CN85105551A - No wax sizing agent prescription based on polyvinyl alcohol - Google Patents
No wax sizing agent prescription based on polyvinyl alcohol Download PDFInfo
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Abstract
The polyvinyl alcohol based slurries, it comprises the low content ethylene oxide adduct of a small amount of branched-chain alcoho, in starching with when weaving, has excellent properties, improves the arrangement performance of fabric.
Description
The invention relates to sizing agent composition used in the textile industry, more specifically, is about containing the PVA-based sizing agent of low amount ethylene oxide adduct.
Thin warp thread must be used the water-soluble polymer starching, so that it has the face coat of protectiveness, this is desired when yarn is made into various fabric.Weave finish after, the grey cloth that is produced also must remove the protective coating above it by desizing carrying out various arrangements processing particularly before the dyeing.Slurry agent with polyvinyl alcohol base-material or polyvinyl alcohol and starch associating base-material generally must be used with the wax additive, so that when starching, makes the drying drum in the Sizing machines reduce to adhere to.These wax additives are difficult to remove from grey cloth when destarch, usually will bathe temperature with special solvent and higher destarch it is removed.As a result, in arrangement processing factory (or workshop), because technology is more complicated, energy consumption is higher, and ropy grey cloth proportion is bigger, makes production cost increase.
In U.S. Patent No. 4,383, in 063, once disclosed adopt contain a small amount of quaternary amine or season the imidazoline salt additive PVA-based sizing agent.These additives do not exist under the wax situation, improve transaction capabilities, improve the arrangement performance of fabric.But this prescription also has critical defect: the non-renewable of a kind of slurry usually occur.This defect is that it and cationic additive interact, and can not prediction ground be removed by cationic additive at random owing to usually accumulate anionic impurity in starching solution.The main source of these anionic impurities is exactly a spun yarn of having gone up slurry.
US Patent No 4,251, in 403, the low ethoxylate of straight chain class alcohol that discloses the amount seldom of adding (maximum ratio be polyvinyl alcohol weight 0.05%) in the slurry agent that with the polyvinyl alcohol is base-material is as defoamer.Have found that this material is invalid as the sub of wax, thereby can not in the warp sizing agent of no wax, replace wax.
The invention provides following slurry agent prescription:
(a) be made up of vinyl alcohol condensate that extracts from the mixed liquor of polyvinyl alcohol, vinyl alcohol/methyl methacrylate copolymer and the polyvinyl alcohol that contains the solvable comonomer of non-butenoic acid formicester substantially, weight accounts for overall 45.5-99.9%.Vinyl alcohol polymer has saponification number and is about 1-160, and the viscosity of 4% solution is about 3-70mPa.s in the time of 20 ℃;
(b) contain the non-anionic adduct of liquid low content oxirane (branched-chain alcoho or side chain alcohols mixture) that weight accounts for 0.1-3%, wherein, the average content of oxirane is about 1-7 unit, and the mean carbon content of alcohol is about 8-18 carbon atom;
(c) starch weight is about 0-49.9%;
(d) weight of ethylene oxide oligomer is about 0-5%, the about 200-800 of its molecular weight (mean value);
(e) carboxymethyl cellulose, weight accounts for 0-49.9%;
(f) Fu Zhu ethylene oxide adduct, weight accounts for about 0-1% at least, choose from following one group of compounding substances, this group material comprises in (the about 8-18 of the mean carbon content unit) of the low content ethylene oxide adduct (the about 1-7 of an oxirane average content unit) of straight chain alcohol or straight chain alcohols mixture (the about 8-18 of a mean carbon content unit) and straight or branched alcohol the ethylene oxide adduct (the on average about 8-40 of an ethylene oxide content unit) to high-load.The gross weight of starch and carboxymethyl cellulose is no more than the weight of vinyl alcohol polymer.
According to the present invention, also provide the concentrate of the low content ethylene oxide adduct that is mixed with vinyl alcohol polymer, a kind of aqueous solution that does not have the agent of wax slurry.It comprises prescription of the present invention, wherein solid weight 2-20%; Also be provided for the no wax aqueous solution sizing technique of filament yarn, have the last sizing that promptly has no wax protective surface coating on it with component of the present invention.
Terminology used here " basic composition " means that the batching of being mentioned is the essential part of prescription, and still, other do not hinder the batching that realizes advantage of the present invention may to comprise some yet.
Have found that, the low content ethylene oxide adduct (3% or less) of the non-ionic branched-chain alcoho of liquid is added to in the agent of ethene alcohol radical slurry, can eliminate go up sizing and stick to disadvantage on the drying box in the Sizing machines, thereby make weaving efficiency become excellent, be easy to remove the slurry agent under gentle destarch condition, the slurry grey cloth that taken off that is produced has also shown fabulous dye receptiveness.Sizing agent component of the present invention has been recommended to be used for the traditional starching of weaving mill, heat setting and water-based destarch operation.
Concerning component of the present invention, the vinyl alcohol condensate can have saponification number (in and 1 gram polymeric KOH milligram number) and be about 1-160, and 4% solution viscosity is about 3-70mPa.s.
