CN1301895A - Fabric finishing agent and finishing method for cellulose based fabric thereof - Google Patents
Fabric finishing agent and finishing method for cellulose based fabric thereof Download PDFInfo
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- CN1301895A CN1301895A CN00135797A CN00135797A CN1301895A CN 1301895 A CN1301895 A CN 1301895A CN 00135797 A CN00135797 A CN 00135797A CN 00135797 A CN00135797 A CN 00135797A CN 1301895 A CN1301895 A CN 1301895A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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Abstract
Provided is a fiber-treating agent contains the methyloldihydroxyethyleneurea-based compound methylolated or methoxymethylated within the range of 1.4-2mol per 1mol of an ethyleneurea ring; 5 to 40 pts.wt. of a small molecule polyhydroxylated compound having 200 molecular or less and more than 5 pts.wt. of a polyethylene glycol having more than 1,000 average molecular weight per 100pts.wt. or more than 5 pts.wt. of a polyethylene glycol having 400 to 1,000 average molecular weight per 100pts.wt. of the methyloldihydroxyethyleneurea-based compound. According to the invention, the processing of the cellulosic fabric using the fiber-treating agent can reduce the generation of free formaldehyde without lowering processing effect.
Description
The present invention relates to a kind of fabric finishing agent that is applicable to the finish of cellulose base fabric, particularly a kind of methylol dihydroxy ethylidene-urea compounds that contains, and be used for the fabric finishing agent that cellulose based fabric arrangement can minimizing formaldehyde produces.The invention still further relates to the method for sorting of using above-mentioned fabrics finishing agent finish of cellulose base fiber.
The fabric finishing agent that contains methylol dihydroxy ethylidene-urea compounds at present is widely used in improving the wrinkle resistance of fabric, various physical properties such as shrink resistance.But this method has individual problem, produces formaldehyde exactly in the finish fabric process.Therefore people propose and have tested many methods and reduced and suppresses the formaldehyde generation.
Reduce formaldehyde mole ratio, increasing degree of methylating is the method that the extensive at present minimizing formaldehyde that adopts produces, but only by these measures, the reduction of formaldehyde can not reach desirable level, and can cause putting in order result and chlorine resistance deterioration, the result is not very good.So people have proposed many method for distinguishing again.
A most frequently used technology that reduces the formaldehyde amount is used formaldehyde scavenger exactly.Common formaldehyde scavenger generally is the auxiliary agent of nitrogenous class, as urea, thiocarbamide, ethylidene-urea, dicyandiamide, glyoxal list uride etc.This class formaldehyde scavenger is widely used in the cellulose based fabric, common using method is that these reagent are added in the dressing liquid of easy generation formaldehyde, as described in USP2833670, or behind the compound finish fabric that easily produces formaldehyde, be adsorbed on the fiber these reagent sprinklings and other similar approach.
Although these formaldehyde scavengers can reduce the generation with formaldehyde in N-methylol compound such as the methylol dihydroxy ethylidene-urea compounds finish of cellulose base fabric effectively, but some problems are arranged still in other respects, as serious chlorine damage occurring with urea and glyoxal list uride, can obviously influence the light fastness of the fabric that dyes with chemically-reactive dyes with ethylidene-urea, although it is relatively low with the dicyandiamide chlorine damage, also lighter to light fastness influence with the chemically-reactive dyes DYED FABRICS, but had a strong impact on finishing effect.
On the other hand, use unazotized compound not have chlorine damage, the light fastness of coloured fibre is not had harmful effect yet, JP-A-59-21782 (=USP4396391) and JP-A-61-34381 (=USP4585827+USP4652268) suggestion is with polyol and dihydroxymethyl dihydroxy ethylidene-urea or alkylation dihydroxymethyl dihydroxy ethylidene-urea product.
And the JP-A-8-325939 suggestion mixes the back as fabric finishing agent by a certain percentage with the methylol dihydroxy ethylidene-urea compounds and the diethylene glycol (DEG) of particular range degree of methylating.Handle many fabrics with this fabric finishing agent and typically good arrangement performance is arranged as cotton products.But it is different with processing method according to handled material, this fabric finishing agent also can cause some problems, as be used for arrangement and resemble the viscose glue spiral shell when entangling regenerated cellulose such as silk grade, the formaldehyde amount that produces is still bigger, and contain the higher cotton of terylene amount/when washing mixed yarn, the fiber feel sclerosis of arrangement back with higher concentration arrangement.
The objective of the invention is in methylol dihydroxy ethylidene-urea compounds finish of cellulose base fabric, further to reduce the free formaldehyde content that produces from the fabric of arrangement, the finishing effect of avoiding so causing reduces, do not cause simultaneously that chlorine resistance and light fastness with the chemically-reactive dyes DYED FABRICS reduce, not the feel hardening phenomenon.
The inventor has carried out deep research to realize a kind of like this target.And having obtained good result by methylate methylol dihydroxy ethylidene-urea compounds and specific polyol blend with specific composition, the present invention has realized this target.
The invention provides a kind of like this fabric finishing agent, this finishing agent contains methylol dihydroxy ethylidene-urea based compound, the methylolation of every mole of ethylidene-urea ring or methoxymethylation rate are at 1.4～2 moles in this compound, it is that 5～40 parts molecular weight is no more than 200 micromolecule polyol that the above-mentioned methylol dihydroxy ethylidene-urea compounds of per 100 weight portions also contains weight portion, and weight portion is no less than 5 parts mean molecule quantity and is not less than mean molecule quantity that 1000 polyethylene glycol or weight portion be no less than 5 parts at 400～1000 polyethylene glycol.
The present invention provides a kind of like this fabric finishing agent simultaneously, this finishing agent contains the methylol dihydroxy ethylidene-urea compounds that methylates, the methylolation rate of every mole of ethylidene-urea ring is at 1.0～2 moles in this compound, all methylols on this ring all methylate, and the above-mentioned methylol dihydroxy ethylidene-urea compounds that methylates of per 100 parts of weight portions also contains the glycols compound that weight portion one of is no less than in 5 parts ethylene glycol or the diethylene glycol.
