CN1032047A - Water-soluble active methylenes as formaldehyde scavenger - Google Patents
Water-soluble active methylenes as formaldehyde scavenger Download PDFInfo
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- CN1032047A CN1032047A CN 88103032 CN88103032A CN1032047A CN 1032047 A CN1032047 A CN 1032047A CN 88103032 CN88103032 CN 88103032 CN 88103032 A CN88103032 A CN 88103032A CN 1032047 A CN1032047 A CN 1032047A
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Abstract
With replacement or unsubstituted polyalcohol diethyl malonate or ethyl acetoacetate are carried out transesterification,, prepare formaldehyde scavenger thus to obtain water-soluble active methylenes compound (molecular formula is referring to Figure of abstract).R is-CH in the molecular formula
3Or H[O (CH
2m]
n-O-; R ' is H[O (CH
2)
m']
n-O-; M and/or m ' are 1-3; N and/or n ' are 1-19; Y is-CH
2-or-CH
2-CO-CH
2-.Described activity methene compound has unique effect for reducing with formaldehyde release rate aspect in fabric after the permanent set finishing agent processing that contains the N-methylol crosslinking agent and the flakeboard, and does not influence the performance of fabric or flakeboard.
Description
The present invention submitted on May 20th, 1987, application number is to submit on May 20th, 053,606,1987, application number is 052, submitted on July 8th, 842 and 1987, application number is the part continuation application of each application case of 071,032, they are respectively to submit on September 2nd, 1986, application number is the continuation application of 902,750 application case, divides an application and the part continuation application.The present invention submitted on May 2nd, 1988, application number is the part continuation application of unknown application case also, it is to submit on July 8th, 1987, application number 071, the continuation application of 032 application case, the latter submitted on September 2nd, 1986, and application number is the part continuation application of 902,750 application case.
The present invention relates to can be used for reduce composition such as from fabric of handling through durable press and the formaldehyde amount that the process of making flakeboard, discharges.More particularly, the present invention relates to can be used as to reducing especially effectively and do not reduce the composition of formaldehyde scavenger of the performance of fabric or flakeboard thereafter from the fabric of handling through permanent set and the formaldehyde amount that during making the flakeboard process, discharges.
Term " fabric " used herein " be meant by natural fabric; for example jute, sisal hemp, piemarker, hemp and cotton and many organic synthetic fibers; for example viscose, cellulose esters, vinylite fiber, polyacrylonitrile and copolymer, olefin polymer and copolymer, for example product and the article made of ethene, polyimides or nylon-type or the like.Used fabric can be the BLENDED FABRIC of the fabric or the multiple fiber of one pack system.
Term used herein " through the fabric of permanent set processing " is meant the employing finishing agent, the for example dimethyl ether of glyoxal resin, formalin, Lauxite, dimethylol urea, ureaformaldehyde, melamine formaldehyde resin, ethylene urea urea formaldehyde, for example dimethylol urea, triazine formaldehyde resin, triazinone formaldehyde resin and known and do not need the analog that is described in detail at this in field of the present invention, by heating, dry and curing, the aforesaid fabric that under the condition of doing and wetting, has anti-folding line and fold performance.
Term used herein " flakeboard " is meant goods used in the fabric structure.It is by making the sawdust pressurization and the heating that are mixed with a kind of resin that this resin solidification is made.Usually, this resin is a formaldehyde resin.
Formaldehyde and formaldehyde-derived product are mainly used in the dry fabrication technology of the modernized chemical finishing and the flakeboard industry of textile industry.Yet, follow the application of these products, in fabric after arrangement or the facing and in the heating process that flakeboard is made, if particularly through the plate of arrangement be exposed to heat and (or) in the moisture, can form free or releasable formaldehyde.
The formaldehyde that discharges has serious stimulation to eye, mucous membrane and skin.Can poison if suck, being in for a long time may be carcinogenic in this environment.Therefore, environment, consumer and labor group more and more strong request make such as reducing to minimum from the formaldehyde amount that through chemically treated fabric or flakeboard, discharges.At present, U.S.'s employment security and health control office [The federal Occupational Safety and Health Administration(" OSHA ")] are studying ask for something the formaldehyde in the workplace air are being limited in the low proposal that reaches 0.1～0.5ppm.Federal yearbook, 24 C.F.R., Part 3280 adopts FSM-2 big chamber test method (Large Chamber Test Method), thinks the present acceptable formaldehyde emission amount of flakeboard to be limited to 0.3ppm on it.
Adopt the chemical finishing process of formaldehyde and formaldehyde derivatives be mainly used in by or completely or partially cellulose fibre, the i.e. fabric that constitutes of cotton and viscose.These fibers chemically have reactive site (hydroxyl), and it makes fiber itself energy chemical modification and processing.The particularly importantly processing carried out with the difunctionality reagent that can make the cellulose chain chemical crosslinking that comprises fiber of viscose and cotton-containing fabrics of this respect.Such reaction can improve the elasticity of fiber, thereby strengthens crease-resistant folding and recovery, and makes treated fabric have the permanent set characteristic.
Modern permanent stabilised finish method is the original TBL(Tootal that is next to based on water-soluble methylolurea, Broadhurst, and Lee) method occurs.Processed fabric is through padding, and foaming arrangement, or opposite is with the solution continuous impregnating of the arrangement chemicals of crosslinking agent that contains formaldehyde-derived and curing catalysts.Finishing agent contains additional component usually, and for example heavy builder and feel modifier are as softener and curing agent.After the dipping, fabric is done typing and curing at high temperature through supportting.Can think that the fabric of in this way making has memory.For example, when the crosslinked flat and fabric done is done its fold to brush lightly when having an opportunity in tumble-dryers, will be returned to that state afterwards of washing again.
From nineteen sixty-five enthusiasm client accept from use ring-type urea stab clever ┗ river which rises in the northeastern part of Anhui Province ⑻ emigrant ┖ leg and Qi τ eyebrow now the ┦ head macerate be bald turn round and look at the extensive paper of badger capsule melt the poor of the low spoon poor of where take off strange broken fragrant high mountain stand tall and upright block the gown cover tool make a noise be greedy for money or food melt the strong extensive pen of please the glyoxal formaldehyde adduct, 1,3-dihydroxymethyl-4,5-dihydroxy ethylidene-urea (DMDHEU).The DMDHEU best at present crosslinking agent of representative that is a kind of N-methylol crosslinking agent aspect the fabric that is used for completely or partially constituting by cellulose fibre.Can think that DMDHEU and cellulosic cross-linking reaction mainly present by DMDHEU N-methylol side group and cellulosic hydroxyl reaction.
Before nineteen sixty-five, through the product of arrangement, discharge 3 concerning what wash, 000-5,000ppm formaldehyde are extremely usual, data AATCC test method(s) 112-1978[air-tight bottle method (Sealed Jar Method)].The air-tight bottle method is according to the formaldehyde of being measured release by the fabric in the air-tight bottle that leaves fills with water under 20 hours or 65 ℃ at the steam that was disengaged through 4 hours under 49 ℃.The formaldehyde that discharges is reduced to 2,000ppm and after to 1,000ppm on degree greatly by in the permanent set method, adopting DMDHEU reaching as main crosslinking agent.
Can also (temperature: 23 ° ± 1 °, relative humidity: the steam that 55% ± 2%) sheds from fabric be measured the formaldehyde amount that discharges under ambient air conditions with dynamic cell-type test method(s) (dynamics chamber test method).（Roberts，Eugene C.and Rossano，Anthony J，Tr，AATCC;Volume 16，No.3，P.29，1984）。
As everyone knows, by one or more polyalcohols, for example diethylene glycol (DEG) and sorbierite add to and make DMDHEU modification or alkylation can further reduce the formaldehyde amount of handling through permanent set that fabric discharged in the finishing agent.Can prevent in whole dose forming of free formaldehyde by polyalcohol end-blocking DMDHEU N-methylol side group, the formaldehyde that can reduce release is up to 50%.However, the formaldehyde amount that discharges in the fabric that personal improved or alkylating DMDHEU handles still is higher than the acceptable level of environment, consumer and labor group.In addition, in the chemical treatment of fabric, in general, DMDHEU is not unique source of free formaldehyde.Usually, the chemical requirement of dyeing and arrangement, but augmented the chemicals of formaldehyde person formaldehyde-derived, as color-fixing agent, feel modifier etc., the release that formaldehyde is described can be much higher than the formaldehyde that the single permanent set finishing agent be made up of only crosslinking agent and catalyst obtained and discharge.
