonwoven fabric product.The manufacture method of conventional P VA nonwoven fabric product is to be raw material with the PVA fiber, utilizes nonwoven fabric or non-weaving cloth net-forming process, as water thorn, acupuncture or method such as hot sticky, and laying net for shaping and making.That is to say, in existing nonwoven fabric moulding process, be that water thorn, acupuncture, hot sticky method all are to make fibrous finished product earlier, does raw material with it then, carries out secondary operations and obtain the nonwoven fabric product, and the processing separate operation of fiber, nonwoven fabric is independently carried out.The process that this fiber, nonwoven fabric separately carry out makes the performance of PVA nonwoven fabric product both be subjected to the influence of front end fiber product quality, and is relevant with the processing technology of nonwoven fabric again, nonwoven fabric preparation technology more complicated, and product quality is also restive.
About the modification of PVA fiber and the existing many reports of patent documentation of manufacture method and nonwoven fabric product thereof.Japan Kuraray Co., Ltd has just applied for many patents to the modification and the nonwoven fabric product thereof of PVA fiber in China.For example, Chinese patent CN94118659 bibliographical information a kind of method of making water-soluble hot pressing polyvinyl alcohol binder fiber and nonwoven fabric thereof.It at first makes spinning solution with low melting point water-soluble polymer (B) is miscible with high-melting-point PVA polymer (A) in the solvent of polymer (A), carrying out low-temp spinning makes it solidify the formation sea-island shaped area, (A) as sea component, (B) exist as the island component, and fiber surface does not contain the island component substantially.Then at high temperature during pressurized, low melting point polymer (island component) is pushed to fiber surface and makes heat bonding takes place between the fiber, utilizes this character to make nonwoven fabric by this fiber.The nonwoven fabric that Chinese patent CN03158691 document discloses a kind of high absorption polyvinyl alcohol fibre and comprised them, this high-hydroscopicity vinal is to introduce linked in water-solubility PVA, utilize nonwoven fabric moulding process such as existing acupuncture, water thorn, hot pressing again, preparation comprises their nonwoven fabric.Chinese patent CN200410031459 document provides a kind of PVA polymer fiber of easy fibrillation, and it has good chemical resistance, hydrophily, weatherability and WATER RESISTANCE, utilizes water thorn or needling process to be processed into nonwoven fabric again.Chinese patent CN200410033004 document has been introduced a kind of polyvinyl alcohol binder fiber, it is characterized in that this fiber has maximum 30% cross section circularity, in 30 ℃ water, have at least 100% swellbility, and maximum therein 20% solubility, and then be processed into nonwoven fabric.Chinese patent CN200510003804 document discloses a kind of water-soluble polyvinyl alcohol fiber and has comprised the manufacture method of the nonwoven fabric of this fiber, being about to the degree of polymerization is that 1000-4000 and the above vinol series polymer of 88 moles of % of saponification degree are dissolved in the organic solvent, the spinning solution that obtains is carried out solvent spinning, and make fiber obtain fiber by a kind of extraction bath that contains the glyoxalated compound of ionic base, method through hot pressing obtains nonwoven fabric again, can be used for very effectively with a lot of purposes headed by the burnt-out lace usefulness base fabric.Prepare in the method for modified PVA fiber and nonwoven fabric product thereof at above-mentioned these, solid content is less than 20% in the spinning solution, and raw material is essentially single PVA.Because the content of water is more in the spinning solution, thereby when polymer dope directly being extruded into net, because the moisture in the strand is many, can only adopt and fiber be solidified the method for strand by the coagulating bath curing molding, and then make the fiber lay down net forming, also promptly be divided into two steps manufacturing nonwoven fabric.This two step method nonwoven fabric manufacturing technique has not only increased the curing molding step of fiber in coagulating bath, and the fiber after solidifying wants directly to carry out continuously the mechanical carding of fiber, lapping manufacturing nonwoven fabric to also have many technological difficulties still unresolved in the production of reality, thereby want to adopt time processing technology also infeasible in reality.At present, solid content adopts solwution method to prepare the method for PVA fiber greater than 20%, and utilizes the patent documentation that gained PVA fiber directly is processed into nonwoven fabric not appear in the newspapers as yet.
Summary of the invention
At the deficiencies in the prior art, the technical problem to be solved in the present invention is that the manufacture method of a kind of PVA fiber and nonwoven fabric thereof is provided.Contain inorganic micro powder in this PVA fiber, the solid content in spinning solution can be up to 50-85%; This PVA fibre manufacture adopts existing spinning equipment, small investment, and technology is simple, produces easily; And this PVA fiberizing is processed and can directly be carried out continuously and finish by its processing of further making nonwoven fabric, and technological process is shortened, simplified control, and efficient greatly improves, and quality is also guaranteed.