The present invention also provides a kind of method for sorting of cellulose based fabric, and wherein, the dressing liquid of employing also contains acid catalyst except that containing the above-mentioned fabrics finishing agent.
Methylol dihydroxy ethylidene-urea compounds of the present invention comprises by urea, glyoxal and formaldehyde reaction and obtains the compound (methylol dihydroxy ethylidene-urea compounds methylates) that compound (methylol dihydroxy ethylidene-urea compounds itself) and this compound further obtain with the methyl alcohol methyl-etherified.Usually the methylol dihydroxy ethylidene-urea compounds of using in the present invention be available below the mixture of several compounds of general molecular formula (I) expression:
Wherein: R and R ｀ represent hydrogen, methylol or methoxyl methyl respectively, but R and R ｀ can not be hydrogen simultaneously; R
4, R
5Represent hydrogen or methyl respectively.
Methylol dihydroxy ethylidene-urea can obtain by urea, glyoxal and formaldehyde reaction, but the product that obtains often is a mixture, and its general molecular formula can be represented with (II):
Wherein: R
2And R
3Represent hydrogen or methylol respectively, but can not be hydrogen simultaneously.The methylol dihydroxy ethylidene-urea compounds that methylates can further react by methylol dihydroxy ethylidene-urea and methyl alcohol, with R in (II) formula
2And/or R
3In a methylol methyl-etherified obtain.
In the methyl-etherified process, the part on the ethylidene-urea ring or comprehensive hydroxyl can carry out the methyl-etherified reaction simultaneously in (II) formula sometimes, and these methyl-etherifieds reactions obtain compound and have the form of describing in the above-mentioned general formula (I).The ethylidene-urea fourth finger of mentioning in this specification above-mentioned is the five-membered ring in general formula (I) and (II).
Containing methylol dihydroxy ethylidene-urea compounds, a kind of molecular weight is no more than in 200 micromolecule polyol and a kind of mean molecule quantity fabric finishing agent greater than 1000 polyethylene glycol, or contain in the fabric finishing agent that methylate methylol dihydroxy ethylidene-urea compounds and a kind of mean molecule quantity are 400～1000 polyethylene glycol, the methylol in the methylol dihydroxy ethylidene-urea compounds and the total amount of methoxyl methyl are 1.4～2 moles on every mole of ethylidene-urea ring, on average have 1.4～2 to be methylol or methoxyl methyl among R that is to say at general formula (I) and the R ｀.When the total amount of the methylol of every mole of ethylidene-urea ring and methoxyl methyl was less than 1.4 moles, its effect of improving fabric property obviously descended.When preparation methylol dihydroxy ethylidene-urea compounds, the amount of methylol can be controlled by the glyoxal in the change reaction system and the mol ratio of formaldehyde.
And the methylol that surpasses 1 mole is preferably arranged in above-mentioned methylol dihydroxy ethylidene-urea by methyl etherified.This methylol dihydroxy ethylidene-urea that methylates can have the methylol dihydroxy ethylidene-urea of 1.4～2 moles of methylols and methoxyl methyl and methyl alcohol reaction to make by every mole of above-mentioned ethylidene-urea ring, and the amount of methoxyl methyl can be controlled by the amount that changes the methyl alcohol in the course of reaction.
This methylol dihydroxy ethylidene-urea compounds with specific methylolation degree simultaneously and molecular weight be no more than 200 micromolecule polyol and mean molecule quantity and constituted fabric finishing agent of the present invention greater than 1000 polyethylene glycol blending.
Perhaps, have the methylol dihydroxy ethylidene-urea compounds of specific methylolation degree and mean molecule quantity be 400～1000 polyethylene glycol blending constituted fabric finishing agent of the present invention.
Molecular weight is no more than 200 micromolecule polyol and refers to contain two hydroxyls on the molecule at least, and molecular weight is not more than 200 non-aromatic compounds, for example ethylene glycol, diethylene glycol, propylene glycol, glycerine, trimethylolpropane etc.These polyols can use separately, also can two or several common uses, especially make spent glycol or diethylene glycol better effects if.Ethylene glycol and diethylene glycol also can use together.
The mean molecule quantity that is no more than the polyethylene glycol that 200 micromolecule polyol uses together with molecular weight should surpass 1000, if the molecular weight of polyethylene glycol is no more than 1000, just can not fully show with the effect of using the micromolecule polyol, the mean molecule quantity of preferred polyethylene glycol surpasses 2000, the restriction that the upper limit of polyethylene glycol mean molecule quantity is not strict, but the mean molecule quantity of normally used polyethylene glycol is no more than 10000.
The mean molecule quantity that per 100 parts of weight portion methylol dihydroxy ethylidene-urea compounds contain the micromolecule polyol of 5～40 parts of weight portions and surpass 5 parts of weight portions surpasses 1000 polyethylene glycol.Preferred per 100 parts of weight portion methylol dihydroxy ethylidene-urea compounds contain the micromolecule polyol of 5～30 parts of weight portions and the mean molecule quantity of 5～30 parts of weight portions surpasses 1000 polyethylene glycol.The content of micromolecule polyol and polyethylene glycol is low excessively in the methylol dihydroxy ethylidene-urea compounds, with the finishing effect that can not get expecting, micromolecule polyol too high levels is unfavorable from the angle of economy, sometimes in addition finishing effect also can reduce.On the other hand, increase molecular weight and also can cause economically uneconomical, because by increasing the imagination that improvement degree that polyethylene glycol obtains finishing effect can not reach expection greater than the ratio of 1000 polyethylene glycol.