The polymeric example of vinyl alcohol that is suitable for comprises:
(a) fully hydrolysis vinyl alcohol/methylmethacrylate copolymer (containing 3.5-6 mole % methylmethacrylate approximately), the about 3-60mPa.s(of its viscosity records 20 ℃ the time with 4% the aqueous solution).This copolymer can carry out alcoholysis by the copolymer of vinylacetate (ester)/methylmethacrylate and make.
(b) polyvinyl alcohol of partial hydrolysis, contained vinylacetate (fat) accounts for 4-12 mole %, and its viscosity is about 3-60mPa.s;
(c) polyvinyl alcohol of abundant hydrolysis, viscosity is about 3-70mPa.s;
(d) contain the polyvinyl alcohol of " solubility comonomer " (for example methacrylate, the maleic acid hydrogen methyl esters) that is not methylmethacrylate;
(e) the various mixtures of above-mentioned vinyl alcohol condensate class.
Nonionic additives among the present invention is the low content ethylene oxide adduct (the about 1-7 of the average content of an oxirane unit) of a kind of branched-chain alcoho or side chain alcohols mixture (the about 8-18 of a mean carbon content unit).The preferable composition of this additive is: contain the oxirane of 2-5 unit approximately, the branched-chain alcoho of being with on average contains 10-15 carbon atom.Best composition is: the oxirane of average about 3 units, about 13 of the average carbon atom number of branched-chain alcoho.Product " Tergit01 " 15-S-3 that Union Carbide Corporation produces is exactly the representative of this optimum addn.
The polymeric amount of vinyl alcohol is about 45.5-99.9%(and calculates by weight in the present composition).The scope of preferable composition is 63-99.8% approximately, and the best scope of forming is 72.7-99.6% approximately.In typical PVA-based slurry agent prescription, the polyvinyl alcohol content of slurry in the agent is higher, and be then higher by the last sizing shown efficient of weaving cotton cloth.Generally speaking, along with the content of polyvinyl alcohol in the slurry agent increases, slurry agent addition is the corresponding minimizing of consumption.
The about 0.1-3% of nonionic additives weight among the present invention.The antiseized need of drier rotating cylinder add the additive of 0.1% weight, and if surpass 3%, then may reduce weaving efficiency.The preferable range of weight of additive is 0.2-1.5%, and in this scope, most of benefit of the present invention just can obtain.The optimum range of additive concentration is 0.4-0.8 weight %.The additive that contains this quantitative range can best be adjusted the dye receptiveness after deposition properties, erosion resistance and the destarch of rotating cylinder.
Starch optionally joins in the slurry agent composition of the present invention, and weight can reach 49.9%.Amount of starch reaches this numerical value, and the benefit that additive produced of the not content of wax of the present invention then can obviously show.The preferred values of amount of starch is below 33%, and optimum value then approximately is below 25%.In the vinyl alcohol condensate/starch mixture of the best, the effect of nonionic additives of the present invention is with approaching as the viewed effect of the prescription of unique polymerization component by the vinyl alcohol condensate.Various types of starch and in prescription of the present invention, all can be used as the additive of selecting for use by its starch that develops out.These starch comprise the acetylated starch that " Kofilm " 50(is supplied with by national starch company) and the starch of " Astrogum " 3010(moderately viscous receiving of carboxymethyl) and the starch of " Astrogum " 3020(low viscous carboxymethyl sodium), the latter is supplied by Penick company and Ford company.
Carboxymethyl cellulose (CMC) is optional as the batching in the composition of the present invention, and weight can account for about 50%, and is better to account for 33%, account for 25% best.
The shared gross weight of starch and carboxymethyl cellulose should not surpass the polymeric weight of vinyl alcohol in this composition.
Another additive that can Gong select for use is the low ethylene oxide oligomer that arrives (the average 200-800) of intermediate molecular weight, can join in the vinyl alcohol condensate as the dust removal agent.4,389, in No. 506 United States Patent (USP)s, the polyethylene glycol product of " Carbowax " 600(Union Carbide Corporation production of employing 3% weight is proposed, can produce the additive of best dust removing effects).When the concentration of " Carbowax " 600 reaches 5% left and right sides, only make the benefit that produces by the existence of nonionic additives of the present invention that small minimizing is arranged, the upper limit of the additive capacity that this representative is recommended.The preferable upper limit is 3%, and the best upper limit is 1.5%.Under the upper limit concentration situation of the best, almost all can realize by the benefit that nonionic additives produced among the present invention.
The additive that can Gong select for use in addition is the auxiliary low content ethylene oxide adduct (the about 1-7 of the average content of an oxirane unit) of straight chain alcohol or straight chain alcohols mixture (the about 8-18 of a mean carbon content unit), or straight or branched alcohols (mean carbon content 8-18 unit) in to the ethylene oxide adduct (the about 8-40 of the average content of an oxirane unit) of high-load.These additives can be present in the composition of the present invention by low concentration (promptly being not more than 1% weight approximately).