As everyone knows, formaldehyde scavenger is combined in reduces the formaldehyde amount that in fabric that permanent set is handled and flakeboard, discharges in permanent set finishing agent and the urea-formaldehyde resins respectively.It is reported that formaldehyde scavenger works by two kinds of mechanism.In first kind of mechanism, but formaldehyde scavenger can work with the free formaldehyde in the finishing agent person urea-formaldehyde resins, be formed on additive compound stable under the solidification temperature.Another mechanism, formaldehyde scavenger can generate the formation that free N-methylol prevents free formaldehyde in the finishing agent by end-blocking DMDHEU N-methylol side group with by crosslinked hydrolysis.
A kind of effective formaldehyde scavenger of using in finishing agent must be water miscible and can be in the reactive site permeable fiber.In addition, a kind of effective formaldehyde scavenger must be nonvolatile under condition of cure, and compatible with the chemicals of finishing agent or urea-formaldehyde resins composition.It needn't be such alkalescence, to cause catalysqt deactivation and to promote the N-methylol to be hydrolyzed into N-H and formaldehyde.Simultaneously, it also needn't be such acidity, to cause crosslinked hydrolysis in the air-tight bottle test.A kind of formaldehyde scavenger must not impair the performance of fabric, and feel is for example shunk, the mechanical property of Miu Lun bursting strength (mullins burst) and color and luster or whiteness or flakeboard.Certainly, it uses aborning is economical, and just effectively, for example solids accounts for the 1-3% of immersion liquid weight (" owb ") under suitable content.
So far, prior art does not disclose a kind of formaldehyde scavenger as yet, this agent is applicable to that the permanent set of fabric handles or be applicable to the maintenance flakeboard, and it in that the formaldehyde that discharges is reduced to the low-level of present requirement fabric or flakeboard performance not to be had adverse effect be effective.At present, the formaldehyde scavenger of being used widely in the permanent set finishing agent is a polyalcohol, and as diethylene glycol (DEG) and sorbierite, what use in making flakeboard is nitrogenous compound such as urea, melamine, diazine, triazine and amines (United States Patent (USP) the 4th, 559, No. 097).Yet these compounds are being reduced to content of formaldehyde the low-level very ineffective of present requirement.
Specifically, well-known, can reduce the formaldehyde amount effectively such as the nitrogen-containing compound of urea, vinyl urea and carbohydrazide, but be cost only with the performance of rerum natura fabric.Amide residues in the treated fabric (CONH) can cause that the reservation of chlorine and the light resistance that can make fabric yellowing and some azo dyes reduce.These side effects hinder nitrogen-containing compound to be widely used as formaldehyde scavenger in permanent set arrangement process.In addition, the nitrogen-containing compound of urea-formaldehyde resins composition and resin Composition can reduce the intensity of flakeboard.These side effects have also hindered nitrogen-containing compound being used as formaldehyde scavenger widely in flakeboard.
At Textile Chemist and Colorist, Vol, 16, No is among 12 Dec.1985, people such as Thomasino had proposed 1 already, 3-dimethyl acetone-1,3-dicarboxylate, diethyl malonate and ethyl acetoacetate, these three kinds of activity methene compounds are because 1, the 3-dimethyl acetone-1,3-dicarboxylate is effective especially to reducing formaldehyde release under laboratory condition, can be used as formaldehyde scavenger.In experimental test, find that these compounds are effectively to the formaldehyde amount that reduces the fabric release of handling with the permanent set finishing agent that comprises DMDHEU, and the performance of fabric is not had injurious effects.Yet these compounds are water insoluble, so be not suitable for this permanent set finishing method.
Therefore, one object of the present invention is to provide a kind of novel composition that is used for formaldehyde scavenger, and it for example can reduce the formaldehyde amount that discharges and effectively without detriment to the performance of fabric and the formaldehyde amount that discharges and without detriment to the mechanical property of flakeboard from flakeboard from the fabric of handling through permanent set.
Another object of the present invention is to provide formaldehyde amount that a kind of reduction for example discharges and without detriment to the performance of fabric and the formaldehyde amount that discharges and without detriment to the method for the mechanical property of flakeboard from flakeboard from the fabric of handling through permanent set.
With reference to following narration and claim, can to these purposes of the present invention and other purpose with and advantage have more completely and understand.
According to the present invention, above-mentioned purpose is to be by containing molecular formula
The novel composition of water-soluble active methylenes compound realize that as formaldehyde scavenger in the formula R is-CH
3Or H[O(CH
2) m) n] O-; R ' is-CH
3Or H[O(CH
2) m '] n ' O-; M and/or m ' are 1-3, and n and/or n ' are 1-19; Y is-CH
2Or-CH
2-CO-CH
2-, but best m and/or m ' they are 2; N and/or n ' are 1-3; Y is-CH
2Composition of the present invention is applicable to permanent set technology and flakeboard manufacturing technique.
According to the present invention, said water-soluble active methylenes compound is by under anhydrous condition, with dialkyl malonate or Acetacetic acid alkyl ester and replacement or unsubstituted polyalcohol, and suitable transesterification catalyst [as the concentrated sulfuric acid (99%)] limit heating, stir on the limit, so that above-mentioned dialkyl malonate or Acetacetic acid alkyl ester generation transesterification.In above-described transesterification process, preferable dialkyl malonate and Acetacetic acid alkyl ester are respectively diethyl malonate and ethyl acetoacetate; And preferable replacement or unsubstituted polyalcohol are diethylene glycol (DEG)s.Yet reaction is not limited to Arrcostab as starting material.The present invention mainly uses this class ester to be because they can be buied from the market, and price is also inexpensive.Said mixture is heated and stirs.Also above-mentioned reactant mixture can be placed under the vacuum, so that remove the alkanol that produces in the esterification process.By to mixture sampling, and check its water-soluble completeness of determining reaction.In addition, the ester compounds class that comprises acetoacetic ester also can prepare by diketene (vinyl acetyl-β-lactone) and the suitable replacement or the addition reaction of unsubstituted polyalcohol.
The water-soluble active methylenes compound of gained can use by the mode that is similar to known formaldehyde scavenger.For example, for the ester compounds class that comprises two (2-hydroxyl ethoxy ethyl) malonates, water-soluble active methylenes diluted chemical compound to solid content can be about 90% solution, and for the ester compounds class that comprises (2-hydroxyl ethoxy ethyl) acetoacetic ester, then can be diluted to solid content and be about 50%.The solution that is produced is neutralized to pH value 6-7, so that residual sulfuric acid (resin catalyst) is converted into Ma
2SO
4, the problem of fabric yellowing and so on after avoiding whereby handling.Water-soluble active methylenes solution can be added in the permanent set finishing agent that contains the N-methylol cross-linking system (such as DMDHEU or modified DMDHEU).
The fabric of partly or entirely being made up of cellulose fibre can pad with the permanent set finishing agent, foam finishing (form finished) or flood.
If when padding fabric with the permanent set finishing agent, said finishing agent composed as follows:
Table 1
The preferable solid content of component solid content (%) owb (%)
DMDHEU 3-10 8
Catalyst 0.5-3 1.6
Diethylene glycol (DEG) 1-5
Two (2-hydroxyl-oxethyl second
Base) malonate solution 1.25-5 1.9
(2-hydroxyl ethoxy ethyl)
Acetoacetic ester 1-4
When with the permanent set finishing agent fabric being carried out foam finishing, foam solution is highly concentrated, and each component concentrations increases in proportion in the solution.For example, each component concentrations can be 2 times of corresponding each concentration of component in the leach mill solution, in such cases, system is added to water-soluble active methylenes solution in the finishing agent, and the amount of being added is for two (2-hydroxyl ethoxy ethyl) malonate compounds, and its scope is at the 2-10%(solid content, owb), and for for the compound (2-hydroxyl ethoxy ethyl) acetoacetic ester, its amount is the 2-8%(solid content, owb).
Fabric after finishing agent is handled carries out drying and baked and cured (cure) by common mode.
In another example, activity methene compound can directly be added to the urea formaldehyde resin that is used for making flakeboard, perhaps behind the dilute with water, is sprayed on its surface before the flakeboard compacting.The scavenger amount that applies or add depends on the character of adding resin in the flakeboard to, and condition of cure.Yet, any correct consumption under the particular case can be tested by the scavenger to different amounts, and the formaldehyde amount that assay plate discharged is determined.