When not using molecular weight less than 200 micromolecule polyol, methylol dihydroxy ethylidene-urea compounds that fabric finishing agent of the present invention can be by having specific methylolation degree and mean molecule quantity are that 400～1000 polyethylene glycol mixes and obtains.It is 400～1000 polyethylene glycol that per 100 parts of weight portion methylol dihydroxy ethylidene-urea compounds contain the mean molecule quantity that is no less than 5 parts of weight portions.The mean molecule quantity that preferred per 100 parts of weight portion methylol dihydroxy ethylidene-urea compounds contain 5～50 parts of weight portions is 400～1000 polyethylene glycol.It is that 400～1000 polyethylene glycol ratio is low excessively that per 100 parts of weight portion methylol dihydroxy ethylidene-urea compounds contain mean molecule quantity, with the finishing effect that can not get expecting.On the other hand, the ratio that increases mean molecule quantity and be 400～1000 polyethylene glycol also can cause economically uneconomical, because can not reach the imagination of expection by the improvement degree that increases the finishing effect that polyethylene glycol obtains.
When fabric finishing agent contains methylol dihydroxy ethylidene-urea compounds and during from one of them glycols compound of ethylene glycol, diethylene glycol, should use the methylol dihydroxy ethylidene-urea compounds that methylates, the methylolation degree of every mole of ethylidene-urea ring is 1.0～2.0 moles in this compound, that is to say among the R of general formula (I) and the R ｀ to have at least one to be methoxyl methyl, the surplus next one is a hydrogen.
This methylol dihydroxy ethylidene-urea compounds that methylates is that all methylols with R2 in the general formula (II) and R3 carry out methyl etherified reaction and obtain.
Per 100 parts of weight portions methylol dihydroxy ethylidene-urea compounds that methylates contains one of them glycols compound of the ethylene glycol that is no less than 5 parts of weight portions, diethylene glycol.Preferred per 100 parts of weight portions methylol dihydroxy ethylidene-urea compounds that methylates contains the glycols compound of 5～50 parts of weight portions.Per 100 parts of weight portions methylate, and to contain glycols compound ratio low excessively for methylol dihydroxy ethylidene-urea compounds, with the finishing effect that can not get expecting.And, the ratio of increase glycols compound, the improvement of finishing effect does not reach the degree of expection yet.Therefore per 100 parts of weight portions methylol dihydroxy ethylidene-urea compounds that methylates contains at the most that the glycols compound of 50 parts of weight portions is favourable economically.As the glycols compound can be to make spent glycol or diethylene glycol separately, and both also can mix use.
Fabric finishing agent of the present invention can only obtain by the above-mentioned methylol dihydroxy ethylidene-urea compounds of blend and glycol etc.Although not necessarily need reaction between each component, may react between component, for example when temperature raises.When this finishing agent is not when using with the form of reactant, each component can now add before use in promptly fixed ratio, also can be pre-mixed.This fabric finishing agent is prepared into the form of the aqueous solution usually.
The fabric finishing agent of the invention described above is to use jointly with acid catalyst when being used for the finish of cellulose base fabric.The acid catalyst that uses comprises inorganic salts such as the chloride, sulfate, nitrate, borofluoride of two valencys such as magnesium, aluminium, zinc or polyvalent metal; Ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium phosphate; Organic ammonium salt and various organic acid and inorganic acids such as hydrochloric acid monoethanolamine.These catalyst can use separately also can two or more mix use.
When containing methylol dihydroxy ethylidene-urea compounds, a kind of molecular weight, use is no more than 200 micromolecule polyol and a kind of mean molecule quantity fabric finishing agent greater than 1000 polyethylene glycol, or use and to contain the fabric finishing agent that methylate methylol dihydroxy ethylidene-urea compounds and a kind of mean molecule quantity are 400～1000 polyethylene glycol, before cellulose based fabric is put in order, the temperature that contains in the dressing liquid of fabric finishing agent and acid catalyst is controlled at 25 ℃, pH value in the groove is controlled in 2.5～5 scopes, preferably is controlled in 3.0～4.5.If pH is too high or too low in the dressing liquid, can cause each the physical property imbalance that is organized the back fabric.
In the dressing liquid that contains fabric finishing agent of the present invention and above-mentioned acid catalyst, each component can now add in use to scale, also the part component can be pre-mixed, and remaining component adds before use, and perhaps all components all are pre-mixed.
When compound that the reaction of using methylol dihydroxy ethylidene-urea compounds and glycols compound obtains, acid catalyst can in blend.
In the dressing liquid that contains fabric finishing agent of the present invention and above-mentioned acid catalyst, can add various functional aids such as softener, feel modifying agent, thickening agent, formaldehyde scavenger, water repellent, water absorbing agent, wetting agent, oil-repellent agent, antistatic additive, dust-proofing agent, antiseptic, deodorant, ultra-violet absorber, fire retardant and dyestuff, pigment, fluorescent whitening agent, color-fixing agent etc. as required.But should consider each compatibility between components and Expected Results of the present invention.
Cellulose based fabric of the present invention is meant cellulose fibre, as cotton, fiber crops, regenerated cellulose etc., and one or more and synthetic fiber such as polyester, nylon, vinylon, acrylic fiber, cellulose acetate in these cellulose fibres, animal fibers such as hair, silk, the mixture of inorfils such as glass fibre, carbon fiber.Fabric finishing agent of the present invention is especially effective to regenerated fiber.These cellulose based fabrics can be forms such as filler, line, woven, establishment fabric, nonwoven fabric and sewing piece.
The using method that contains the dressing liquid finish fabric of fabric finishing agent of the present invention and acid catalyst requires not strict especially.The RESIN FINISH method of various fabrics commonly used all can adopt, and that is to say finishing agent to be measured in accordance with regulations according to methods such as spray-on process, coating, pad dyeing method, injection back centrifugal separations to be added on the fiber.If necessary, fabric can be in that to bake (130～180 ℃ down sclerosis 15 seconds to 10 minutes) preceding elder generation predrying.In this operation, can add a kind of baking before can to fabric sew up and push so-called after bake and handle and other processing and sorting processes such as folding arrangement, glazing arrangement, modification arrangement.