The technical scheme that the present invention solves described PVA fibre technology problem is: design a kind of PVA fiber, this quality of fiber percentage prescription is: PVA 5-15%, inorganic, metal oxide micro mist 20-85%, dispersant 0-5%, antiprecipitant 0-5%, surplus is a water, each component sum is 100%; The degree of polymerization of described PVA is 1700-2000, and described inorganic, metal oxide micro mist is meant ZnO, Al
2O
3, TiO
2, SiO
2Or in the ceramic powder any one or more, particle diameter is 0.5-60 μ m; Described dispersant is meant any one or more in polyethylene glycol, tween or the polyacrylic acid; Described antiprecipitant is meant any one or more in sucrose, glucose, Arabic gum, polyacrylamide, soluble starch or the beeswax.
The technical scheme that the present invention solves described PVA fabric nonwoven cloth manufacture method technical problem is: design a kind of manufacture method of PVA fabric nonwoven cloth, it adopts following technology:
1. prepare the PVA spinning solution: adopt PVA fiber prescription of the present invention to prepare the PVA spinning solution;
2. preparation PVA fiber: carry out wet method or dry spinning promptly with the 1st PVA spinning solution that goes on foot gained; When adopting wet spinning, coagulating bath is the saturated saltcake aqueous solution, and spinning temperature 80-98 ℃, the spinneret hole diameter is 0.2-2mm, and draw ratio is 0-10 times; When adopting dry spinning, the temperature of hot-air is 120-150 ℃, ring-like blowing, the same wet spinning of other technological parameter;
3. prepare the PVA nonwoven fabric: can make through high temperature hot pressing with resultant PVA fiber of the 2nd step; Hot pressing temperature is 80-120 ℃, pressure 30-60Nmm
-1
4. nonwoven fabric post processing: carry out acetalation in the PVA nonwoven fabric immersion hydroformylation bath to the 3rd step gained and handle promptly.What hydroformylation was bathed consists of: sulfuric acid 200-250g/L, sodium sulphate 50-90g/L, formaldehyde 15-35g/L; 50-90 ℃ of hydroformylation temperature, 10-20 minute hydroformylation time.
Another technical scheme that the present invention solves described PVA fabric nonwoven cloth manufacture method technical problem is: design a kind of manufacture method of PVA fabric nonwoven cloth, it adopts following technology:
1. prepare the PVA spinning solution: adopt claim 1 or 2 described PVA fiber prescriptions to prepare the PVA spinning solution;
2. prepare the PVA nonwoven fabric: with the PVA spinning solution of the 1st step gained, on extruder, extrude strand, spinning temperature is 80-98 ℃, and under temperature 120-150 ℃ hot-air, stretching 0-10 doubly, and then be that random laying net for shaping on hot-rolling promptly obtains the PVA nonwoven fabric under 120-150 ℃ the hot air flow effect in temperature dry strand;
3. nonwoven fabric post processing: carry out acetalation in the PVA nonwoven fabric immersion hydroformylation bath to the 2nd step gained and handle, what hydroformylation was bathed consists of: sulfuric acid 200-250g/L, sodium sulphate 50-90g/L, formaldehyde 15-35g/L; 50-90 ℃ of hydroformylation temperature, 10-20 minute hydroformylation time.
Compared with prior art, the solid content in the PVA fibre spinning solution of the present invention can be up to 50-85%, but still spinning smoothly; Manufacture method by its preparation nonwoven fabric product, both can adopt traditional two step method manufacturing, also can adopt new one-step method manufacturing---the manufacture method that the moulding of polymer fiber and the processing of nonwoven fabric are carried out simultaneously continuously, technological process is shortened, simplified control, efficient improves, and quality also improves synchronously, cost reduces, and has favorable economic benefit; No matter and be that conventional method or new method are made nonwoven fabric, used equipment all can adopt existing technical equipment, does not need to increase equipment investment, and it is convenient to implement, and promotes easily.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment:
PVA fiber of the present invention, its mass percent prescription is: PVA 5-15%, inorganic, metal oxide micro mist 20-85%, dispersant 0-5%, antiprecipitant 0-5%, surplus is a water, each component sum is 100%.
The degree of polymerization of PVA of the present invention is 1700-2000.Test shows that after the PVA in this degree of polymerization scope added the inorganic, metal oxide micro mist of described high-load, spinnability was still better.