Aqueous slurry agent of the present invention generally contains the about 2-20% weight of amount of solid.The solids content that preferable slurry agent is bathed is 5-15% approximately.Optimum content is 7-12% approximately, because in most of the cases, the solids content of this quantitative range has enough slurry agent additions, can make sizing have suitable erosion resistance.It is unique that the PVA-based slurry agent aqueous solution is considered to, and must not use the wax additive because it does not contain at general normal factory condition.
The method for making of the slurry agent aqueous solution is at room temperature the pulp of polyvinyl alcohol water, then nonionic additives is added together with any additives of selecting for use.Then, mixture is heated to 77 ℃ under stirring, till obtaining perfect slurries.
Slurries of the present invention also can directly mix the vinyl alcohol condensate and make with the nonionic additives of the present invention of low amount.Polyvinyl alcohol of the present invention/nonionic additives mixture is made by under uniform temperature (in the liquefy all of additive component under this temperature) and high strength stirring condition various polyvinyl alcohol and additive being carried out anhydrous mixing.And, if adopted more than a kind of nonionic additives, then they can be pre-mixed together, add as single component.For example, the Z-blade mixer that adopts Read company to make, polyvinyl alcohol and additive " Tergitol " 15-S-3 or " Tergitol " 15-S-3/ " Carbowax " 600 mixtures were stirred 30 minutes under the temperature conditions more than 20 ℃, make it evenly to mix.This preparation method is at ambient temperature, with vinyl alcohol condensate/nonionic additives fusion pulping in water of aequum, obtains desirable slurry agent and bathes solid.Then with the mixture agitating heating under 77 ℃ of conditions that is generated, until forming perfect slurries.
Can be added to preparation slurries of the present invention in the vinyl alcohol condensate to nonionic additives concentrate of the present invention.Concentrate mainly accounts for the vinyl alcohol polymer of 45-90% by weight and nonionic low content oxirane liquid additive that weight accounts for 10-55% constitutes.The composition content of concentrate can freely be selected, it can contain the starch up to about 45% weight, the polyethylene glycol (Carbowax) that perhaps contains the highest about 45% weight, perhaps contain the following carboxymethyl cellulose of about 45% weight or contain the low content ethylene oxide adduct of following straight chain alcohol of about 45% weight or straight chain alcohols mixture or straight or branched alcohol in to the high-load ethylene oxide adduct.Join in the ready-made vinyl alcohol polymer solution by concentrate, can produce slurry agent of the present invention aequum.Adopt this concentrate can produce unique and astonishing advantage.Generally speaking, even when adding the vinyl alcohol condensate in the hydrothermal solution under vigorous stirring, vinyl alcohol contact generation and melts and touch with hot water, and is difficult to be dissolved in wherein.If opposite above-mentioned concentrate contains the nonionic additives of 30% left and right sides weight among the present invention at least, when then directly joining in the hot water, just be scattered in wherein than being easier to.The optimal addn of nonionic additives should about 40%-50%(be calculated by weight).If be higher than about 50%, then the vinyl alcohol condensate often can not absorb all additives.The concentrate of being introduced above adopting can have desirable advantage: the quantity that can readjust nonionic additives in given heat slurry agent is bathed rapidly.To be fit to the requirement of concrete factory.
The preferable composition of the top concentrate of addressing is the vinyl alcohol condensate that contains the 45-70% weight of having an appointment, the nonionic additives of about 30-55% weight, reach the following starch of 20% weight, the carboxymethyl cellulose that following polyethylene glycol of 20% weight (Carbowax) and 20% weight are following.The best of concentrate is formed: calculate by weight, the about 50-60% of vinyl alcohol condensate, nonionic additives account for the following % of 40-50, and starch accounts for 5%, and polyethylene glycol accounts for below 5%, and carboxymethyl cellulose accounts for below 5%.
The slurry agent is used on the warp on yarn or the Sizing machines.Sizing machines is equipped with the slurry agent case that had heated already that contains certain slurry agent prescription.Unsized yarn is taped against on the dryer drum of a series of heating by drawing in the hot slurries and starching is removed unnecessary slurries with the press for extracting juice roller again.By the clavate device warp thread is twined each spool end, be collected on the bobbin at last.When the warp thread of going up slurry of requirement when being collected on the bobbin, latter's loom of packing into, yarn is made into grey cloth.
Utilize slurry agent prescription of the present invention and the spun yarn of starching has the protective coating of no wax, have unique weaving performance, although in the agent of ethene alcohol radical slurry the content of wax not.And weave no wax grey cloth destarch easily under general destarch condition of coming, become the grey cloth of destarch with good dye receptiveness.During destarch, earlier the grey cloth of starching is bathed by neutralizing treatment, then by hot water (about 65-85 ℃) rinsing several times.Much stricter with desired washing of fabric and rinsing condition that traditional content of wax slurry agent makes than adopting under the slurry agent prescription situation of the present invention.Grey cloth requires grey cloth to remove residual slurry agent component before sending into dressing floor and handling high-levelly, but so that can carry out on fabric effectively and dual-staining and other readjusting operations.Sizing and no wax grey cloth are all thereby be considered to uniqueness on the no wax of making therefrom.