Water-soluble active methylenes compound of the present invention is burst size of methanal in reducing such as the fabric after handling with the permanent set finishing agent, and the burst size aspect that comprises formaldehyde in the urea formaldehyde resin of flakeboard, have unique effect, said finishing agent can comprise the N-methylol crosslinking agent of DMDHEU or modified DMDHEU and so on.Free formaldehyde in this class finishing agent or the formaldehyde resin and the active methylene group group in the formaldehyde scavenger react under condition of cure, form stable additive compound, as methylene malonate, methylene acetoacetic ester or its polymer.Use the formaldehyde amount of handling according to the prepared permanent set finishing agent of the present invention that fabric discharged, and the formaldehyde amount that wherein discharges in the manufacture process of the flakeboard crossed with the present invention's compound treatment already of urea formaldehyde resin is reduced to all acceptable low-level.The amount of formaldehyde is reduced to below the 100ppm, has no adverse effect for the textile properties such as feel, contraction, Miao's synthetic fibre bursting strength and color and luster or whiteness in the fabric applications; And the amount of formaldehyde is reduced to 65% of original vol, the PARA FORMALDEHYDE PRILLS(91,95) catalyst adhere to and/or inactivation influential, but in flakeboard is used, its intensity be there is no adverse effect.
In addition, activity methene compound of the present invention can be used for preparing fiberboard and other fibres (as hardboard, sound panel), chipboard, glued board, directional fiber plate (oriented strand board) and flat board.
Following non-limiting example system is in order to illustrating composition of the present invention, method and product, and their advantage.
Embodiment 1
In following method, with diethylene glycol (DEG) ethyl acetoacetate is carried out transesterification, with the preparation molecular formula be
(2-hydroxyl ethoxy ethyl) acetoacetic ester, a kind of water-soluble active methylenes compound, R is-CH in the formula
3; Y is-CH
2-; R ' is H[O(CH
2) m '] n-O-; M is 2; And n ' is 2.
With ethyl acetoacetate and diethylene glycol (DEG) mixed in molar ratio, to prevent to form polymer with 1: 1.1.In said mixture, add then a certain amount of 99% concentrated sulfuric acid (0.2 milliliter of sulfuric acid: 1 mole of ethyl acetoacetate), with to having reacted catalytic action.Under agitation the temperature with mixture is heated to 95 ℃ to 100 ℃.Use the current air ejector, the ethanol that is produced to help removing in the esterification process.Determine by the water-soluble of sampling and measuring reactant mixture whether reaction finishes.
Finally obtain (2-hydroxyl ethoxy ethyl) acetoacetate ester products with high yield.The structure of this product is confirmed by FT IR and proton and carbon-13 magnetic resonance.
(2-hydroxyl ethoxy ethyl) acetoacetic ester is to have a moderately viscous transparency liquid, and is soluble in water and form solution, and it is diluted to solid content is 90% solution, and to be neutralized to pH be 6.75, the use that can pay.
Embodiment 2
With diethylene glycol (DEG) diethyl malonate is carried out transesterification, preparing two (2-hydroxyl ethoxy ethyl) malonates, a kind of water-soluble active methylenes compound, its molecular formula is
In the formula, R is H[O(CH
2) m] n-O-; Y is-CH
2-; R ' is H[O(CH
2) m '] n '-O-; M and/or m ' are 2, and n and/or n ' are 2.
With diethyl malonate and diethylene glycol (DEG) mixed in molar ratio with 1: 2.2, add then a certain amount of concentrated sulfuric acid (0.2 milliliter of sulfuric acid: 1 mole of diethyl malonate), with to having reacted catalytic action.Under agitation the temperature with mixture is heated to 95 ℃-100 ℃.The ethanol that uses the current air ejector to be produced to help removing in the esterification process.By to reaction mixture sampling, and measure it and water-solublely determine whether reaction finishes.
Finally obtain two (2-hydroxyl ethoxy ethyl) malonate products with high yield.The structure of this product is by FTIR, and proton and carbon-13 magnetic resonance are confirmed.
Two (2-hydroxyl ethoxy ethyl) malonate is a kind of moderately viscous transparency liquid that has, and is soluble in water and form solution, and it is diluted to solid content is 50% liquid, and to be neutralized to pH be 6.75, the use that can pay.
Embodiment 3
White double rib braided fabric with bleaching carries out a series of tests, to determine that (2-hydroxyl ethoxy ethyl) acetoacetic ester is for the effect that reduces already burst size of methanal aspect in the fabric of handling with the permanent set finishing agent that contains DMDHEU.
Permanent set finishing agent composed as follows:
Table 2
Component solid content (%) owb
DMDHEU 8.0
Catalyst 1.4
Feel builder (Hand Builder) 5.5
Softener 1.4
(2-hydroxyl ethoxy ethyl) acetyl 1.4
Acetate solution (referring to table 3)
Place Fab Con tubular knitting resin impregnation section (Fab Contubular Knit resinating range) to handle fabric sample.In each batch product 50%(1000/batch) pad and all the other 50% fabrics in contrast with the permanent set finishing agent that contains (2-hydroxyl ethoxy ethyl) acetoacetate.Bleaching polyester cotton double rib braided fabric sample is dry under 275 temperature, and 310 (loop) baked and cured that circulate down.Regulation by AATCC test method(s) 112-1984 is tested the sample after solidifying.Test result is summarized in table 3.
Table 3
Product be pair (2-hydroxyl-oxethyl formaldehyde release formaldehyde burst size
The test ethyl) acetoacetic ester amount (ppm) reduction value (%)
Solution solid content (%) owb
1. white double rib 0(contrast) 393 0
Braided fabric 1.4 252 36
Condition: use resin impregnation, and dry down at 275 °F; The circulation baked and cured is carried out under 310 °F.
To the analysis showed that of above-mentioned data, in test 1, with the fabric after the permanent set finishing agent processing that contains (2-hydroxyl ethoxy ethyl) acetoacetic ester, the release rate of its formaldehyde significantly reduces.Because two (2-hydroxyl ethoxy ethyl) acetoacetic esters are added in the permanent set finishing agent, and the release rate of formaldehyde is reduced to acceptable low-level.
Embodiment 4
Carry out a series of tests with bleaching PC double rib braided fabric, to determine that two (2-hydroxyl ethoxy ethyl) malonates are for the effect of handling formaldehyde release rate in the fabric of back in the presence of diethylene glycol (DEG) with DMDHEU.
Permanent set finishing agent composed as follows:
Table 4
Component solid content (%) owb
DMDHEU(resin phase) 8
Catalyst 1.6
Diethylene glycol (DEG) 2.0
Two (2-hydroxyl ethoxy ethyl) malonate 1.25-5.00
With the permanent set finishing agent that contains two (2-hydroxyl ethoxy ethyl) malonate solution (solid content is 1.25-5.00%owb) pad fabric sample to 80%WPU(adhesion amount when moistening), sample after will padding places 250 dryings down together, then be cured in 295-310 curing oven respectively, the time is 30 seconds to 120 seconds again.
Solidifying the back sample tests by the regulation of AATCC test method(s) 112-1984.This test method(s) is similar to AATCC test method(s) 112-1987, measures the content of formaldehyde in the sample bottle of insulation back but replace receiving uncommon (Nash) reagent with chromotrope acid colorimetry.Result of the test is summarized in table 5.
Table 5
The laboratory is two, and (the 2-'-hydroxyethoxy solidifies formaldehyde formaldehyde and discharges
Test basic ethyl) reduction of malonic acid temperature-time burst size amount
Ester solution, solid content (°F) (second) (ppm) be worth (%)
(%) owb 1 0(tester) 310 120
231 0
1.25 310 120 152 34
2.50 310 120 102 56
2 0(testers) 310 30 628 0
2.5 310 30 437 30.4
The 0(tester) 310 60 634 0
2.5 310 60 320 49.8
The 0(tester) 310 120 245 0
The 0(tester) 310 120 176 39.2
3 0(testers) 295 80 376 0
1.25 295 80 273 27.4
2.50 295 80 185 50.8
3.75 295 80 176 53.2
5.00 295 80 154 59.0
To the analysis showed that of above-mentioned data, in all tests, with the fabric after the permanent set finishing agent processing that contains two (2-hydroxyl ethoxy ethyl) malonates, its burst size of methanal significantly reduces.
Shown in laboratory test number 1,, can make by this finishing agent and handle the burst size of methanal minimizing of back fabric more than 50% by two (2-hydroxyl ethoxy ethyl) malonates are added in the permanent set finishing agent.
In laboratory test numbering 2, can observe hardening time and be on the not completely crued fabric sample of 30 seconds and 60 seconds and obtain effective formaldehyde removing effect.Because the curing percentage of fabric is not quite similar in process of production, and two (2-hydroxyl ethoxy ethyl) malonate can keep its effect in sizable curing percentage scope, this character is vital.
Shown in laboratory test number 3, a spot of two (2-hydroxyl ethoxy ethyl) malonates promptly demonstrate its effect.The optimum amount of two (2-hydroxyl ethoxy ethyl) malonate solution is the 2.5%(solid in finishing agent) owb.