Inorganic, metal oxide micro mist of the present invention (hereinafter to be referred as inorganic micro powder) is meant ZnO, Al
2O
3, TiO
2, SiO
2Or in the ceramic powder any one or more, the solid content in spinning solution can be up to 20-85%, preferred 50-85%.During concrete prescription, the solid content in spinning solution can be that the 5-20 of PVA doubly comes to determine according to inorganic micro powder content.The kind of inorganic micro powder can be selected according to the needs of actual product, for example, adds inorganic micro powder ZnO, TiO
2, can make PVA fiber and bonded fabric product thereof have certain antibiotic property; And interpolation inorganic micro powder Al
2O
3, then can make PVA fiber and nonwoven fabric thereof have heat-resisting quantity etc.The particle diameter of inorganic micro powder is controlled at 0.5-60 μ m, and grain makes spinneret orifice stop up when too big easily, is not easy into silk; And the grain through hour, cost is too high, exceeds actual needs.But in the scope of conditions permit, should reduce the particle diameter of inorganic micro powder as far as possible, so that spinning is carried out smoothly.
Dispersant of the present invention is meant one or more in polyethylene glycol, tween or the polyacrylic acid, and consumption is the 0-5% of PVA prescription.This mainly be consider in the PVA spinning solution, added inorganic micro powder after, evenly disperse in PVA solution in order to make inorganic micro powder, improve the interaction of inorganic micro powder and PVA.During concrete prescription, dispersant kind and quantity can be decided according to the kind and the quantity of inorganic micro powder.The quantity of dispersant should be determined according to the size and the content of inorganic micro powder particle diameter.The particle diameter of inorganic micro powder is big, the content height, and the quantity of dispersant is also wanted corresponding increase, to slow down the reunion deposition of inorganic micro powder in the PVA spinning solution.In the selection of dispersant, preferentially select the dispersant of polyethylene glycols for use, because the molecular structure of polyethylene glycol and polyvinyl alcohol are close, all contain hydrophilic hydroxyl in the molecule, to the good dispersion of inorganic micro powder, not obvious to the influence of PVA spinning solution.
Antiprecipitant of the present invention is meant one or more in Arabic gum, polyacrylamide, soluble starch or the beeswax, and its consumption is the 0-5% of PVA fiber prescription.This mainly is to consider that solid content is higher in the PVA spinning solution, in order to reduce or reduce the settlement action of inorganic micro powder in spinning process, makes spinning carry out smoothly adding.During concrete prescription, the kind of antiprecipitant and quantity also will be decided according to the kind and the quantity of inorganic micro powder.But ordinary priority is selected the antiprecipitant that contains hydroxyl structure in the molecular structure for use, as soluble starch etc.The hydrophily of this class antiprecipitant is strong, and good water solubility can effectively be slowed down the settlement action of inorganic micro powder in the PVA spinning solution.The quantity of antiprecipitant should determine that the particle diameter of inorganic micro powder is big according to the size and the content of inorganic micro powder particle diameter, the content height, and the quantity of antiprecipitant is also wanted corresponding increase.Though also should be noted that in the PVA fiber prescription of the present invention not add described dispersant and antiprecipitant, the content that also is them is 0%; But after adding them, can improve the solid content in the PVA fiber solution, and can prevent effectively that them from precipitating, help them and be uniformly dispersed, improve spinnability and product quality.
In the prior art, because PVA adopts solwution method to carry out spinning more, comprise wet spinning and dry spinning.The solid content of PVA only is about 18-22% in the conventional wet spinning, in order to remove the large quantity of moisture in the strand, the fiber of extruding must be contained saturated Na by one
2SO
4Coagulating bath, make fiber in coagulating bath, carry out double diffusion, thereby reach the purpose that strand solidifies.Conventional dry spinning also can prepare the PVA fiber, and the solid content in the spinning solution can reach about 40%, after the process spinnerets is extruded strand, utilizes the moisture in the hot-air removal strand, and drawn and HEAT SETTING obtain traditional PVA fiber again.Domestic most of chemical fibre factories still more at present adopts wet spinning to prepare the PVA fiber.
PVA fiber of the present invention is to join as additive and carry out the PVA fibre modification in the spinning solution containing a certain amount of selected inorganic micro powder.This design both can remain with the spinnability and the pliability of organic fiber polymer, can increase the rigidity and the ABRASION RESISTANCE of inorganic matter again, thereby can give its some new capabilities on the original feature base of PVA fiber.For example, this non-woven fabric of the present invention when being used for filtering material, optionally kills the bacterium in the filtrate owing to contain inorganic, metal oxide micro mist particle in the fiber, thus purifying filter liquor; When the Wiping material, can carry out meticulous polishing, polishing to wood furniture, daily utensil etc., make goods have characteristics such as best bright finish, smooth surface, texture are good.
The manufacture method essence of PVA fiber of the present invention is same as prior art, does not have statement newly.
PVA fiber of the present invention mainly is to be used for making nonwoven fabric.The present invention has designed the manufacture method of PVA nonwoven fabric simultaneously.According to described PVA fiber prescription, the present invention has designed the manufacture method of two kinds of PVA nonwoven fabric: a kind of is according to improved conventional two-step technology, promptly makes the PVA fiber earlier, is reprocessed into the process of PVA nonwoven fabric; Another kind is the one-step technology that the present invention creates, i.e. the continuous one step completed process of PVA fibre spinning and nonwoven fabric moulding.