Following embodiment can further describe the present invention, but does not limit category of the present invention.In an embodiment, " % " represents content, do not specify, amount is represented with weight.Among each embodiment, the methylol in the methylol dihydroxy ethylidene-urea compounds that methylates and the amount of methyl are to measure by following method below.
Methylol: the total amount of methylol and free formaldehyde can iodine be an indicator, obtain with the sodium thiosulfate titration methylol dihydroxy ethylidene-urea compounds that methylates, and the available sodium sulfite of amount of the free formaldehyde in the methylol dihydroxy ethylidene-urea compounds that methylates is an indicator, and the acid-base titration by hydrochloric acid obtains.The amount that the amount of methylol just can deduct free formaldehyde by the total amount of methylol and free formaldehyde obtains.
Methyl: methylol dihydroxy ethylidene-urea compounds and acid fully hydrolysis together will methylate earlier, quantity of methyl alcohol in the product can quantitatively detect by gas-chromatography and obtain, the quantity of methyl alcohol in the methylol dihydroxy ethylidene-urea compounds of methylating simultaneously also can quantitatively detect by gas-chromatography and obtain, and both subtract each other the amount that has just obtained methyl.Synthetic embodiment 1: the methylol dihydroxy ethylidene-urea compounds that methylates synthetic
The formalin that in the four-hole boiling flask of reflux condensing tube is housed, adds 162g (2mol) 37%, the urea of the glyoxal water solution of 145g (1mol) 40% and 60g (1mol), at 50～60 ℃ of reaction 3hr, pass through dropping sodium solution hierarchy of control pH in the course of reaction about 7.Adding 64g (2mol) methyl alcohol then, is 2 with sulfuric acid regulation system pH, then at 40 ℃ of reaction 2hr.Adding sodium hydroxide solution regulation system pH again is 7.Unreacted methanol is removed by decompression distillation.Add entry and make system concentration be controlled at 50%, the pH of this aqueous solution is shown as 6.5.Every mole of ethylidene-urea ring has 0.8 mole of methylol and 1.0 moles of methoxyl methyls in the methylol dihydroxy ethylidene-urea that methylates that obtains like this.The preparation of embodiment 1～4 and comparative examples 1～3 (a) fabric finishing agent and dressing liquid
Will by micromolecule polyol shown in the table 1 and polyethylene glycol be added to 150g concentration be 50% by obtaining fabric finishing agent in the synthetic embodiment 1 synthetic methylol dihydroxy ethylidene-urea aqueous solution that obtains methylating.Only add micromolecule polyol (ethylene glycol) in comparing embodiment 1, only add polyethylene glycol in comparing embodiment 2, in comparing embodiment 3, micromolecule polyol and polyethylene glycol do not add.In these fabric finishing agents, add 45gSumitex Accelerator X-110 (fibre finish acid catalyst, Sumiyomo chemical Co.Ltd produces), and add entry and make the total amount of dressing liquid reach 1L, the pH value during 25 ℃ of these dressing liquids is as shown in table 1.(b) arrangement of fiber and test
To be impregnated in the dressing liquid of preparation in the above-mentioned steps (a) through the wide cloth of polyester/cotton (65/35) blending of refining and bleaching, be expressed to cloth weightening finish 65% then, use 105 ℃ hot-air seasoning 3min again.Then at 150 ℃ of cloth that descend after sclerosis 3min obtain putting in order.The cloth through arrangement that obtains carries out following test, and the result is as shown in table 1.
Wash the back folding line: press JIS L 1096-1990,6.23.1, method A, (C) roll-drying is tested;
Free formaldehyde total amount (F.F amount): press JIS L 1041-1994,5.3.1 (II), method B tests;
Bending resistance: press JIS L 1096-1990,6.19.5, method E (feel method of testing) carries out.
Table 1
*1 EG: ethylene glycol
| Embodiment number | The micromolecule polyalcohol *1 | Polyethylene glycol *2 | Dressing liquid pH | The physical property of arrangement back cloth | |||||
| Wash the back rivel | The F.F amount | Bending resistance | |||||||
| Embodiment 1 | ??EG/5g | ?PEG-4000/5g | ????3.9 | 3.9 level | ????63ppm | ????225.5g | |||
| Embodiment 2 | ????EG/10g | ????PEG- ??4000/10g | ????3.8 | 3.8 level | ????42ppm | ????202.6g | |||
| Embodiment 3 | ????DEG／10g | ????PEG- ??6000/10g | ????3.8 | 3.8 level | ????48ppm | ????192.3g | |||
| Embodiment 4 | ?DEG/10g | ????PEG- ??2000/10g | ????3.9 | 3.9 level | ????51ppm | ????213.8g | |||
| Comparative examples 1 | ??EG/10g | Do not have | ????3.8 | 3.7 level | ????50ppm | ????427.1g | |||
| Comparative examples 2 | Do not have | ????PEG- ??4000/10g | ????3.9 | 3.9 level | ????133ppm | ????192.9g | |||
| Comparative examples 3 | Do not have | Do not have | ????3.9 | 3.6 level | ????143ppm | ????193.4g | |||
DEG: diethylene glycol
*2 PEG: polyethylene glycol (back data representation mean molecule quantity)
As shown in table 1, a blend has the comparative examples 1 of ethylene glycol to compare with the comparative examples 3 of not adding additives such as polyalcohol, and the amount of free formaldehyde has obvious decline.But counter-bending value is bigger, and feel is bad.On the contrary, in the comparative examples 2 of blend polyethylene glycol only, counter-bendingly remain on good level, but almost do not have effect suppressing free formaldehyde.Have among the embodiment 1～4 of ethylene glycol (or diethylene glycol) and polyethylene glycol in blend, suppress the respond well of free formaldehyde, also kept simultaneously good as the finishing effect sign wash the back folding line, counter-bending value does not increase yet, and illustrates that its feel is good.