Will two (2-hydroxyl ethoxy ethyl) malonates mix the performance that does not influence in the finishing agent after the processing.With the fabric sample after the permanent set finishing agent processing that contains two (2-hydroxyl ethoxy ethyl) malonates, its feel is all identical with control fabric with whiteness.
In the presence of diethylene glycol (DEG), discharging significantly with two (2-hydroxyl ethoxy ethyl) formaldehyde that malonate obtained, reduction shows, the mechanism that reduces burst size of methanal is that the free formaldehyde in two (2-hydroxyl ethoxy ethyl) malonates and the finishing agent reacts, and forms stable additive compound.In the presence of replacement or unsubstituted polyalcohol (as diethylene glycol (DEG)), with pair (2-hydroxyl ethoxy ethyl) malonates that DMDHEU N-methylol is pendant end-capped, estimate meeting reduction effect, its reason is the reaction of alcohol and DMDHEU contention and formaldehyde scavenger.
In the presence of diethylene glycol (DEG), remarkable reduction with two (2-hydroxyl ethoxy ethyl) burst size of methanal that malonate obtained also shows, two (2-hydroxyl ethoxy ethyl) malonate is active methylene group position in the formaldehyde scavenger as the effect of formaldehyde scavenger, rather than unreacted diethylene glycol (DEG) in the reactant mixture, the ethoxy ethyl ester group in perhaps two (2-hydroxyl ethoxy ethyl) malonates.
Embodiment 5
Carry out a series of tests with pink double rib braided fabric, to determine that (2-hydroxyl ethoxy ethyl) acetoacetic ester is for reducing the effect of handling burst size of methanal in the fabric of back with the permanent set finishing agent that contains modified DMDHEU.
Above-mentioned permanent set finishing agent composed as follows:
Table 6
Component solid content (%) owb
Modified DMDHEU 9.88
(pre-catalysis)
Feel builder 5.5
Softener 1.4
(2-hydroxyl ethoxy ethyl) 1.4
Acetoacetate ester solution (referring to table 7)
Place Fab Con circular machine knitting resin impregnation section to handle fabric sample.The permanent set finishing agent that 50% usefulness contains (2-hydroxyl ethoxy ethyl) acetoacetic ester in each batch (1,000/batch) pads, and all the other 50% are used as control fabric.Pink double rib braided fabric sample carries out drying under 275 temperature, then 310 circulation curing down.Solidifying the back sample tests by the regulation among the AATCC test method(s) 112-1984.Result of the test is summarized in table 7.
Table 7
Product (2-hydroxyl-oxethyl formaldehyde release formaldehyde burst size
Ethyl) the reduction value of acetoacetic ester amount (ppm)
Test solution solid content (%) (%)
owb
1. pink 0(tester) 98 0
Look double rib 1.4 43 56
Braided fabric
Condition: carry out resin impregnation and drying under 275 °F, circulation is solidificated under 320 °F to be carried out.
To the analysis showed that of above-mentioned data, in test 1, with the fabric after the permanent set finishing agent processing that contains (2-hydroxyl ethoxy ethyl) acetoacetic ester, its burst size of methanal significantly reduces.Because (2-hydroxyl ethoxy ethyl) acetoacetic ester is added in the permanent set finishing agent, the burst size of formaldehyde is reduced to acceptable low-level.
Embodiment 6
Carry out a series of tests with bleaching PC and red as fire look double rib braided fabric, to determine that two (2-hydroxyl ethoxy ethyl) malonates are for the effect that reduces with burst size of methanal aspect in the fabric after the pre-catalysis DMDHEU of the modification resin treatment.
The composition of above-mentioned permanent set finishing agent is summarized in table 8.
Table 8
Component solid content (%) owb
Modified DMDHEU 9.88
(pre-catalysis)
Feel builder 5.5
Softener 1.4
Two (2-hydroxyl-oxethyl 2.2-2.5
Ethyl) malonate
Solution
Place Fab Con circular machine knitting resin impregnation section to handle fabric sample.The permanent set finishing agent that 10% usefulness contains two (2-hydroxyl ethoxy ethyl) malonates in each batch (1000/batch) pads, and all the other 90% are used as control fabric.Red as fire yarn-dyed fabric sample is dry under 275 °F, carries out under 320 °F and circulate to be solidificated in; The white fabrics sample of bleaching is dry under 275 ℃, and circulation is solidificated under 310 °F to be carried out.Solidifying sample tests by the regulation among the AA AATCC test method(s) 112-1978.Result of the test is summarized in table 9.
Table 9
Product (2-'-hydroxyethoxy formaldehyde release formaldehyde burst size
The base ethyl) the reduction value of malonic acid amount (ppm)
Test ester solution solid content (%)
（%）owb
1. red as fire look 0(tester) 190 0
Double rib compiles 2.2 80 58
Woven fabric
(condition: carry out resin impregnation and drying under 275 °F, circulation is solidificated under 320 °F to be carried out)
2. white two 0(testers) 248 0
Ribbed knitting 2.5 95 62
Fabric
(condition: set under 275 °F dip in polished slightly meal shield carry out under 10 of the )
To the analysis showed that of above-mentioned data, in each test, with the fabric after the permanent set finishing agent processing that contains two (2-hydroxyl ethoxy ethyl) malonates, its burst size of methanal all significantly reduces.Because two (2-hydroxyl ethoxy ethyl) malonates are added in the permanent set finishing agent, the formaldehyde release rate in above-mentioned arbitrary test reduces more than 50%.The burst size of methanal reduction of handling the back fabric is acceptable at least low-level, below 100ppm.
With the fabric after the permanent set finishing agent processing that contains two (2-hydroxyl ethoxy ethyl) malonates, its performance and control fabric are basic identical.Result of the test is summarized in table 10.
Table 10
Pilot production is shunk Miu Lun bursting strength tone feel
1, red as fire look double rib 1 * 5 76 no change no changes
Braided fabric
Control fabric 1.5 * 5 81
2, white double rib is compiled 3 * 4 89 no change no changes
Woven fabric
Control fabric 2 * 4 85
Can find out obviously that by the result shown in the table 10 being incorporated into two (2-hydroxyl ethoxy ethyl) malonates in finishing agent does not have adverse influence for the performance of treated fabric.
At modification N, N '-dihydroxymethyl dihydroxy ethylidene-urea (DMDHEU) exists the effect of following pair of (2-hydroxyl ethoxy ethyl) malonate to show, the mechanism that the formaldehyde amount that discharges reduces is the absorption of free formaldehyde in the described finishing agent under solidification temperature, active methylene group position on two (2-hydroxyl ethoxy ethyl) malonate and free formaldehyde react to form a kind of stable additive compound, for example methylene malonate or its polymerized form.
4,7 examples 7
Employing is through the white double rib 50/50(PC of bleaching) braided fabric, carried out the effect of a series of tests, permanent set finishing agent composed as follows with the quantitative aspects of determining the formaldehyde that two (2-hydroxyl ethoxy ethyl) malonates and (2-hydroxyl ethoxy ethyl) acetoacetate discharge in reducing by the fabric of handling with melamine resin:
Table 11
Component percent solids (is benchmark owb with immersion liquid weight)
Melamine 9
Catalyst 2.4
Two (2-hydroxyl ethoxy ethyl) 1.9(sees Table XII)
Malonate
(2-hydroxyl ethoxy ethyl) second 1.4-2.7(sees Table XII)
The acyl acetate
Under 80%wpu, with the permanent set finishing agent that comprises two (2-hydroxyl ethoxy ethyl) malonates and (2-hydroxyl ethoxy ethyl) acetoacetic acid ester solution fabric sample is padded, 265 °F down will be through padding sample dry together, and under 320 °F, respectively it is baked and solidified 120 seconds.According to American Association of Textile Chemists and Colorists test method 112-1984, these are sent to test through the sample that bakes curing.Table 12 has been summed up the result:
Table 12
The laboratory be pair (release that 2-hydroxyl-oxethyl (2-'-hydroxyethoxy ethyl) discharges
The test ethyl) malonate acetoacetate formaldehyde formaldehyde
% solid owb % solid owb ppm reduces %
1 0(contrast) 0(contrast) 3,420 0
1.9 0 3488 0
0 1.9 2577 25
2-0(contrast) 3,323 0
- 1.4 2672 20
- 2.8 2599 22
4.8 example 8
Using the white 50/50(PC of bleaching) the double rib braided fabric carries out the effect of a series of tests with the quantitative aspects of determining the formaldehyde that (2-hydroxyl ethoxy ethyl) acetoacetate discharges in reducing by the fabric of handling with DMDHEU type resin-based finishes, and definite efficient for two (2-hydroxyl ethoxy ethyl) malonate.