No wax slurry agent composition of the present invention is specially adapted to polyester/cotton blending spun yarn, especially is specially adapted to ratio and is 65/35,50/50,40/60 polyester/cotton blending spun yarn, also can be used for 100% cotton yarn.
To not have the wax additive joins with in the vinyl alcohol condensate base slurry agent prescription, need with wax with being additive, thereby can prepare last sizing with excellent starching and weavability, under typical weaving condition (as fly-shuttle loom, air-jet loom, Rapier looms) produces various fabrics.The characteristics of no wax fabric are: the slurry agent is easily removed, and the fabric that has taken off slurry demonstrates excellent dye receptiveness.
For some example purposes are to specify the present invention below.Except as otherwise noted, said umber or percentage all are by weight calculation.
Example
The preparation of slurries is to carry out in the pot of steam jacket is arranged: the vinyl alcohol condensate is added in the room temperature water of institute's required amount, obtaining desired is that slurries are bathed solid particle.The temperature of pulping is 77 ℃, and stirs.Will test any additives in prescription at this moment all add.
Made slurries are used for the polyester/cotton blended yarn of 24 terminations is carried out starching." Callaway board Sizing machines " 51 types that adopt Western-style pastry casting and machines corporation to make, running speed is 10 meters/minute, pressurizes on squeezing roller.After yarn sizing, the addition of slurry agent is by measuring with the loss in weight shown behind the sizing on the extracting in boiling water.The characteristic of starching the performance of agent prescription when the test procedure below adopting is estimated sizing and having gone up the yarn of slurry itself.
(a) cylinder deposit
Sediment yield on No. 1 drying drum in Sizing machines directly and given slurry agent prescription cause that the tendency that single the end of a thread adheres on the drying drum is relevant.For making the yarn that adheres on the Sizing machines drying part reduce to minimum, in the slurry agent prescription, added antitack agent, its effect can accurately be measured.Sizing machines is turned round under above-mentioned condition, the temperature of No. 1 drying drum is fixed on 190 ℃, other three cylinders fix on 220 ℃.In about 1 minute, reach equilibrium valve at the sediment yield of accumulating on No. 1 cylinder.In case reach balance, the deposit on this cylinder, available squeegee is periodically removed during rotating cylinder turns around.Then deposit is dried up and claimed, the deposit quantity of being collected can be used for directly measuring the performance of slurry agent prescription, that is to say that the deposition on the rotating cylinder is big more, and formula constituent will cause that the tendency that drying drum adheres to is big more.In current research process, the various vinyl alcohol condensate bases that estimate are starched in the agent prescriptions, and it is the highest to observe on the cylinder deposit quantity with unmodified prescription PVA No.2 the time.This PVA No.2 prescription is the vinyl alcohol/acrylic acid formicester copolymer of abundant hydrolysis, and the viscosity of 4% solution is 13.5mPa.s, and saponification number is 40.In the above in Yin Shu each example, sedimental actual quantity and all be presented on the viewed cylinder with the proportional nominal value of the value of PVA No.2 (except that other is annotated).The practicality of (the vinyl alcohol polymerization somaplasm agent with 100%) under the typical plant condition must or be hanged down a little nominal values with 0.200.
(b) anti-erosion performance of going up sizing is determined with the abrasion detector in the laboratory.Used test method is: 21 the end of a thread of going up sizing are passed a side of traditional loom reed, controlledly strain each single the end of a thread.Reed is vibrated, per second one-period with respect to yarn and thread head.Cause that each the end of a thread desired vibration period number that ruptures goes on record.Second group of 21 yarn and thread head is by the then test of same mode.Two groups of data that obtained are added up then, average, and with the end of a thread of using in the test of must sening as an envoy to half desired vibration period number that ruptures are arranged.This vibration period number is called the F50 nominal value of given slurry agent prescription.
The anti-erosion performance height depends on slurry agent additive amount.For ease of relatively, all F50 data all must be standardized for the additive capacity of a given slurry agent (promptly 10%).Preferably,, obtain the F50 value and be 6 or more additive capacity, then the data that produced are carried out linear regression analysis for given slurry agent prescription.All handle in this way in all F50 values of being reported in each routine characteristic of lift.Viewed F50 maximum is to belong to slurry agent with PVA No.1 formulation (vinyl alcohol/methyl acrylate copoly body that PVA No.1 is abundant hydrolysis, the viscosity of 4% solution is 28mPa.s, saponification number is 30).In all examples of being quoted from, viewed actual F50 value and all provide with the comparison nominal value of PVA No.1 slurry agent (unless otherwise noted).The latter calculates like this: i.e. the logarithm F50 value of PVA No.1 slurry agent when 10% slurry agent addition is its definite value 1, specific slurry agent prescription viewed logarithm F50 value when 10% slurry agent addition in the example, then proportional with it relation.When 10% additive capacity, be applicable to that the nominal value of (the vinyl alcohol polymerization somaplasm agent with 100%) under the typical factory condition should be 0.875 or higher.
(c) dye receptiveness.