Synthetic embodiment 2: methylol dihydroxy ethylidene-urea compounds synthetic
The formalin that in the four-hole boiling flask of reflux condensing tube is housed, adds 146g (1.8mol) 37%, the urea of the glyoxal water solution of 145g (1mol) 40% and 60g (1mol), at 50～60 ℃ of reaction 3hr, pass through dropping sodium aqueous solution hierarchy of control pH in the course of reaction about 8.Add entry then and make system concentration be controlled at 45%, the pH of this aqueous solution is shown as 6.4.Every mole of ethylidene-urea ring has 1.7 moles of methylols in the methylol dihydroxy ethylidene-urea that methylates that obtains like this.The preparation of embodiment 5 (a) fabric finishing agent and dressing liquid
With 10g ethylene glycol and 10g mean molecule quantity be 6000 polyethylene glycol be added to 100g concentration be 45% obtain obtaining fabric finishing agent in the methylol dihydroxy ethylidene-urea aqueous solution by synthetic embodiment 2 is synthetic.Adding 30g concentration and be 25% magnesium chloride brine in these fabric finishing agents, and add entry and make the total amount of dressing liquid reach 950ml, is 3.8 by the pH value that drips the maleic acid regulation system then, adds water again and makes whole system volume reach 1L, promptly obtains dressing liquid.(b) arrangement of fiber and test
Use the dressing liquid that obtains in the above-mentioned steps (a), and adopt the described method for sorting of embodiment 1 (b) to put wide cut (No. 40) the fluorescent brightening cloth of 100% cotton, the cotton after obtaining putting in order in order.Cotton through arrangement needs to carry out the mensuration of free formaldehyde content by 1 method of testing that provides is provided, but also need according to JIS L 1059-1992, method B (Meng Shan is method) measures the dried wrinkle resistance that this puts the back cotton in order under without the preliminary finish condition, its result is as shown in table 2.Synthetic embodiment 3: the methylol dihydroxy ethylidene-urea compounds that methylates synthetic
The formalin that in the four-hole boiling flask of reflux condensing tube is housed, adds 98g (1.2mol) 37%, the urea of the glyoxal water solution of 145g (1mol) 40% and 60g (1mol), at 50～60 ℃ of reaction 3hr, pass through dropping sodium aqueous solution hierarchy of control pH in the course of reaction about 7.Adding 64g (2mol) methyl alcohol then, is 2 with sulfuric acid regulation system pH, at 40 ℃ of reaction 2hr.Hydro-oxidation sodium water solution regulation system pH to 7 in the solution that obtains.Unreacted methanol is removed by decompression distillation.Add entry then and make system concentration be controlled at 45%, the pH of this aqueous solution is 6.7.Every mole of ethylidene-urea ring has 0.1 mole of methylol and 1.0 moles of methoxyl methyls in the methylol dihydroxy ethylidene-urea that methylates that obtains like this.Comparative examples 4
Use is by the 45% synthetic methylol dihydroxy ethylidene-urea aqueous solution that methylates of synthetic embodiment 3, and the same quadrat method that provides by embodiment 5 prepares dressing liquid.The test result of arrangement process and physical property is as shown in table 2.
Table 2
As seen from Table 2, in embodiment 5, methylol amount in the methylol dihydroxy ethylidene-urea of using is under control, thereby obtained good physical property, but in comparative examples 4, because the methyl etherified rate of methylol in the methylol dihydroxy ethylidene-urea of using is lower, so wrinkle resistance is also lower.The preparation of embodiment 6 to 9 and comparative examples 5 to 7 (a) fabric finishing agents and dressing liquid
| Embodiment number | Methylol dihydroxy ethylidene-urea compounds | Dressing liquid pH | The physical property of arrangement back fabric | |||
| Every mole of ethylidene-urea ring | The F.F amount | Wrinkle resistance | ||||
| Methylol | Methoxyl methyl | Warp-wise | Broadwise | |||
| Embodiment 5 | 1.7 mole | - | 3.9 | 31ppm | 78％ | 73％ |
| Comparative examples 4 | 0.1 mole | 1.0 mole | 3.9 | 29ppm | 64％ | 62％ |
By requirement shown in the table 3 with the glycols compound be added to 150g concentration be 50% by obtaining fabric finishing agent in the synthetic methylol dihydroxy ethylidene-urea aqueous solution that methylates of synthetic embodiment 1.In comparing embodiment 3, do not add the glycols compound.In this fabric finishing agent, add 45gSumitex Accelerator X-110 (fibre finish acid catalyst then, Sumiyomo chemical Co.Ltd produces), and add entry and make the total amount of dressing liquid reach 1L, the pH value during 25 ℃ of these dressing liquids is as shown in table 3.(b) fibre finish and test
The dressing liquid that uses above-mentioned steps (a) to obtain, the fibre finish method and the method for testing that adopt embodiment 1 (b) to provide, the result who obtains is as shown in table 3.