The durable shaping finishing agent is following composition:
Table 13
Component percent solids (owb)
The DMDHEU(resin binder) 8
Catalyst 1.6
Two (2-hydroxyl ethoxy ethyl) malonate 1.9(sees Table the X IV)
(2-hydroxyl ethoxy ethyl) acetoacetate 1-4(sees Table the X IV)
Under 80%wpu, with comprising the permanent set finishing agent that two (2-hydroxyl ethoxy ethyl) malonate solution that concentration is 1.9% solid (owb) or concentration is (2-hydroxyl ethoxy ethyl) acetoacetate of 1-4% solid (owb) fabric sample is padded, 265 °F down will be through padding sample dry together, and respectively it is baked in the stove 320 bake and to solidify 120 seconds.According to American Association of Textile Chemists and Colorists test method 112-1984, these are baked sample send to test, this method is similar to American Association of Textile Chemists and Colorists test method 112-1978, different is, the chromotropic acid colorimetric method is used as and is used for determining the substitute of insulation back at Na Xi (Nash) reagent of the content of sample bottle formaldehyde, and result of the test is summarised in the table 14.
Table 14
The laboratory be pair (release that 2-hydroxyl-oxethyl (2-hydroxyl ethoxy ethyl) discharges
The test ethyl) malonate acetoacetate formaldehyde formaldehyde
% solid owb % solid owb ppm reduces %
1 0(contrast) 0(contrast) 593 0
1.9 0 489 18
0 1.9 359 39
2 0(contrast) 0(contrast) 635 0
1.9 0 460 28
0 1.9 298 53
3 0(contrast) 0(contrast) 776 0
1.9 0 472 39
0 1.9 362 53
4 0(contrast) 616 0
- 1 424 31
- 2 336 45
- 4 211 66
(condition: predrying under 265 °F, under 320 °F, baked 220 seconds)
5*-0(contrast) 515 0
- 1 313 39
- 2 213 59
- 3 125 76
6**-0(contrast) 702 0
- 1.4 413 41
- 2.8 290 59
* the test by one independently the laboratory on 50/50 PC thin plate, carry out.Sample baked under 350 °F 1.5 minutes.
The method preparation that discloses in the U. S. application series number 902,750 of * by my 1986.9.2 application.
To the analysis showed that of these data, in each test, by the minimizing that has reached the formaldehyde that discharges in the fabric of handling with the permanent set finishing agent that comprises two (2-hydroxyl ethoxy ethyl) malonates and (2-hydroxyl ethoxy ethyl) acetoacetate.
In laboratory test 1-3, under 1.9% solid (owb) concentration, two kinds of scavengers are compared, result's (2-hydroxyl ethoxy ethyl) acetoacetate on this level is more effective than two (2-hydroxyl ethoxy ethyl) malonates.
Laboratory test 1-5 shows that for the DMDHEU resin, the optimum value of (2-hydroxyl ethoxy ethyl) acetoacetate scavenger is about 2%(owb).
4.9 example 9
Use the white 50/50 PC double rib fiber of bleaching, carried out the effect of a series of tests aspect the formaldehyde amount of determining two (2-hydroxyl ethoxy ethyl) malonates and (2-hydroxyl ethoxy ethyl) acetoacetate and in the fabric that reduces by pre-catalysis DMDHEU resin treatment, discharging, and determined efficient with respect to separately two kinds of scavengers with modification.The permanent set finishing agent is composed as follows.
Table 15
Component percent solids (owb)
Modified DMDHEU (pre-catalysis) 8
Two (2-hydroxyl ethoxy ethyl) malonate 1.9(sees Table 16)
(2-hydroxyl ethoxy ethyl) acetoacetate 1.4-2.8(sees Table 16)
Under 80%wpu, with comprising the permanent set finishing agent that two (2-hydroxyl ethoxy ethyl) malonates that concentration is 1.9% solid (owb) or concentration is (2-hydroxyl ethoxy ethyl) acetoacetate of 1.4-2.8% solid (owb) sample is padded, under 265 °F,, and solidified 120 seconds baking under 320 °F in the stove it is baked samples dried through padding.According to American Association of Textile Chemists and Colorists test method 112-1984, these are sent to test through the sample that bakes curing, result of the test is summarized in the table 16.
Table 16
The laboratory be pair (release that 2-hydroxyl-oxethyl (2-hydroxyl ethoxy ethyl) discharges
The test ethyl) malonate acetoacetate formaldehyde formaldehyde
% solid owb % solid owb ppm reduces %
1 0(contrast) 0(contrast) 197 0
1.9 0 153 22
0 1.9 70 64
2 0(contrast) 0(contrast) 90 0
1.9 0 65 28
0 1.9 28 69
3 0(contrast) 0(contrast) 101 0
1.9 0 74 27
0 1.9 20 80
4-0(contrast) 105 0
- 1.4 5 95
- 2.8 0 100
(condition: predrying under 265 °F, under 320 °F, baked 120 seconds)
To the analysis showed that of these data, in each test, when concentration level was 1.9% solid and the pre-catalytic resin of use modified DMDHEU, (2-hydroxyl ethoxy ethyl) acetoacetate scavenger was more much effective than two (2-hydroxyl ethoxy ethyl) malonates aspect the formaldehyde that reduces release.
4.10 example 10
Use eight kinds of different fabric groups, wherein four kinds is control group, carries out a series of tests to determine the effect of the formaldehyde quantitative aspects that two (2-hydroxyl ethoxy ethyl) malonates (FSD-90) discharge in reducing by the fabric of handling with the permanent set finishing agent that comprises DMDHEU.
The permanent set finishing agent is made up of following:
Table 17
Component percent solids (owb)
DMDHEU 9.88
Contrast component 5.5
Softening agent 1.4
Two (2-hydroxyl ethoxy ethyl) malonate solution 2
Fabric sample is carried out in Fei Baikeen (Fab Con) tubular knitting resin impregnation scope, eight different fabric groups (1000/ group) are padded with the permanent set finishing agent that comprises two (2-hydroxyl ethoxy ethyl) malonates, and wherein four fabric groups are control groups.Described eight different fabric groups are baked curing 275 following dryings and 310 following circulations, to send to through the sample that bakes curing and carry out according to American Association of Textile Chemists and Colorists test method 112-1984 and the dynamically described test of chamber test method, with the described fabric group test degassing 96 hours, result of the test was summarized among table 18 and Fig. 1 and 2.
Table 18
The formaldehyde ppm that the formaldehyde that pilot production discharges discharges
Ppm (dynamically chamber test method)
(AATCC-112) bleed the time (hour)
1 24 48 72 96
A. contrast
1. white 237 .78 .30 .20 .17 .11
2. pink 105 .25 .11 .08 .06 .05
3. red 136 .44 .18 .13 .09 .08
4. blue 230 .40 .21 .15 .13 .09
B. test
5. white 125 .44 .22 .16 .13 .10
6. white 123 .54 .18 .12 .08 .07
7. yellow 53 .15 .07 .05 .04 .03
8. red 85 .20 .11 .08 .07 .06
When color (for example white fabrics for dyed) grouping and the mean time of data about the formaldehyde amount that discharges shown in table 18 with fabric, in sampling in 1 hour, discharge 0.57ppm formaldehyde by the control fabric of dynamic chamber test method measuring, as one group in finishing agent, contain 2%(owb) the test fabric of two (2-hydroxyl ethoxy ethyl) malonates of level has then provided 0.33ppm or the formaldehyde emission reduces 42%.Usually the levels of formaldehyde that can expect white fabrics is higher, because the white fabrics of bleaching bakes under the temperature more much lower than dyed fabric, thereby has prevented thermal discoloration.The formaldehyde data odorous of white fabrics when grouping and mean time, are expressed the formaldehyde amount of disengaging and have been reduced 46%.
Test for data clearly illustrates that, two (2-hydroxyl ethoxy ethyl) malonate is when being used in the normal resin mixture (DMDHEU type), really reduced the levels of formaldehyde odorous in the fabric, this just is scaled the minimizing of formaldehyde emission from described fabric.
4.11 example 11
Make 24,000 pounds of flakeboards with plant layout according to following manner:
Formaldehyde scavenger in 6 pounds of (is that benchmark is about 0.3% with the solution weight) examples 2 is joined in the mixture of 250 gallons of urea formaldehyde resins (65% solid) and wax (about 2.3%, be benchmark), and it is sprayed on the particulate sawdust particle with the solid.
By translator sawdust is distributed on the charging tray then, make two-layer fine grained layer be positioned at the surface of plate, and coarse granule is positioned at core, subsequently under 375 °F with its hot pressing 4 minutes.
Test baking the sample that solidified according to 24 hours drier methods of standard, described drier method is a kind of quality control testing, big chamber test method (the Large Chamber Test Method) FTM-2 of its each machine run and reference, 1987.The formaldehyde (0.1ppm) that discharges has reduced 35%.