In this test used on sizing at first be heat treated, promptly be 200 ℃ stove by a temperature, 45 seconds duration.Yarn after the heat treatment carries out destarch then under temperate condition: with yarn at 55 ℃ 0.5% alkanol WXN(a kind of modification alkylaryl sodium sulfonate by E.I.Du Pont Company's supply) soaked for 15 seconds in the solution.Then 75 ℃ of following three 45 seconds of rinsing yarn.The most handy drying press is thoroughly dried up yarn.Used the yarn of destarch dry, its dye receptiveness can be determined that the aqueous solution of that is: measuring " agriculture chemistry " green (Chemurgy green) dyestuff is to infiltration one inch used time (in second) on the dried reeled yarn alignment by following method.Supply with by Milliken company at " Synchem " 110 waxes-a kind of animal adipocere that is dispersed in the hot water that contains 8% with PVA No.1() when testing, viewed dye receptiveness is the poorest.This value is decided to be 1, then the proportional with it relation of the dye receptiveness of every other example.Like this, in each example of being given, observed nominal value to dye receptiveness all gives report.Under common factory condition, to reach good its nominal value of dye receptiveness and must reach 3.5 or higher.
Example 1 and example 2 and comparative example 1 and comparative example 2.
To a kind of with PVA No.2 (containing 0.4% " Tergitol " 15-S-3(example 1)) be that the slurries of base-material are tested under 12 kinds of different slurry agent addition agent amount conditions (5-15% is with the yarn re-computation), and with three kinds similarly prescription compare.These three kinds of prescriptions are: only make (routine C-1) by PVA No.2; By the PVA No.2(example C-2 that contains " Synchem " 110 waxes of 8% (typical plant formula)) make; By the PVA No.2(example 2 that contains 0.4%Tergitol 15-S-3 and 1.5% " Carbowax " 600) make.In the result of the test tabulation 1.
As what see from top data, example 1 and routine 2(imbody the present invention) yarn that meets three kinds of crucial combination properties is provided, but the data of comparative example 1 and example 2 are then undesirable, because comparative example 1(C-1), on the cylinder sediment yield too high and at comparative example 2(C-2) in, the dye receptiveness extreme difference.
Example 3 and example 4 and comparative example 3 and comparative example 4
To being that base-material is that slurries divide 12 kinds of different additive amount (scope 5-15% with PVA No.1 (containing 0.4% " Tergitol " 15-S-3(example 3), calculate with yarn weight) estimate, and compare with similar three kinds of prescriptions, these three kinds of prescriptions are: only with PVA No.1(example C-3); PVA No.1+8% " Synchem " 110 waxes (typical plant prescription) (routine C-4); PVA No.1+0.4% " Tergitol " 15-S-3+1.5% " Carbowax " 600(example 4).The results are shown in the table 2.
Top data declaration, the same advantage that is embodied in example 1 and example 2 can utilize additive of the present invention (the vinyl alcohol condensate can have multiple alternative amount) to realize.
Example 5 and comparative example 5 and comparative example 6
This group example is used is that the mixture 75/25(of " Vinol " 425 and " Vinol " 205 two kinds of polyvinyl alcohol is supplied with by aeronautical product company)." Vinol " the 425th, the intermediate product of hydrolysis (94% weight hydrolysis), " Vinol " the 205th, the PVA level of partial hydrolysis (88% weight hydrolysis).A kind of polyvinyl alcohol admixture (adding " Targitol " 15-S-3 of 0.4%) (example 5) that comprises divides 12 kinds of slurry agent addition agent amount (scope 5-15%, calculate with yarn weight) situation under estimate, and compare with (routine C-6) that similar Formulation Example C-5 that contains unmodified admixture and another kind contain the admixture of 8% " Synchem ", 110 waxes.The result all is listed in the table 3.
From top data as can be seen, additive of the present invention is to providing identical advantage based on middle with the polyvinyl alcohol prescription of partial hydrolysis, and this vinyl alcohol condensate prescription that can introduce in example 1, example 2, example 3 and example 4 is observed and obtained.
Example 6 and comparative example 7 and comparative example 8
A kind of slurry agent prescription (example 6) that contains " Carbowax " 600 of 75/25 PVA No.2/ " Kofilm ", 50 starch blends, 0.4% " Tergitol " 15-S-3 and 1.5% divides 12 kinds of additive capacity (scope 5-10%, calculate with yarn weight) situation under estimated, and with similar recipe ratio, be a kind of be not contain additive (routine C-7), another kind is to contain 8% " Synchem ", 110 waxes (routine C-8).The results are shown in the table 4.
Top data show, in the PVA/ starch base additive system of the present invention, have significantly reduced the deposit on the cylinder, have improved the dye receptiveness of yarn.Additive of the present invention according to observations, is not more than " Synchem " 110 wax patterns aspect the adverse effect of erosion resistance.
Example 7 and comparative example 9 and comparative example 10
The slurry agent prescription that obtains from the admixture of 50/50PVA No.2/ " Kofilm " 50 starch, and contain 0.4% " Tergitol " 15-S-3 and 1.5% " Carbowax " 600(example 7), divide 12 kinds of different additive amount (scope 5-15%, calculate with yarn weight) estimated under the situation, and with two kinds, the similar prescription that does not promptly contain additive (routine C-9) and contain 8% " Synchem ", 110 waxes (routine C-10) is compared.The results are shown in the table 5.