In order to make the PVA fabric nonwoven cloth product of this high-load inorganic micro powder, when adopting traditional two-step method making fabrication technique, can adopt improved wet method or dry method to carry out solvent spinning.Owing to added the inorganic micro powder of high-load in the spinning solution, so the orifice diameter of spinnerets is at 0.2-2mm in the filament spinning component, be 5-25 times of conventional spinning spinneret aperture.In addition, because the inorganic micro powder content in this PVA fiber is very high, the 5-20 that is about PVA content doubly, can reduce the intensity of PVA fiber to a certain extent, thereby in spinneret draft and follow-up stretching-heat setting process, should suitably reduce draw ratio, the draw ratio of the present invention's design is 0-10 times, in order to avoid strand ruptures under the condition of high draw ratio.The above-mentioned this PVA fiber that obtains is carried out laying net for shaping again, can obtain corresponding nonwoven fabric product.The concrete technology that two-step method is made nonwoven fabric is as follows:
1. prepare the PVA spinning solution: adopt PVA fiber prescription of the present invention to prepare the PVA spinning solution;
2. preparation PVA fiber: carry out wet method or dry spinning promptly with the 1st PVA spinning solution that goes on foot gained; When adopting wet spinning, coagulating bath is the saturated saltcake aqueous solution, and spinning temperature 80-98 ℃, preferred 90-95 ℃, orifice diameter is 0.2-2mm, and preferred 0.5-1.0mm, draw ratio are 0-10 times, and preferred 0-5 doubly; When adopting dry spinning, the temperature of hot-air is 120-150 ℃, preferred 130-140 ℃, and ring-like blowing, the same wet spinning of other technological parameter;
3. prepare the PVA nonwoven fabric: can make through high temperature hot pressing with resultant PVA fiber of the 2nd step; Hot pressing temperature is 50-120 ℃, preferred 60-80 ℃, and pressure 30-60Nmm-1, preferred 40-50Nmm
-1
4. nonwoven fabric post processing: handle carrying out acetalation in the PVA nonwoven fabric immersion hydroformylation bath of the 3rd step gained, what hydroformylation was bathed consists of: sulfuric acid 200-250g/L, preferred 225g/L, sodium sulphate 50-90g/L, preferably 70g/L, formaldehyde 15-35g/L, preferably 25g/L; Hydroformylation temperature: 50-90 ℃, preferred 70-80 ℃, 10-20 minute hydroformylation time, preferred 10-15 minute.PVA nonwoven fabric resistance to elevated temperatures after acetalation is handled can be brought up to 110 ℃, and the heat-resisting coolant-temperature gage of traditional PVA nonwoven fabric only is 40-80 ℃.
Although adopt improved traditional two-step process can make the nonwoven fabric of the present invention prescription, the intensity of the PVA nonwoven fabric product of this high-load inorganic micro powder that is obtained by two-step method is not high, poor-performing.This is owing to two-step process itself determines: the performance of rear end nonwoven fabric product is subjected to the influence of front end PVA fibre property, content owing to its inorganic micro powder in the PVA fiber that front end obtains is very high, can not improve the orientation of fiber by effective stretching, thereby the intensity of gained fiber is lower; In follow-up nonwoven fabric moulding process, in order to make fiber have certain mixed and disorderly degree, need carry out mechanical carding to front end PVA staple fibre and become net, this mechanical carding need be realized by means such as certain current, prickers, and the effect meeting of technological means such as current, pricker further reduces the PVA quality of fibre, even make fibrous fracture, thereby finally influence the performance and the quality of PVA nonwoven fabric product.
For the PVA nonwoven fabric product of the high-load inorganic micro powder that obtains excellent performance, the present invention has designed the step process method that the lapping technology with the spinning moulding of polymer P VA and nonwoven fabric continues simultaneously and carries out.This new method adopts following technology:
1. prepare the PVA spinning solution: adopt PVA fiber prescription of the present invention to prepare the PVA spinning solution;
2. prepare the PVA nonwoven fabric:, on extruder, extrude strand, spinning temperature 80-98 ℃ with the PVA spinning solution of the 1st step gained, preferred 90-95 ℃, orifice diameter is 0.2-2mm, preferred 0.5-1.0mm, and under temperature 120-150 ℃ hot-air, stretching 0-10 times, preferred 0-5 doubly; And then be that preferred 130-140 ℃, random laying net for shaping on hot-rolling promptly obtains the PVA nonwoven fabric under 120-150 ℃ the hot air flow effect in temperature dry strand;
3. nonwoven fabric post processing: handle carrying out acetalation in the PVA nonwoven fabric immersion hydroformylation bath of the 2nd step gained, what hydroformylation was bathed consists of: sulfuric acid 200-250g/L, preferred 225g/L, sodium sulphate 50-90g/L, preferably 70g/L, formaldehyde 15-35g/L, preferably 25g/L; Hydroformylation temperature: 50-90 ℃, preferred 70-80 ℃, 10-20 minute hydroformylation time, preferred 10-15 minute.PVA nonwoven fabric resistance to elevated temperatures after acetalation is handled can be brought up to 110 ℃, and the heat-resisting coolant-temperature gage of traditional PVA nonwoven fabric only is 40-80 ℃.