4.12 example 12
Make 24,000 pounds of flour plates with plant layout according to following manner:
Formaldehyde scavenger in 6 pounds of (about 0.3%, be benchmark with the solution weight) examples 1 or the example 2 is joined the mixture of 250 gallons of urea formaldehyde resins (65% solid) and wax (about 2%, be benchmark with the solid), and it is sprayed on the particulate sawdust particle.
By translator sawdust is distributed on the powder dish then, make two-layer fine grained layer be positioned at the surface of plate, and coarse granule is positioned at core, subsequently under 375 °F with its hot pressing 4 minutes.
Adopt two hours drier methods to finish the measurement that two (2-hydroxyl ethoxy ethyl) malonates of two kinds of scavengers and (2-hydroxyl ethoxy ethyl) acetoacetate is baked the formaldehyde reduction of the release under hardening time and the two kinds of resinous type three kinds of usage levels, two kinds, low be fuming and mol ratio that the high resin type of being fuming has respectively is formaldehyde: urea=1.1: 1 and 1.5: 1.
Result of the test is summarised in table 19, in 20 and 21:
Table 19
Adopt two hours drier methods, to high mole and low mol ratio resin, the result of the measurement of the formaldehyde that two kinds of formaldehyde scavengers under three kinds of concentration that three layers of flakeboard suppressing down with two kinds of press times are compared disengage.
Scavenger
Plate numbering resin mol ratio differentiates that concentration extrudes time formaldehyde and determines
% (minute) amount mean value
（μg/ml）
73,75,77 1.1: 1 contrast 0 3.5 0.762
79,81,83 1.1: 1 contrast 0 4.5 0.873
1，13，25 1.1∶1 FSD＊ 0.5 3.5 0.531
37，49，61 1.1∶1 FSD 0.5 4.5 0.547
5，17，29 1.1∶1 FSD 1.0 3.5 0.602
41，53，65 1.1∶1 FSD 1.0 4.5 0.513
9，21，33 1.1∶1 FSD 1.5 3.5 0.674
45，57，69 1.1∶1 FSD 1.5 4.5 0.602
3，15，27 1.1∶1 FSD-2+ 0.5 3.5 0.426
39，51，63 1.1∶1 FSD-2 0.5 4.5 0.489
7，19，31 1.1∶1 FSD-2 1.0 3.5 0.582
43，55，67 1.1∶1 FSD-2 1.0 4.5 0.522
11，23，35 1.1∶1 FSD-2 1.5 3.5 0.604
47，59，71 1.1∶1 FSD-2 1.5 4.5 0.510
74,76,78 1.5: 1 contrast 0 3.5 4.246
80,82,84 1.5: 1 contrast 0 4.5 4.118
2，14，26 1.5∶1 FSD 0.5 3.5 3.621
The continuous table of going up
Scavenger
Plate numbering resin mol ratio differentiates that concentration extrudes time formaldehyde and determines
% (minute) amount mean value
（μg/ml）
38，50，62 1.5∶1 FSD 0.5 4.5 4.486
6，18，30 1.5∶1 FSD 1.0 3.5 3.828
42，54，66 1.5∶1 FSD 1.0 4.5 4.102
10，22，34 1.5∶1 FSD 1.5 3.5 3.444
46，58，70 1.5∶1 FSD 1.5 4.5 3.719
4，16，28 1.5∶1 FSD-2 0.5 3.5 4.541
40，52，64 1.5∶1 FSD-2 0.5 4.5 4.352
8，20，32 1.5∶1 FSD-2 1.0 3.5 3.682
44，56，68 1.5∶1 FSD-2 1.0 4.5 3.438
12，24，36 1.5∶1 FSD-2 1.5 3.5 3.603
48，60，72 1.5∶1 FSD-2 1.5 4.5 4.292
* two (2-hydroxyl ethoxy ethyl) malonates of FSD=
+ FSD-2=(2-hydroxyl ethoxy ethyl) acetoacetate
Table 20
Adopt two hours drier methods, to high mole and low mol ratio resin, with two kinds of press times down the result's of the measurement of the formaldehyde that disengages of two kinds of formaldehyde scavengers under three layers of flakeboard of compacting, three kinds of concentration of comparing Duncan classify.
Differentiate mean value Duncan (Duncan)
Grouping
1.1: 1 Resin A
Scavenger
There is not 0.817 A
FSD 0.578 B
FSD-2 0.522 B
Scavenger concentration
0% 0.817 A
0.5% 0.498 B
1.0% 0.555 B
1.5% 0.597 B
Press time
3.5 minute 0.597 A
4.5 minute 0.579 A
1.5: 1 resin B
Scavenger
There are not 4.182 A
FSD 3.867 A
FSD-2 3.985 A
Scavenger concentration
0% 4.182 A
0.5% 4.250 A
1.0% 3.763 A
1.5% 3.764 A
Press time
3.5 minute 3.852 A
4.5 minute 4.073 A
The mean value of * same letter does not have a great difference
In the table 20, Duncan test (Duncan, David B., multiregion and many F test, biometrics, March, Xin Haiwen (New Haven), CT, page or leaf 1-42(1955); Steel, Robert G.D. and James H. holder Buddhist nun, Statistics and process, second edition, Mike's lattice are old-Hei Er (Mc Graw-Hill) books limited company, and New York, New York, page or leaf 187-188(1980)) be used to determine adopting high molar ratio and low mol ratio resin, and two kinds of press times down three layers of flakeboard of compacting contrast between the formaldehyde measurement of two kinds of formaldehyde scavengers of three kinds of concentration of comparison whether have statistical difference.
The Duncan test compares various processing mean values and other each processing mean value; and determine that those difference are conspicuousnesses; in order to prevent to find wrong conspicuousness difference; the notion that has replaced significance with the notion of special protection level; these levels are based on the processing of the free degree; the probability of finding the conspicuousness difference on the statistical significance when corresponding true average equates between any two mean values is the significance of setting forth in the table that is less than or equal to as this test, " the conspicuousness department that is used for the new multiregion test of 5% and 1% level (Studentized) scope of all pausing that it is by name.
During data, distinguish the mean value that compared with letter at report, those have, and same letter recognizes, for example A does not have the difference on the statistical significance on 5% level; And those are distinguished by different letters, and for example B then has the difference on the statistical significance on 5% level.
Result of the test in the table XX shows, is used for the formaldehyde of resin: the mol ratio of urea, the formaldehyde removing dosage that uses in the 0-1.5% scope are being the parameters of conspicuousness on the statistical significance aspect the formaldehyde amount of decision release.Also show on the other hand and adopt the 3.5-4.5 minute press time in the scope that the formaldehyde amount that discharges is not had influence on the statistics.
Table 21 has been summed up the reduction percentage on maximum usage level.
Table 21
Reduce percentage
The low resin height of the being fuming resin of being fuming
Reduction % reduction %
Bake time FSD FSD-2 and bake time FSD FSD-2
3.5 minutes 30.3 44.1 3.5 minutes 18.9 15.1
4.5 minute 37.3 44.9 4.5 minutes 12.4 nothings
Contrast .762 .873 contrasts 4.246 4.118
（μg/ml） （μg/ml）
The height resin of being fuming is the resinous type that a class not be used in woodwork industry usually, and its reason is because the high-load level of formaldehyde odorous (4.1-4.2 μ g/ml).Data show the FSD-2 of minimum minimizing FSD and to(for) these resins, and the data shown in table X XI show, use two hours drier methods, at 0.5%(owb) to hang down the resin of being fuming under the level and provided best result, its formaldehyde reduction is greater than 44%.
Above-described example is the use aspect the formaldehyde amount that discharges in reducing by fabric and flakeboard under not damaging fabric or flakeboard performance prerequisite for the composition that the water-soluble formaldehyde scavenger of (but not placing restrictions on) the present invention is described, their preparation and its, but will be appreciated that, do not breaking away under the scope of the invention prerequisite, can as following claim limits, do some variations at this.
Claims (77)
1, the composition of the formaldehyde scavenger formed of a kind of water-soluble active methylenes compound that is used for representing by following general expression,
It is characterized in that in the said general expression:
R is-CH
3Perhaps H[O (CH
2) m] n-O-,
R ' is-CH
3Perhaps H[O (CH
2) m '] n '-O-,
M and (or) m ' be 1-3, n with (or) n ' is 1-19,
Y is-CH
2-or-CH
2-CO-CH
2-.
2, composition according to claim 1, it is characterized in that n and (or) n ' is 1-3.
3, composition according to claim 1, it is characterized in that n and (or) n ' is 2.