Above data show that when using 50/50 vinyl alcohol condensate/starch admixture, additive of the present invention is all producing favorable influence aspect cylinder deposit characteristic and the dye receptiveness.This additive reduces erosion resistance, and the degree of being fallen is about the same with the degree that " Synchem " 110 wax additives are fallen.
Comparative example 11-13
PVA No.2 base slurry agent prescription is prepared from the low ethylene oxide adduct of several straight chain alcohols, and said straight chain alcohols be " Tergitol " 25-L-3, the routine C-11 to 13 of " Alfonic " 1012-40 and " Alfonic " 1412-40().
Low ethylene oxide adduct performance data is listed as follows.
Hydrophobic substance in the table is a straight chain alcohol in " Alfonic " and " Tergitol " 25-S-3.But in " Tergitol " 15-S-3 is secondary alcohol.The data of last table show that " Alfonic " 1412-40 and " Tergitol " 25-L-3 almost just in time are the straight chain homologues of " Tergitol " 15-S-3." Alfonic " product is supplied with by Conoco company, and " Tergitol " product is supplied with by Union Carbide Corporation.
Table 6 has been listed composition and the character (example 1) with the slurry agent prescription of top straight chain alcohol of deriving from ethylene oxide adduct and additive of the present invention preparation.
By top data as can be known, contain the slurry agent prescription (routine C-11 to 13) of straight chain alcohol based additive viewed numerical value with the time and compare, have much bad cylinder deposit and anti-erosion performance with additive of the present invention.
Example 8-10 and comparative example 14-20
With the modification scope is the slurry agent prescription of the modified PVA No.2 preparation of " Tergitol " 15-S product of containing the 3-40 ethylene oxide unit(s) (that is to say, from " Tergtiol " 15-S-3 to " Tergitol " 15-S-40).The weight of the additive in the prescription " Tergitol " accounts for 0.4%, also has 3.0% " carbowax " 600.Table 7 has been listed these prescriptions and has only been contained the prescription of " Carbowax " 600 additives.
Data by table 7 show that additive of the present invention (" Tergitol " 15-S-3,15-S-5 and 15-S-7) has improved effect (routine 8-10)." Tergitol " 15-S-9 to 40(example C-15 to 20) cylinder deposit poor performance.And the value of viewed anti-erosion performance also reduces gradually along with the increase of the number of ethylene oxide units in " Tergitol " additive.
Example 11 and comparative example 21
Making the made fabric sample of fabric sample and the last sizing that has been coated with the agent of commercial PVA/ adipocere prescription slurry with the last sizing that has been coated with slurries of the present invention compares, the two all (for example soaked 15 seconds, and then carry out water rinse three times under 65 ℃) destarch earlier at 55 ℃ under temperate condition.The dye receptiveness of starching the sizing fabric of agent with the present invention is 8 times with the sizing fabric of traditional content of wax slurry agent.And the former is regular and even to the absorption of dyestuff, and the latter is irregularity and inhomogeneous then.
Used fabric is a kind of 65/35 polyester/cotton warp thread (36 yarns) and 100% polyester weft yarn in example 11 and comparative example 21, is made into the fabric of 92/83 the structure ratio of parallel (warp with).Warp thread is with containing 12.5% solid particle and containing the 15.0% sizing agent starching of starching agent addition agent.Slurries used in example 11 are just corresponding to used in the example 2.Used slurries and used roughly the same in comparative example 2 in comparative example 21, its difference are with 10% " Snychem ", 110 waxes, rather than 8%.
Claims (20)
1, the basic composition of slurry agent of the present invention is:
(a) the vinyl alcohol condensate of about 45.5-99.9% weight, it is from by polyvinyl alcohol, vinyl alcohol/methylmethacrylate copolymer with contain one group of mixture of solvable comonomer of non-methylmethacrylate and choose out, said vinyl alcohol condensate has saponification number and is about 1-160, is about 3-70mPa.s during 20 ℃ of 4% solution viscosities;
(b) the low amount of the liquid nonionic of the branched-chain alcoho of about 0.1-3% weight or side chain alcohols mixture ethylene oxide adduct, wherein, the average content of oxirane is 1-7 unit approximately, the phosphorus content of alcohol on average is about 8-18 carbon atom;
(c) starch of 0-49.9% weight;
(d) ethylene oxide oligomer of 0-5% weight, the about 200-800 of its mean molecule quantity;
(e) carboxymethyl cellulose of 0-49.9% weight;
(f) the auxiliary ethylene oxide adduct of at least one 0-1% weight, it is from by choosing out in the one group of mixture of substances that constitutes to high-load ethylene oxide adduct (average content of oxirane is about 3-40 unit) the low content oxirane (the oxirane average content is about 1-7 unit) of straight chain alcohol or straight chain alcohols mixture (mean carbon content 8-18 unit) and the straight or branched alcohols (mean carbon content 8-18 unit), and the gross weight of regulation starch and carboxymethyl cellulose is no more than the polymeric weight of vinyl alcohol.