One-step method PVA nonwoven fabric manufacture method principal character of the present invention is to have saved the PVA fiber production operation of traditional handicraft method, make the PVA fiber after being extruded by spinnerets, utilize temperature 120-150 ℃ hot-air directly to remove excessive moisture in the fiber immediately, make then strand under near the condition of bone dry directly on hot-rolling laying net for shaping obtain nonwoven fabric.Because solid content very high (total content of PVA and inorganic micro powder has accounted for 50-85% in the preferred PVA spinning solution) in the PVA fiber prescription of the present invention, moisture content seldom, thereby in the process of processing that continues, utilize hot-air can take away excessive moisture in the fiber.In addition, hot-air except can taking away the moisture in the fiber, thereby also can carry out the intensity that the low power drawing-off has improved fiber to a certain extent to strand.Clearly, the moulding process that this one-step method prepares the PVA nonwoven fabric is simple, and suitability for industrialized production can be used existing chemical fiber machinery and non-woven fabrics apparatus processing, perhaps they is carried out simple refit and realizes.In addition because the PVA fiber is being extruded directly laying net for shaping of back, has avoided in the two-step method mechanical carding such as current or acupuncture to the damage of fibre strength, thereby can further improve the quality and the performance of PVA nonwoven fabric.
One-step method PVA nonwoven fabric manufacture method of the present invention has been used for reference the dry-press process technology and the nonwoven fabric melt-blown process of PVA fiber, merges some technical characterstic of these two kinds of methods, thereby does not address part and be applicable to
Prior art.
Provide specific embodiments of the invention below:
Embodiment 1
Two-step method prepares the PVA nonwoven fabric: carry out wet spinning earlier and prepare the PVA fiber, be reprocessed into nonwoven fabric.
Wet spinning: 8%PVA 50g, water 230g, the grain warp is the Al of 1-40 μ m
2O
3350g, PVA/Al
2O
3Mass ratio 7: 1.PVA wet spinning technology: 8%PVA 50g is dissolved in 80 ℃ of 230g water, adds described Al in batches
2O
3350g, warming while stirring to 95 ℃ makes spinning solution.Carry out wet spinning with resulting spinning solution, orifice diameter 0.8mm, 90 ℃ of spinning temperatures, coagulating bath is the saturated saltcake aqueous solution, draw ratio is 7 times;
The nonwoven fabric moulding process: make nonwoven fabric with resulting PVA fiber through hot pressing, hot pressing temperature is 80 ℃, pressure 40Nmm
-1
Acetalation is handled: after carrying out the acetalation processing during PVA nonwoven fabric immersion hydroformylation is bathed, promptly get the PVA bonded fabric product.Hydroformylation is bathed and is consisted of: sulfuric acid 225g/L, sodium sulphate 70g/L, formaldehyde 25g/L; 70 ℃ of hydroformylation temperature, 15 minutes hydroformylation time.
Embodiment 2
Two-step method prepares the PVA nonwoven fabric: carry out wet spinning earlier and prepare the PVA fiber, be reprocessed into nonwoven fabric.
Wet spinning technology: 9.5%PVA 50g is dissolved in 80 ℃ of 180g water, adds ceramic powder 300g (particle diameter 0.5-30 μ m) in batches, polyethylene glycol 3mL, warming while stirring to 98 ℃.The above-mentioned spinning solution that obtains is carried out the wet spinning moulding, and the spinneret hole diameter is 0.5mm, 95 ℃ of spinning temperatures, and coagulating bath is the saturated saltcake aqueous solution, is 9 times to the drafting multiple of fiber.
The nonwoven fabric moulding process: make nonwoven fabric with resulting PVA fiber through hot pressing, hot pressing temperature is 110 ℃, pressure 30Nmm
-1
Acetalation is handled: after carrying out the acetalation processing during PVA nonwoven fabric immersion hydroformylation is bathed, promptly get the PVA bonded fabric product.Hydroformylation is bathed and is consisted of: sulfuric acid 240g/L, sodium sulphate 90g/L, formaldehyde 35g/L; 80 ℃ of hydroformylation temperature, 10 minutes hydroformylation time.
Embodiment 3
Two-step method prepares the PVA nonwoven fabric: carry out dry spinning earlier and prepare the PVA fiber, be reprocessed into nonwoven fabric.