Table 3
| Embodiment number | Glycol | Dressing liquid pH | The physical property of arrangement back fabric | ||||
| Wash the back folding line | The F.F amount | Bending resistance | |||||
| Embodiment 6 | ?PEG-600/30g | ????3.6 | 4.0 level | ??64ppm | ????217.1g | ||
| Embodiment 7 | ?PEG-600/40g | ????3.7 | 3.9 level | ??41ppm | ????199.6g | ||
| Embodiment 8 | ?PEG-400/40g | ????3.7 | 3.9 level | ??38ppm | ????221.5g | ||
| Embodiment 9 | ????PEG- ??1000/40g | ??3.8 | 3.9 level | ??66ppm | ????188.1g | ||
| Comparative examples 5 | ?DEG-??/40g | ????3.6 | 4.0 level | ??35ppm | ????401.3g | ||
| Comparative examples 6 | ????PEG- ??2000/40g | ????3.7 | 3.8 level | ??138ppm | ????189.5g | ||
| Comparative examples 7 | Do not have | ????3.6 | 3.8 level | ??143ppm | ????193.4g | ||
*PEG: polyethylene glycol (the unequal molecular weight of back tables of data)
DEG: diethylene glycol
As shown in table 3, to compare with the comparative examples 7 of not adding additives such as polyol in the comparative examples 5 of blend diethylene glycol, the amount of free formaldehyde has obvious decline.But counter-bending value is bigger, and feel is bad.On the contrary, be in the comparative examples 6 of 2000 polyethylene glycol at blend mean molecule quantity only, counter-bendingly remain on good level, but almost do not have effect suppressing free formaldehyde.In blend mean molecule quantity being arranged is among the embodiment 6～9 of 400～1000 polyethylene glycol, suppresses the respond well of free formaldehyde, also kept simultaneously good as the finishing effect sign wash the back folding line, counter-bending value does not increase yet, and illustrates that its feel is good.The preparation of embodiment 10 (a) fabric finishing agent and dressing liquid
With the 25g mean molecule quantity be 600 polyethylene glycol be added to 100g concentration be 45% obtain making fabric finishing agent in the methylol dihydroxy ethylidene-urea aqueous solution by synthetic embodiment 2 is synthetic.Adding 30g concentration and be 25% magnesium chloride brine in this finishing agent, and add water and make the cumulative volume of dressing liquid reach 950ml, is 3.8 by the pH value that adds the maleic acid hierarchy of control then, adds water again and makes whole system volume reach 1L, promptly obtains dressing liquid.(b) fibre finish and test
Use the dressing liquid that obtains in the above-mentioned steps (a), and adopt the described method for sorting of embodiment 1 (b) to put wide cut (No. 40) the fluorescent brightening cloth base of 100% cotton, the cotton after obtaining putting in order in order.Cotton through arrangement needs according to JIS L 1059-1992, and method B (Meng Shan is method) measures the dry wrinkle resistance of this arrangement back cotton under not preliminary finish condition, and its result is as shown in table 4.Comparative examples 8
Use is by the 45% synthetic methylol dihydroxy ethylidene-urea aqueous solution that methylates of synthetic embodiment 3, and the same quadrat method that provides by embodiment 10 prepares dressing liquid.The test result of arrangement process and physical property is as shown in table 4.
Table 4
As seen from Table 4, in embodiment 10, methylol amount in the methylol dihydroxy ethylidene-urea of using is under control, thereby obtained good physical property, but in comparative examples 8, because the methyl etherified rate of methylol in the methylol dihydroxy ethylidene-urea of using is lower, so wrinkle resistance is also lower.Synthetic embodiment 4: the methylol dihydroxy ethylidene-urea compounds that methylates synthetic
| Embodiment number | Methylol dihydroxy ethylidene-urea compounds | Dressing liquid pH | Wrinkle resistance | ||
| Methylol | Methoxyl methyl | Warp-wise | Broadwise | ||
| Embodiment 10 | 1.7 mole | - | 3.8 | 78％ | 73％ |
| Comparative examples 8 | 0.1 mole | 1.0 mole | 3.9 | 64％ | 62％ |
The formalin that in the four-hole boiling flask of reflux condensing tube is housed, adds 162g (2mol) 37%, the urea of the glyoxal water solution of 145g (1mol) 40% and 60g (1mol), at 50～60 ℃ of reaction 3hr, pass through dropping sodium aqueous solution hierarchy of control pH in the course of reaction about 7.Adding 128g (4mol) methyl alcohol then, is 2 with sulfuric acid hierarchy of control pH, at 40 ℃ of reaction 2hr.Hydro-oxidation sodium water solution regulation system pH to 7 in the solution that obtains.Unreacted methanol is removed by decompression distillation.Add water management then and make system concentration 50%, the pH of this aqueous solution is 6.5.2 moles of methoxyl methyls of every mole of ethylidene-urea ring do not detect methylol in the methylol dihydroxy ethylidene-urea that methylates that obtains like this.The preparation of embodiment 11 to 14 and comparative examples 9 to 11 (a) fabric finishing agents and dressing liquid
By requirement shown in the table 5 with the glycols compound be added to 100g concentration be 50% by obtaining fabric finishing agent in the synthetic methylol dihydroxy ethylidene-urea aqueous solution that methylates of synthetic embodiment 4.In comparative examples 11, do not add the glycols compound.In this fabric finishing agent, add 30gSumitex Accelerator X-110 (fibre finish acid catalyst, Sumiyomo chemical Co.Ltd production) then, and add entry and make the total amount of dressing liquid reach 1L.(b) fibre finish and test
To entangle plain weave wrinkle silk through viscose glue spiral shell refining and that bleach and be impregnated in the dressing liquid of preparation in the above-mentioned steps (a), behind the dipping fabric presses be arrived cloth weightening finish 75%, use 105 ℃ hot-air seasoning 3min again.Then at 150 ℃ of fabrics that descend after sclerosis 3min obtain putting in order.The cloth through arrangement that obtains carries out shrinkage factor and free formaldehyde quantitative determination test, and the result is as shown in table 5.