2, composition in the claim 1, therein ethylene alcohol condensate is the polyvinyl alcohol (the about 3-70mPa.s of viscosity) from abundant hydrolysis, abundant vinyl alcohol/methylmethacrylate the copolymer of the hydrolysis (comonomer of methylmethacrylate that contains the copolymerization of 3.5-6% weight approximately, the about 3-60mPa.s of its viscosity) and the polyvinyl alcohol (vinylacetate that contains 4-12 mole % approximately of partial hydrolysis, viscosity is about 3-60mPa.s) to choose out in the mixture group that constitutes, the polyvinyl alcohol that contains the solubility comonomer is from by methacrylate, choose out in the mixture group that maleic acid hydrogen methyl esters (viscosity is about 3-70mPa.s) and said vinyl alcohol condensate constitute.
3, the composition of claim 1, the about 63-99.8 of the therein ethylene alcohol shared weight of condensate %, the about 0.2-1% of weight that ethylene oxide adduct is shared, the shared weight of starch is about 0-33%, the shared weight of oxirane oligomer is about 0-3%, the shared weight of carboxymethyl cellulose is about 0-33%, 2-5 unit of the oxirane average content of ethylene oxide adduct wherein, and the mean carbon content of alcohol is about 10-15 carbon atom.
4, the composition of claim 1, the shared weight of therein ethylene alcohol condensate is about 72.7-99.6%, the shared weight of ethylene oxide adduct is about 0.4-0.8%, the shared weight of starch is about 0-25%, the shared weight of oxirane oligomer is about 0-1.5%, and the shared weight of carboxymethyl cellulose is about 0-25%, wherein, the oxirane average content of ethylene oxide adduct is about 3 units, and the mean carbon content of alcohol is about 13 carbon atoms.
5, basic composition is of a kind of composition:
(a) the vinyl alcohol condensate of 45-90% weight, it is to choose out from the mixture group by polyvinyl alcohol and vinyl alcohol/methylmethacrylate copolymer and polyvinyl alcohol (the solubility comonomer that contains non-methylmethacrylate) formation, said vinyl alcohol condensate, its saponification number is about 1-160, is about 3-70mPa.s during 20 ℃ of the viscosity of 4% solution;
(b) the liquid nonionic low content ethylene oxide adduct of the branched-chain alcoho of about 10-55% weight or side chain alcohols mixture, wherein, the about 2-7 of the average content of an oxirane unit, the mean carbon content of alcohol is about 8-18 carbon atom;
(c) starch of about 0-45% weight;
(d) the oxirane oligomer of about 0-45% weight, the about 200-800 of its mean molecule quantity;
(e) carboxymethyl cellulose of about 0-45% weight;
(f) a kind of auxiliary ethylene oxide adduct of about 0-45% weight, it is to choose out from the mixture group that the medium ethylene oxide adduct to high-load (average content of oxirane is about 8-40 unit) by the low content ethylene oxide adduct (the oxirane average content is about 1-7 unit) of straight chain alcohol or straight chain alcohols mixture (mean carbon content is about 8-18 unit) and straight or branched alcohols (mean carbon content 8-18 unit) constitutes.
6, the composition of claim 5, therein ethylene alcohol condensate is to be selected from the mixture group that is made of following ingredients, it is the polyvinyl alcohol (its viscosity is about 3-70mPa.s) of abundant hydrolysis, vinyl alcohol/methylmethacrylate the copolymer (the methylmethacrylate comonomer (its viscosity is about 3-60mPa.s) that contains the copolymerization of 3.5-6% weight) of abundant hydrolysis and the polyvinyl alcohol (vinylacetate that contains 4-12 mole % of partial hydrolysis, viscosity is about 3-60mPa.s), the polyvinyl alcohol that contains the solubility comonomer is from by methacrylate, choose out in the mixture group that maleic acid hydrogen methyl esters (viscosity is about 3-70mPa.s) and vinyl alcohol condensate constitute.
7, the composition of claim 5, the shared weight of therein ethylene alcohol condensate is about 45-70%, the shared weight of ethylene oxide adduct is about 30-55%, the shared weight of starch is about 0-25%, the shared weight of oxirane oligomer is about 0-25%, and the shared weight of carboxymethyl cellulose is about 0-25%, wherein, the about 3-5 of an average ethylene oxide content unit of ethylene oxide adduct, the mean carbon content of alcohol is about 10-19 carbon atom.
8, the composition of claim 5, the shared weight of therein ethylene alcohol condensate be about 50-60 %, the shared weight of ethylene oxide adduct is about 40-50%, the shared weight of starch is about 0-5%, the shared weight of oxirane oligomer is about 0-5%, and the shared weight of carboxymethyl cellulose is about 0-5%, wherein, the oxirane average content of ethylene oxide adduct is about 3 units, and the mean carbon content of alcohol is about 13 carbon atoms.
9, contain and comprise that the shared weight of solid is about 2-20% in a kind of no wax slurry agent aqueous solution that claim 1,2,3 or 4 composition form.
10, contain and comprise that the shared weight of solid is about 5-15% in a kind of no wax slurry agent aqueous solution that claim 1,2,3 or 4 composition form.