Dry-spinning process: 6%PVA 50g is dissolved in 80 ℃ of 230g water, adds ceramic 500g (particle diameter 0.5-30 μ m) in batches, tween 7mL, Arabic gum 6g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out dry spinning.The spinneret hole diameter is 0.8mm, and 80 ℃ of spinning temperatures, hot air temperature are 130 ℃, ring-like blowing, and hot-air is 3 times to the drafting multiple of fiber.
Nonwoven fabric moulding process: 60 ℃ of hot pressing temperatures, pressure 60Nmm
-1
Acetalation is handled: after carrying out the acetalation processing during PVA nonwoven fabric immersion hydroformylation is bathed, promptly get the PVA bonded fabric product.Hydroformylation is bathed and is consisted of: sulfuric acid 220g/L, sodium sulphate 60g/L, formaldehyde 35g/L; 80 ℃ of hydroformylation temperature, 15 minutes hydroformylation time.
Embodiment 4
Two-step method prepares the PVA nonwoven fabric: carry out dry spinning earlier and prepare the PVA fiber, be reprocessed into nonwoven fabric.
Dry-spinning process: 15%PVA 50g is dissolved in 90 ℃ of 80g water, adds Al in batches
2O
3200g (particle diameter 10-50 μ m), polyethylene glycol 2mL, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out dry spinning.The spinneret hole diameter is 1mm, and 95 ℃ of spinning temperatures, hot air temperature are 120 ℃, ring-like blowing, and hot-air is 2 times to the drafting multiple of fiber.
Nonwoven fabric moulding process: 80 ℃ of hot pressing temperatures, pressure 50Nmm
-1
Acetalation is handled: after carrying out the acetalation processing during PVA nonwoven fabric immersion hydroformylation is bathed, promptly get the PVA bonded fabric product.Hydroformylation is bathed and is consisted of: sulfuric acid 210g/L, sodium sulphate 70g/L, formaldehyde 35g/L; 80 ℃ of hydroformylation temperature, 15 minutes hydroformylation time.
Embodiment 5
One-step method prepares the PVA nonwoven fabric.
5.3%PVA 50g is dissolved in 80 ℃ of 150g water, adds ZnO 750g (particle diameter 30-60 μ m) in batches, polyacrylic acid 10g, soluble starch 12g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 0.8mm, and 90 ℃ of spinning temperatures, hot air temperature are 130 ℃, ring-like blowing, and hot-air is 0 to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of 130 ℃ of thermal air currents, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is consisted of: sulfuric acid 240g/L, sodium sulphate 70g/L, formaldehyde 25g/L; 80 ℃ of hydroformylation temperature, 11 minutes hydroformylation time.
Embodiment 6
One-step method prepares the PVA nonwoven fabric.
6.4%PVA 50g is dissolved in 80 ℃ of 230g water, adds TiO in batches
2500g (particle diameter 5-60 μ m), tween 7mL, soluble starch 10g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 2mm, and 80 ℃ of spinning temperatures, hot air temperature are 120 ℃, ring-like blowing, and hot-air is 2 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is consisted of: sulfuric acid 210g/L, sodium sulphate 80g/L, formaldehyde 35g/L; 70 ℃ of hydroformylation temperature, 18 minutes hydroformylation time.
Embodiment 7
One-step method prepares the PVA nonwoven fabric.
6.7%PVA 30g is dissolved in 80 ℃ of 100g water, adds ceramic powder 320g (particle diameter 0.5-30 μ m) in batches, Arabic gum 6g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 0.8mm, and 95 ℃ of spinning temperatures, hot air temperature are 140 ℃, ring-like blowing, and hot-air is 3 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is consisted of: sulfuric acid 225g/L, sodium sulphate 70g/L, formaldehyde 25g/L; 70 ℃ of hydroformylation temperature, 13 minutes hydroformylation time.
Embodiment 8
One-step method prepares the PVA nonwoven fabric.
7.7%PVA 50g is dissolved in 80 ℃ of 150g water, adds SiO in batches
2450g (particle diameter 10-50 μ m), polyethylene glycol 8g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 1.5mm, and 85 ℃ of spinning temperatures, hot air temperature are 130 ℃, ring-like blowing, and hot-air is 2 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is consisted of: sulfuric acid 225g/L, sodium sulphate 70g/L, formaldehyde 25g/L; 60 ℃ of hydroformylation temperature, 15 minutes hydroformylation time.
Embodiment 9
One-step method prepares the PVA nonwoven fabric.
7.5%PVA 30g is dissolved in 80 ℃ of 100g water, adds ZnO 320g (particle diameter 30-50 μ m) in batches, soluble starch 10g, Arabic gum 3g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 2mm, and 90 ℃ of spinning temperatures, hot air temperature are 130 ℃, ring-like blowing, and hot-air is 5 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is formed with embodiment 5.