Table 5
| Embodiment number | Glycol | Total amount | The physical property of arrangement back fabric | ||
| Shrinkage factor | The F.F amount | ||||
| Warp-wise | Broadwise | ||||
| Embodiment 11 | Ethylene glycol | 10g | 1.7％ | 2.4％ | 73ppm |
| Embodiment 12 | Ethylene glycol | 20g | 1.6％ | 2.2％ | 71ppm |
| Embodiment 13 | Diethylene glycol | 10g | 1.6％ | 2.3％ | 77ppm |
| Embodiment 14 | Diethylene glycol | 20g | 1.7％ | 2.3％ | 74ppm |
| Comparative examples 9 | Polyethylene glycol (mean molecule quantity 400) | 10g | 1.6％ | 2.4％ | 118ppm |
| Comparative examples 10 | Diethylene glycol | 2g | 1.6％ | 2.5％ | 139ppm |
| Comparative examples 11 | Do not have | 1.6％ | 2.5％ | 140ppm | |
| The original fabrics that does not have arrangement | Do not have | 2.8％ | 7.3％ | - | |
As shown in table 5, with the comparative examples 11 of the methylol dihydroxy ethylidene-urea arrangement of methylating with there not be the wrinkle performance of spinning of the original fabrics of arrangement to compare, but the free formaldehyde content increase.Using the methylate comparative examples 9 of methylol dihydroxy ethylidene-urea and the common arrangement of polyethylene glycol and the comparative examples 10 of putting in order jointly with a small amount of diethylene glycol and the methylol dihydroxy ethylidene-urea that methylates, the production generation of free formaldehyde almost is not suppressed yet.Do not use the comparative examples 11 of glycols compound to compare, make among the embodiment 11～14 of spent glycol and diethylene glycol, suppress the respond well of free formaldehyde, kept the good wrinkle performance of spinning simultaneously yet.Synthetic embodiment 5: the methylol dihydroxy ethylidene-urea compounds that methylates synthetic
The formalin that in the four-hole boiling flask of reflux condensing tube is housed, adds 146g (1.8m01) 37%, the urea of the glyoxal water solution of 145g (1mol) 40% and 60g (1mol), at 50～60 ℃ of reaction 3hr, pass through dropping sodium aqueous solution hierarchy of control pH in the course of reaction about 7.Adding 128g (4mol) methyl alcohol then, is 2 with sulfuric acid hierarchy of control pH, at 40 ℃ of reaction 2hr.Hydro-oxidation sodium water solution regulation system pH to 7 in the solution that obtains.Unreacted methanol is removed by decompression distillation.Add water management then and make system concentration 50%, the pH of this aqueous solution is 6.5.Every mole of ethylidene-urea ring contains 2 moles of methyl in the methylol dihydroxy ethylidene-urea that methylates that obtains like this, does not detect methylol.The preparation of embodiment 15 (a) fabric finishing agent and dressing liquid
With the 10g diethylene glycol be added to 100g concentration be 50% by making fabric finishing agent in the synthetic embodiment 5 synthetic methylol dihydroxy ethylidene-urea aqueous solution that obtain methylating.Adding 30g concentration and be 25% magnesium chloride brine in this finishing agent, and add water and make the cumulative volume of dressing liquid reach 950ml, is 3.8 by the pH value that adds the maleic acid hierarchy of control then, adds water again and makes whole system volume reach 1L, promptly obtains dressing liquid.(b) fibre finish and test
Use the dressing liquid that obtains in the above-mentioned steps (a), and adopt the described method for sorting arrangement of embodiment 11 (b) through Ben Baige ammonia copper wire cloth base refining and bleaching, the cloth base after obtaining putting in order.Cloth grey cloth through arrangement needs to carry out same test according to embodiment 11, and its result is as shown in table 6.Synthetic embodiment 6: the methylol dihydroxy ethylidene-urea compounds that methylates synthetic
The formalin that in the four-hole boiling flask of reflux condensing tube is housed, adds 146g (1.8mol) 37%, the urea of the glyoxal water solution of 145g (1mol) 40% and 60g (1mol), at 50～60 ℃ of reaction 3hr, pass through dropping sodium aqueous solution hierarchy of control pH in the course of reaction about 7.Adding 64g (2mol) methyl alcohol then, is 2 with sulfuric acid hierarchy of control pH, at 40 ℃ of reaction 2hr.Hydro-oxidation sodium water solution regulation system pH to 7 in the solution that obtains.Unreacted methanol is removed by decompression distillation.Add water management then and make system concentration 50%, the pH of this aqueous solution is 6.7.Every mole of ethylidene-urea ring contains 0.7 mole of methylol, 1.0 moles of methoxyl methyls in the methylol dihydroxy ethylidene-urea that methylates that obtains like this.Comparative examples 12
Use is by the 50% synthetic methylol dihydroxy ethylidene-urea aqueous solution that methylates of synthetic embodiment 6, and the same quadrat method that provides by embodiment 15 prepares dressing liquid.The test result of arrangement process and physical property is as shown in table 6.
Table 6
As seen from Table 6, in comparative examples 12, owing to still have methylol in the methylol dihydroxy ethylidene-urea of using that methylates, so the formaldehyde amount is bigger in the system.In embodiment 15, owing to controlled the methyl amount, there is not methylol fully in the methylol dihydroxy ethylidene-urea that methylates of application, blend simultaneously has diethylene glycol, thereby has obtained good physical property.
| Embodiment number | Methylol dihydroxy ethylidene-urea compounds | The physical property of arrangement back fabric | |||
| Every mole of ethylidene-urea ring | The F.F amount | Shrinkage factor | |||
| Methylol | Methyl | Warp-wise | Broadwise | ||
| Embodiment 15 | - | 2.0 mole | 54ppm | 1.8％ | 2.1 ％ |
| Comparative examples 12 | 0.7 mole | 1.0 mole | 102ppm | 1.9％ | 2.4％ |
Contain methylol dihydroxy ethylidene-urea compounds in the fabric finishing agent of the present invention, the methylolation of every mole of ethylidene-urea ring or methoxymethylation rate are at 1.4～2 moles in this compound, to contain weight portion be that 5～40 parts molecular weight is no more than 200 micromolecule polyol to the above-mentioned methylol dihydroxy ethylidene-urea compounds of per 100 parts of weight portions in this finishing agent, and weight portion is no less than mean molecule quantity that 5 parts mean molecule quantity is no less than 5 parts greater than 1000 polyethylene glycol or weight portion at 400～1000 polyethylene glycol.Use fabric finishing agent of the present invention can greatly reduce the generation of free formaldehyde, avoid simultaneously causing that finishing effect reduces, and do not cause that chlorine resistance and light fastness reduce, without any bad feel.