11, contain and comprise that the shared weight of solid is about 7-12% in a kind of no wax slurry agent aqueous solution that claim 1,2,3 or 4 composition form.
12, a kind of use contains the spun yarn sizing technique of the no wax slurry agent aqueous solution (wherein the shared weight of solid is about 2-20%) that comprises that claim 1,2,3 or 4 composition are formed.
13, a kind of use contains the spun yarn sizing technique of the no wax slurry agent aqueous solution (wherein the shared weight of solid is about 5-15%) that comprises that claim 1,2,3 or 4 composition are formed.
14, a kind of use contains the spun yarn sizing technique of the no wax slurry agent aqueous solution (wherein the shared weight of solid is about 7-12%) that comprises that claim 1,2,3 or 4 composition are formed.
15, contain and comprise the last sizing that spun yarn constituted that has been coated with the no wax coating for surface protection that claim 1,2,3 or 4 composition form.
16, contain and comprise that the last sizing that spun yarn constituted that has been coated with the no wax coating for surface protection that claim 1,2,3 or 4 composition form, wherein said spun yarn are to be selected from the spun yarn that cotton and cotton/polyesters are constituted.
17, contain and comprise and be coated with a kind of last sizing that spun yarn constituted that does not have the wax coating for surface protection that claim 1,2,3 or 4 composition are formed, wherein said spun yarn is to be selected from the spun yarn that is made of 65/35,50/50 and 40/60 polyester/cotton class.
18, a kind of fabric by last sizing preparation; saidly go up that sizing is made of the spun yarn that has been coated with the no wax coating for surface protection that claim 1,2,3 or 4 composition form; wherein said spun yarn is to be selected from the spun yarn that is made of 65/35,50/50 or 40/60 polyester/cotton class.
19, a kind of fabric by the preparation of last sizing saidly goes up that sizing is made of the spun yarn that has been coated with the no wax coating for surface protection that claim 1,2,3 or 4 composition form.
20, a kind of fabric of going up the sizing preparation, the said sizing of going up is made of the spun yarn that has been coated with the no wax coating for surface protection that claim 1,2,3 or 4 composition form, and wherein said spun yarn is the spun yarn that selects flee fibre or cotton/polyesters to form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105551 CN1006313B (en) | 1984-08-20 | 1985-07-20 | Polyvinyl alcohol based wax-free size composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64243584A | 1984-08-20 | 1984-08-20 | |
| CN 85105551 CN1006313B (en) | 1984-08-20 | 1985-07-20 | Polyvinyl alcohol based wax-free size composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105551A true CN85105551A (en) | 1987-01-21 |
| CN1006313B CN1006313B (en) | 1990-01-03 |
Family
ID=25741888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105551 Expired CN1006313B (en) | 1984-08-20 | 1985-07-20 | Polyvinyl alcohol based wax-free size composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006313B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103215723A (en) * | 2013-05-07 | 2013-07-24 | 吴江市晨龙新升纺织品有限公司 | Parachute cloth producing technology |
| CN105734975A (en) * | 2016-03-22 | 2016-07-06 | 丁长军 | Sizing agent for shaping of flat-fabric such as silk and wool and preparation method of sizing agent |
| CN110846898A (en) * | 2020-01-08 | 2020-02-28 | 石家庄学院 | Preparation method of antibacterial degradable composite fiber |
| CN112513365A (en) * | 2018-07-30 | 2021-03-16 | 三洋化成工业株式会社 | Sizing composition for fiber, sizing dispersion for fiber, sizing solution for fiber, fiber bundle, fiber product, and composite material |
| CN114318855A (en) * | 2022-01-18 | 2022-04-12 | 苍南县合帮纺织有限公司 | Blended regenerated cotton yarn and preparation method thereof |
-
1985
- 1985-07-20 CN CN 85105551 patent/CN1006313B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103215723A (en) * | 2013-05-07 | 2013-07-24 | 吴江市晨龙新升纺织品有限公司 | Parachute cloth producing technology |
| CN103215723B (en) * | 2013-05-07 | 2015-03-25 | 吴江市晨龙新升纺织品有限公司 | Parachute cloth producing technology |
| CN105734975A (en) * | 2016-03-22 | 2016-07-06 | 丁长军 | Sizing agent for shaping of flat-fabric such as silk and wool and preparation method of sizing agent |
| CN112513365A (en) * | 2018-07-30 | 2021-03-16 | 三洋化成工业株式会社 | Sizing composition for fiber, sizing dispersion for fiber, sizing solution for fiber, fiber bundle, fiber product, and composite material |
| CN110846898A (en) * | 2020-01-08 | 2020-02-28 | 石家庄学院 | Preparation method of antibacterial degradable composite fiber |
| CN114318855A (en) * | 2022-01-18 | 2022-04-12 | 苍南县合帮纺织有限公司 | Blended regenerated cotton yarn and preparation method thereof |
| CN114318855B (en) * | 2022-01-18 | 2024-01-26 | 苍南县合帮纺织有限公司 | Blending regenerated cotton yarn and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1006313B (en) | 1990-01-03 |
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