4, composition according to claim 1 is characterized in that R is H[O(CH
2) m] n-O-,
R ' is H[O(CH
2) m '] n '-O-,
M and (or) m ' is 2, n and (or) n ' is 2,
Y is-CH
2-and the water-soluble active methylenes compound be pair (2-hydroxyl ethoxy ethyl) malonates.
5, composition according to claim 1 is characterized in that R is-CH
3,
R ' is H[O(CH
2) m '] n '-O-, m is 2, n ' is 2,
Y is-CH
2-and the water-soluble active methylenes compound be pair (2-hydroxyl ethoxy ethyl) ethyl acetoacetates.
6, a kind of method for preparing the water-soluble active methylenes compound, it is characterized in that said method comprise with replace or unsubstituted polyalcohol make the dialkyl malonate transesterification.
7, composition according to claim 6 is characterized in that said method may further comprise the steps:
(a) under anhydrous condition, make catalyst mix dialkyl malonate, replacement or unsubstituted polyalcohol and transesterification together;
(b) heat and stir this mixture, to obtain the methylene compound of water-soluble active.
8, method according to claim 7 is characterized in that with 1 mole of dialkyl malonate: ratio 2.2 moles of replacements or unsubstituted polyalcohol makes dialkyl malonate and replacement or unsubstituted polyalcohol mixing.
9, method according to claim 7 is characterized in that with 0.2 milliliter of catalyst: the ratio of 1 mole of dialkyl malonate adds transesterification catalyst.
10, method according to claim 7 is characterized in that the temperature range with said mixture heated to 95 ℃～100 ℃.
11, method according to claim 7 is characterized in that dialkyl malonate is the malonic acid diethyl ester.
12, method according to claim 7 is characterized in that polyalcohol that replace or unsubstituted is a diethylene glycol (DEG).
13, method according to claim 7 is characterized in that transesterification catalyst is dense H
2SO
4(99%).
14, method according to claim 7 is characterized in that with an aspirator said mixture being placed vacuum.
15, a kind of method for preparing the water-soluble active methylenes compound, it is characterized in that said method comprise with replace or unsubstituted polyalcohol make the Acetacetic acid alkyl ester transesterification.
16, preparation water-soluble active methylenes compound method according to claim 15 is characterized in that said method may further comprise the steps:
(a) under anhydrous condition, make Acetacetic acid alkyl ester, replacement or unsubstituted polyalcohol and transesterification catalyst mix;
(b) heat and stir said mixture, to obtain the water-soluble active methylenes compound.
17, method according to claim 16 is characterized in that with 1 mole of Acetacetic acid alkyl ester: ratio 2.2 moles of replacements or unsubstituted polyalcohol makes Acetacetic acid alkyl ester and replacement or unsubstituted polyalcohol mixing.
18, method according to claim 16 is characterized in that with 0.2 milliliter of catalyst: the ratio of 1 mole of Acetacetic acid alkyl ester adds transesterification catalyst.
19, method according to claim 16 is characterized in that the temperature range with said mixture heated to 95 ℃～100 ℃.
20, method according to claim 16 is characterized in that Acetacetic acid alkyl ester is an ethyl acetoacetate.
21, method according to claim 16 is characterized in that polyalcohol that replace or unsubstituted is a diethylene glycol (DEG).
22, method according to claim 16 is characterized in that transesterification catalyst is dense H
2SO
4(99%).
23, method according to claim 16 is characterized in that adopting aspirator that said mixture is placed under the vacuum.
24, a kind of method that reduces the formaldehyde amount that discharges in the fabric that completely or partially cellulose fibre constitutes is characterized in that the permanent set finishing agent processing that comprises the water-soluble active methylenes compound of representing with general expression of said fabric,
It is characterized in that R is-CH
3Perhaps H[O(CH
2) m] n-O-,
R ' is-CH
3, H[O(CH
2) m '] n '-O-,
M and (or) m ' be 1-3, n with (or) n ' is 1-19,
Y is-CH
2-or-CH
2-CO-CH
2-.
25, method according to claim 24, it is characterized in that n and (or) n ' is 1-3.
26, method according to claim 24, it is characterized in that n and (or) n ' is 2.
27, method according to claim 24 is characterized in that R is H[O(CH) m] n-O-,
R ' is H[O(CH
2) m '] n '-O-, m and (or) m ' is 2,
N and (or) n ' is 2,
Y is-CH
2-and the water-soluble active methylenes compound be two (2-hydroxyl ethoxy ethyl) malonates.
28, method according to claim 24 is characterized in that R is-CH
3,
R ' is H[O(CH
2) m '] n '-O-,
M ' is 2, and n ' is 2, and y is-CH
2-and the water-soluble active methylenes compound be (2-hydroxyl ethoxy ethyl) acetoacetic ester.
29, method according to claim 24 is characterized in that preparing said water-soluble active methylenes compound the 1.25-10%(weight that is said permanent set finishing agent).
30, method according to claim 29, the preparation that it is characterized in that said water-soluble active methylenes compound then are the 1.25-5%(weight of said permanent set finishing agent when the permanent set finishing agent is used to pad fabric).
31, method according to claim 29 is characterized in that being prepared as of said water-soluble active methylenes compound be used to the to foam 2.25-10%(weight of said permanent set finishing agent of finish fabric).
32, method according to claim 24 is characterized in that the permanent set finishing agent comprises the N-methylol crosslinking agent.
33, method according to claim 32 is characterized in that the N-methylol crosslinking agent is the DMDHEU resin system of DMDHEU or modification.
34, a kind of preparation comprises the method for the permanent set finishing agent of water-soluble active methylenes compound, it is characterized in that said method may further comprise the steps:
(a) under anhydrous condition, make dialkyl malonate, replacement or unsubstituted polyalcohol and transesterification catalyst mix;
(b) heat and stir said mixture, to obtain the methylene compound of water-soluble active;
(c) dilution water dissolubility activity methene compound is to form water-soluble active methylenes solution;
(d) in and water-soluble active methylenes solution;
(e) water-soluble active methylenes solution is attached in the permanent set finishing agent.
35, method according to claim 34 is characterized in that with 1 mole of dialkyl malonate: ratio 2.2 moles of replacements or unsubstituted polyalcohol makes dialkyl malonate and replacement or unsubstituted polyalcohol mixing.
36, method according to claim 34 is characterized in that with 0.2 milliliter of catalyst: the ratio of 1 mole of dialkyl malonate adds transesterification catalyst.
37, method according to claim 34 is characterized in that in the temperature range with said mixture heated to 95 ℃～100 ℃.
38, method according to claim 34 is characterized in that dialkyl malonate is a diethyl malonate.
39, method according to claim 34 is characterized in that polyalcohol that replace or unsubstituted is a diethylene glycol (DEG).
40, method according to claim 34 is characterized in that transesterification catalyst is dense H
2SO
4(99%).
41, according to right 4 described methods, it is characterized in that adopting an aspirator, said mixture is placed under the vacuum.
42, method according to claim 34 is characterized in that making the water-soluble active methylenes diluted chemical compound to containing 50% solid matter.
43, method according to claim 34, it is characterized in that making the water-soluble active methylenes solution pH value that neutralizes is 6～7.
44, according to the described method of claim 43, it is characterized in that making the water-soluble active methylenes solution pH value that neutralizes is 6.75.
45, method according to claim 34 is characterized in that the amount with 1.25～10% solid matter owb, and water-soluble active methylenes solution is added in the permanent set finishing agent.
46, according to the described method of claim 45, it is characterized in that when the permanent set finishing agent is used to pad fabric, with the amount of 1.25～5.00% solid matter owb, water-soluble active methylenes solution is added in the permanent set finishing agent.
47,, it is characterized in that when the permanent set finishing agent is used to foam finish fabric,, water-soluble active methylenes solution being added in the permanent set finishing agent with the amount of 2.5-10% solid matter owb according to the described method of claim 45.
48, method according to claim 34 is characterized in that the permanent set finishing agent comprises the N-methylol crosslinking agent.
49,, it is characterized in that the N-methylol crosslinking agent is DMDHEU or modified DMDHEU resin system according to the described method of claim 48.
50, a kind of preparation comprises the method for the permanent set finishing agent of water-soluble active methylenes compound, it is characterized in that said method may further comprise the steps:
(a) under anhydrous condition, make Acetacetic acid alkyl ester, replacement or unsubstituted polyalcohol and transesterification catalyst mix;
(b) heat and stir said mixture, to obtain the water-soluble active methylenes compound;
(c) dilution water dissolubility activity methene compound is to form water-soluble active methylenes solution;
(d) in and water-soluble active methylenes solution;
(e) water-soluble active methylenes solution is added in the permanent set finishing agent.