Fabric finishing agent of the present invention can contain the methylol dihydroxy ethylidene-urea compounds that methylates simultaneously, the methylolation rate of every mole of ethylidene-urea ring is at 1.0～2 moles in this compound, and all methylols on this ring have all methylated, and the above-mentioned methylol dihydroxy ethylidene-urea compounds that methylates of per 100 parts of weight portions contains weight portion and is no less than glycols compounds such as 5 parts ethylene glycol or diethylene glycol in this finishing agent.Use fabric finishing agent of the present invention can greatly reduce the generation of free formaldehyde, avoid causing finishing effect reductions such as anti-shrinkage simultaneously.
Claims (9)
1. fabric finishing agent, it contains methylol dihydroxy ethylidene-urea compounds, and the methylolation of every mole of ethylidene-urea ring or methoxymethylation rate are in 1.4～2 moles scope in this compound; With molecular weight based on above-mentioned methylol dihydroxy ethylidene-urea compounds 5～40 weight portions of 100 parts of weight portions be 200 or less micromolecule polyol and 5 weight portions or more mean molecule quantity greater than 1000 polyethylene glycol, or 5 weight portions or more mean molecule quantity are at 400～1000 polyethylene glycol.
2. according to the described fabric finishing agent of claim 1, wherein, 1 mole on every mole of ethylidene-urea ring in the methylol dihydroxy ethylidene-urea or more methylol are by methyl-etherified.
3. according to the described fabric finishing agent of claim 1, wherein, it contains molecular weight 200 or less micromolecule polyol and polyethylene glycol, and wherein the micromolecule polyol is ethylene glycol and/or diethylene glycol.
4. according to the described fabric finishing agent of claim 1, it contains molecular weight 200 or less micromolecule polyol and polyethylene glycol, and wherein the micromolecule polyol is ethylene glycol and/or diethylene glycol.
5. according to the described fabric finishing agent of claim 1, it contains molecular weight 200 or less micromolecule polyol and polyethylene glycol, and wherein the mean molecule quantity of polyethylene glycol is greater than 2000.
6. fabric finishing agent, it contains the methylol dihydroxy ethylidene-urea compounds that methylates, the methylolation rate of every mole of ethylidene-urea ring is all methylated at 1.0～2 moles and all methylols in this compound, also contains 5 weight portions or more is selected from a kind of glycols compound in ethylene glycol and the diethylene glycol based on the above-mentioned methylol dihydroxy ethylidene-urea compounds that methylates of 100 parts of weight portions.
7. the method for sorting of a cellulose based fabric, wherein, the dressing liquid that will contain a kind of acid catalyst and the described fabric finishing agent of claim 1 is applied on the fabric of cellulose base.
8. according to the method for sorting of the described cellulose based fabric of claim 7, wherein, before being used to handle cellulose based fabric, the pH value of dressing liquid in the time of 25 ℃ is controlled at 2.5 to 5.
9. the method for sorting of a cellulose based fabric, wherein, the dressing liquid that will contain a kind of acid catalyst and the described fabric finishing agent of claim 6 is applied on the fabric of cellulose base.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP366978/1999 | 1999-12-24 | ||
| JP36697899A JP2001181968A (en) | 1999-12-24 | 1999-12-24 | Fiber-treating agent and method for processing cellulosic fiber |
| JP366981/1999 | 1999-12-24 | ||
| JP36698199A JP2001181969A (en) | 1999-12-24 | 1999-12-24 | Fiber-treating agent and method for processing cellulosic fiber by using the same |
| JP2000018600A JP2001207383A (en) | 2000-01-27 | 2000-01-27 | Fiber processing agent and method of processing for cellulose fiber using the same |
| JP018600/2000 | 2000-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1301895A true CN1301895A (en) | 2001-07-04 |
Family
ID=27341742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00135797A Pending CN1301895A (en) | 1999-12-24 | 2000-12-21 | Fabric finishing agent and finishing method for cellulose based fabric thereof |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20010062636A (en) |
| CN (1) | CN1301895A (en) |
| ID (1) | ID28737A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638847B (en) * | 2009-07-24 | 2012-10-24 | 东莞市德能化工有限公司 | Formaldehyde-free durable crease-proof finishing agent used for cellulosic fiber fabric |
| WO2018082454A1 (en) * | 2016-11-04 | 2018-05-11 | 香港纺织及成衣研发中心有限公司 | Barrier fabric manufacturing method and barrier fabric |
| CN114687207A (en) * | 2022-04-20 | 2022-07-01 | 武汉纺织大学 | Crease-resistant finishing method for high-density high-count cotton textile based on urea-formaldehyde resin |
-
2000
- 2000-12-21 CN CN00135797A patent/CN1301895A/en active Pending
- 2000-12-22 KR KR1020000080428A patent/KR20010062636A/en not_active Application Discontinuation
- 2000-12-22 ID IDP20001138D patent/ID28737A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638847B (en) * | 2009-07-24 | 2012-10-24 | 东莞市德能化工有限公司 | Formaldehyde-free durable crease-proof finishing agent used for cellulosic fiber fabric |
| WO2018082454A1 (en) * | 2016-11-04 | 2018-05-11 | 香港纺织及成衣研发中心有限公司 | Barrier fabric manufacturing method and barrier fabric |
| CN114687207A (en) * | 2022-04-20 | 2022-07-01 | 武汉纺织大学 | Crease-resistant finishing method for high-density high-count cotton textile based on urea-formaldehyde resin |
| CN114687207B (en) * | 2022-04-20 | 2024-04-26 | 武汉纺织大学 | Anti-wrinkle finishing method for high-density high-count cotton textiles based on urea resin |
Also Published As
| Publication number | Publication date |
|---|---|
| ID28737A (en) | 2001-06-28 |
| KR20010062636A (en) | 2001-07-07 |
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