Embodiment 10
One-step method prepares the PVA nonwoven fabric.
8.7%PVA 40g is dissolved in 80 ℃ of 100g water, adds Al in batches
2O
3320g (particle diameter 1-40 μ m), polyethylene glycol 3mL, soluble starch 5g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 0.8mm, and 95 ℃ of spinning temperatures, hot air temperature are 130 ℃, ring-like blowing, and hot-air is 3 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is formed with embodiment 6.
Embodiment 11
One-step method prepares the PVA nonwoven fabric.
9.5%PVA 50g is dissolved in 80 ℃ of 180g water, adds Al in batches
2O
3300g (particle diameter 1-40 μ m), polyethylene glycol 3mL, polyacrylic acid 5g, polyacrylamide 5g, warming while stirring to 98 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 0.5mm, 90 ℃ of spinning temperatures, and 140 ℃ of hot air temperatures, ring-like blowing, hot-air is 6 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is formed with embodiment 8.
Embodiment 12
One-step method prepares the PVA nonwoven fabric.
11%PVA 50g is dissolved in 80 ℃ of 100g water, adds Al in batches
2O
3300g (particle diameter 1-40 μ m), polyacrylic acid 5g, warming while stirring to 98 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 2mm, and 90 ℃ of spinning temperatures, hot air temperature are 130 ℃, ring-like blowing, and hot-air is 4 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is formed with embodiment 8.
Embodiment 13
One-step method prepares the PVA nonwoven fabric.
12%PVA 50g is dissolved in 90 ℃ of 100g water, adds ceramic 270g (particle diameter 10-50 μ m) in batches, polyethylene glycol 5g, soluble starch 5g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 1mm, and 90 ℃ of spinning temperatures, hot air temperature are 120 ℃, ring-like blowing, and hot-air is 2 times to the drafting multiple of fiber.The fiber that obtains is again through being hot pressed into nonwoven fabric, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is formed with embodiment 8.
Embodiment 14
One-step method prepares the PVA nonwoven fabric.
12%PVA 50g is dissolved in 90 ℃ of 100g water, adds SiO in batches
2270g (particle diameter 10-50 μ m), tween 2mL, beeswax 5g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 0.8mm, and 95 ℃ of spinning temperatures, hot air temperature are 140 ℃, ring-like blowing, and hot-air is 1 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out the acetalation processing again and obtains goods.Hydroformylation is bathed and is formed with embodiment 8.
Embodiment 15
14%PVA 50g is dissolved in 90 ℃ of 100g water, adds Al in batches
2O
3200g (particle diameter 1-40 μ m), polyethylene glycol 2mL, soluble starch 5g, warming while stirring to 95 ℃.The above-mentioned spinning solution that obtains is carried out the moulding of one-step method nonwoven fabric.The spinneret hole diameter is 0.5mm, and 98 ℃ of spinning temperatures, hot air temperature are 140 ℃, ring-like blowing, and hot-air is 6 times to the drafting multiple of fiber.Fiber is random arrangement heat bonding moulding on hot-rolling under the effect of thermal air current, carries out can obtaining the PVA bonded fabric product after acetalation handles again.Hydroformylation is bathed and is formed with embodiment 8.
Claims (6)
1. PVA fiber, its mass percent prescription is: PVA 5-15%, inorganic, metal oxide micro mist 20-85%, dispersant 0-5%, antiprecipitant 0-5%, surplus is a water, each component sum is 100%; The degree of polymerization of described PVA is 1700-2000, and described inorganic, metal oxide micro mist is meant ZnO, Al
2O
3, TiO
2, SiO
2Or in the ceramic powder any one or more, particle diameter is 0.5-60 μ m; Described dispersant is meant any one or more in polyethylene glycol, tween or the polyacrylic acid; Described antiprecipitant is meant any one or more in sucrose, glucose, Arabic gum, polyacrylamide, soluble starch or the beeswax.
2. PVA fiber according to claim 1 is characterized in that inorganic micro powder is 50-85% in the described prescription; The preferred polyethylene glycol of described dispersant; The preferred soluble starch of described antiprecipitant.
3. the manufacture method of a PVA fabric nonwoven cloth, it adopts following technology:
(1) preparation PVA spinning solution: adopt claim 1 or 2 described PVA fiber prescriptions to prepare the PVA spinning solution;
(2) preparation PVA fiber: carry out wet method or dry spinning promptly with (1) the PVA spinning solution that goes on foot gained; When adopting wet spinning, coagulating bath is the saturated saltcake aqueous solution, and spinning temperature 80-98 ℃, preferred 90-95 ℃, orifice diameter is at 0.2-2mm, and draw ratio is 0-10 times; When adopting dry spinning, the temperature of hot-air is 120-150 ℃, ring-like blowing, the same wet spinning of other technological parameter;
(3) preparation PVA nonwoven fabric: can make through high temperature hot pressing with resultant PVA fiber of (2) step; Hot pressing temperature is 80-120 ℃, pressure 30-60Nmm
-1
(4) nonwoven fabric post processing: carry out acetalation in the PVA nonwoven fabric immersion hydroformylation bath to (3) step gained and handle promptly, what hydroformylation was bathed consists of: sulfuric acid 200-250g/L, sodium sulphate 50-90g/L, formaldehyde 15-35g/L; Hydroformylation temperature: 50-90 ℃, preferred 70-80 ℃, 10-20 minute hydroformylation time; Preferred 10-15 minute.
4. the manufacture method of PVA fabric nonwoven cloth according to claim 3 is characterized in that described spinning temperature is 90 ℃; Described nonwoven fabric hot pressing temperature is 100 ℃, pressure 40Nmm
-1Described hydroformylation is bathed and is consisted of: sulfuric acid 225g/L, sodium sulphate 70g/L, formaldehyde 25g/L; 70 ℃ of hydroformylation temperature, 10 minutes hydroformylation time.
5. the manufacture method of a PVA fabric nonwoven cloth, it adopts following technology:
(1) preparation PVA spinning solution: adopt claim 1 or 2 described PVA fiber prescriptions to prepare the PVA spinning solution;
(2) preparation PVA nonwoven fabric:, on extruder, extrude strand, spinning temperature 80-98 ℃ with the PVA spinning solution of (1) step gained, preferred 90-95 ℃, orifice diameter is 0.2-2mm, preferred 0.5-1.0mm, and under temperature 120-150 ℃ hot-air, stretching 0-10 times, preferred 0-5 doubly; And then be that preferred 130-140 ℃, random laying net for shaping on hot-rolling promptly obtains the PVA nonwoven fabric under 120-150 ℃ the hot air flow effect in temperature dry strand;
(3) nonwoven fabric post processing: carry out acetalation in the PVA nonwoven fabric immersion hydroformylation bath to (2) step gained and handle, what hydroformylation was bathed consists of: sulfuric acid 200-250g/L, sodium sulphate 50-90g/L, formaldehyde 15-35g/L; 50-90 ℃ of hydroformylation temperature, preferred 70-80 ℃; 10-20 minute hydroformylation time, preferred 10-15 minute.
6. the manufacture method of PVA fabric nonwoven cloth according to claim 5 is characterized in that described spinning temperature is 90 ℃; Described hot air temperature is 140 ℃; What described hydroformylation was bathed consists of: sulfuric acid 225g/L, sodium sulphate 70g/L, formaldehyde 25g/L; 70 ℃ of hydroformylation temperature, 10 minutes hydroformylation time.
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| CN101949084A (en) * | 2010-07-01 | 2011-01-19 | 东华大学 | Preparation method of ZnO-doped PET ultrafine non-woven fabric |
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| CN102908829A (en) * | 2012-11-20 | 2013-02-06 | 天津工业大学 | Cellulose sodium/micron-cellulose non-woven composite filter material and preparation method thereof |
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| JPS5610533A (en) * | 1979-07-09 | 1981-02-03 | Kuraray Co Ltd | Polyvinyl alcohol porous membrane and production thereof |
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| CN101949084A (en) * | 2010-07-01 | 2011-01-19 | 东华大学 | Preparation method of ZnO-doped PET ultrafine non-woven fabric |
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| CN104404650A (en) * | 2014-11-04 | 2015-03-11 | 张桂华 | Composite fiber |
| CN107683204A (en) * | 2015-05-29 | 2018-02-09 | 王子控股株式会社 | The sheet material of containing metal oxide and/or metal hydroxides |
| CN106637467A (en) * | 2016-11-09 | 2017-05-10 | 上海全宇生物科技遂平有限公司 | A boron-containing nanometer zinc oxide/polyvinyl alcohol composite fiber and a preparing method thereof |
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| CN108951160A (en) * | 2017-05-20 | 2018-12-07 | 宜兴市艺蝶针织有限公司 | A kind of uvioresistant stocking production technology |
| CN109208146A (en) * | 2017-07-05 | 2019-01-15 | 上海水星家用纺织品股份有限公司 | The method for weaving of cotton and the blended hollow yarn man textile fabric of polyvinyl |
| CN108708076A (en) * | 2018-04-09 | 2018-10-26 | 南京捷纳思新材料有限公司 | The method that wet spinning prepares core/shell polyurethane-carbon nanotube conducting non-woven fabrics |
| CN112442771A (en) * | 2020-11-13 | 2021-03-05 | 浙江羊绒世家服饰有限公司 | Water-soluble fiber and high count cashmere yarn spinning process |
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