51, according to the described method of claim 50, it is characterized in that with 1 mole of Acetacetic acid alkyl ester: ratio 2.2 moles of replacements or unsubstituted polyalcohol makes Acetacetic acid alkyl ester and replacement or unsubstituted polyalcohol mixing.
52, according to the described method of claim 50, it is characterized in that with 0.2 milliliter of catalyst: the ratio of 1 mole of Acetacetic acid alkyl ester adds transesterification catalyst.
53,, it is characterized in that the temperature range of said mixture heated to 95 ℃-100 ℃ according to the described method of claim 50.
54,, it is characterized in that the acetate alkyl ethyl ester is an ethyl ethyl acetate according to the described method of claim 50.
55, according to the described method of claim 50, it is characterized in that replacing or not replace polyalcohol be diethylene glycol (DEG).
56,, it is characterized in that transesterification catalyst is dense H according to the described method of claim 50
2SO
4(99%).
57, according to the described method of claim 50, it is characterized in that adopting an aspirator, said mixture is placed under the vacuum.
58,, it is characterized in that making the water-soluble active methylenes diluted chemical compound to containing 50% solid matter according to the described method of claim 50.
59,, it is characterized in that making water-soluble active methylenes solution to neutralize the pH value for 6-7 according to the described method of claim 50.
60, according to the described method of claim 59, it is characterized in that making the water-soluble active methylenes solution pH value that neutralizes is 6.75.
61, according to the described method of claim 50, it is characterized in that amount, water-soluble active methylenes solution is added in the permanent set finishing agent with 1.25-10% solid matter owb.
62, according to the described method of claim 61, it is characterized in that when the permanent set finishing agent is used to pad fabric, with the amount of 1.25-5.00% solid matter owb, water-soluble active methylenes solution is added in the permanent set finishing agent.
63,, it is characterized in that when the permanent set finishing agent is used to foam finish fabric,, water-soluble active methylenes solution being added in the permanent set finishing agent with the amount of 2.5-10% solid matter owb according to the described method of claim 61.
64,, it is characterized in that the permanent set finishing agent comprises the N-methylol crosslinking agent according to the described method of claim 50.
65,, it is characterized in that the N-methylol crosslinking agent is DMDHEU or modified DMDHEU resin system according to the described method of claim 64.
66, a kind of fabric that completely or partially constitutes by cellulose fibre and the fabric handled by the permanent set finishing agent that comprises the water-soluble active methylenes compound of representing with general expression, general expression is represented with following formula:
It is characterized in that R is-CH
3, perhaps H[O(CH
2) m] n-O-,
R ' is-CH
3, perhaps H[O(CH
2) m '] n '-O-,
M and (or) m ' be 1-3, n with (or) n ' is 1-19,
Y is-CH
2-or-CH
2-CO-CH
2-.
67, according to the described fabric of claim 66, it is characterized in that n and (or) n ' is 1-3.
68, according to the described fabric of claim 66, it is characterized in that n and (or) n ' is 2.
69,, it is characterized in that R is H[O(CH according to the described fabric of claim 66
2) m] n-O-, R ' is H[O(CH
2) m '] n '-O-, m and (or) m ' is 2, n and (or) n ' is 2, y is-CH
2-and the water-soluble active methylenes compound be two (2-hydroxyl ethoxy ethyl) malonates.
70,, it is characterized in that R is-CH according to the described fabric of claim 66
3, R ' is [O(CH
2) m '] n '-O-,
M ' is 2, and n ' is 2, and y is CH
2And the water-soluble active methylenes compound is (2-hydroxyl ethoxy ethyl) acetoacetic ester.
71,, it is characterized in that the permanent set finishing agent comprises the N-methylol crosslinking agent according to the described fabric of claim 66.
72,, it is characterized in that the N-methylol crosslinking agent is DMDHEU or modified DMDHEU resin system according to the described fabric of claim 71.
73, a kind of method of making flakeboard, said method comprise makes timber mix with urea-formaldehyde resins, by heating resin is cured; By being joined, a kind of scavenger reduces the formaldehyde amount that discharges from flakeboard in the urea-formaldehyde resins; It is characterized in that said scavenger is selected from the group of being made up of following general expression,
In the formula, R is-CH
3, perhaps H[O(CH
2) m] n-O-,
R ' is-CH
3, perhaps H[O(CH
2) m '] n '-O-,
M and (or) m ' be 1-3, n with (or) n ' is 1-19,
Y is-CH
2-or-CH
2-CO-CH
2-.
74, according to the described method of claim 73, it is characterized in that n and (or) n ' is 1-3.
75, according to the described method of claim 73, it is characterized in that n and (or) n ' is 2.
76,, it is characterized in that R is H[O(CH according to the described method of claim 73
2) m] n-O-, R ' is H[O(CH
2) m '] n '-O-,
M and (or) m ' is 2, n and (or) n ' is 2,
Y is-CH
2-and the water-soluble active methylenes compound be two (2-hydroxyl ethoxy ethyl) malonates.
77,, it is characterized in that R is-CH according to the described method of claim 73
3, R ' is H[O(CH
2) m '] n '-O-, m ' is 2, and n ' is 2, and y is-CH
2-and the water-soluble active methylenes compound be (2-hydroxyl ethoxy ethyl) acetoacetic ester.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5360687A | 1987-05-20 | 1987-05-20 | |
| US5284287A | 1987-05-20 | 1987-05-20 | |
| US053,606 | 1987-05-20 | ||
| US052,842 | 1987-05-20 | ||
| US7103287A | 1987-07-08 | 1987-07-08 | |
| US071,032 | 1987-07-08 | ||
| US18864388A | 1988-05-02 | 1988-05-02 | |
| US188,643 | 1988-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1032047A true CN1032047A (en) | 1989-03-29 |
Family
ID=27489512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88103032 Pending CN1032047A (en) | 1987-05-20 | 1988-05-20 | Water-soluble active methylenes as formaldehyde scavenger |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1032047A (en) |
| ES (1) | ES2010749A6 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384601C (en) * | 2006-03-07 | 2008-04-30 | 北京林业大学 | For maldehyde eliminating agent and prepn. process thereof |
| CN102485275A (en) * | 2011-06-22 | 2012-06-06 | 聂莹琨 | Cleanser for decorated indoor air |
| CN102596843A (en) * | 2009-06-03 | 2012-07-18 | 圣戈班艾德福斯公司 | Mineral fiber mat containing a formaldehyde-trapping agent, and methods for manufacturing same |
| CN103055465A (en) * | 2011-10-18 | 2013-04-24 | 上海格伦化学科技有限公司 | Formaldehyde scavenging agent with oil solubility and preparation method |
| CN106367965A (en) * | 2008-12-19 | 2017-02-01 | 圣戈班艾德福斯公司 | Canvas including an agent capable of trapping formaldehyde and manufacturing process |
| CN106928766A (en) * | 2015-12-31 | 2017-07-07 | 广东华润涂料有限公司 | water-soluble formaldehyde scavenger |
| CN110204441A (en) * | 2013-01-11 | 2019-09-06 | 瑟拉斯公司 | The method for obtaining methylene malonate by the approach of bis- (methylol) malonates |
| CN112661646A (en) * | 2020-12-11 | 2021-04-16 | 江苏长能节能新材料科技有限公司 | Active methylene type aldehyde remover and application thereof |
-
1988
- 1988-05-20 ES ES8801592A patent/ES2010749A6/en not_active Expired
- 1988-05-20 CN CN 88103032 patent/CN1032047A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384601C (en) * | 2006-03-07 | 2008-04-30 | 北京林业大学 | For maldehyde eliminating agent and prepn. process thereof |
| CN106367965A (en) * | 2008-12-19 | 2017-02-01 | 圣戈班艾德福斯公司 | Canvas including an agent capable of trapping formaldehyde and manufacturing process |
| CN102596843A (en) * | 2009-06-03 | 2012-07-18 | 圣戈班艾德福斯公司 | Mineral fiber mat containing a formaldehyde-trapping agent, and methods for manufacturing same |
| CN102485275A (en) * | 2011-06-22 | 2012-06-06 | 聂莹琨 | Cleanser for decorated indoor air |
| CN102485275B (en) * | 2011-06-22 | 2015-11-25 | 聂莹琨 | A kind of for the indoor air purification agent after fitting up |
| CN103055465A (en) * | 2011-10-18 | 2013-04-24 | 上海格伦化学科技有限公司 | Formaldehyde scavenging agent with oil solubility and preparation method |
| CN103055465B (en) * | 2011-10-18 | 2016-01-20 | 上海格伦化学科技有限公司 | A kind of oil-soluble formaldehyde scavenger and preparation method thereof |
| CN110204441A (en) * | 2013-01-11 | 2019-09-06 | 瑟拉斯公司 | The method for obtaining methylene malonate by the approach of bis- (methylol) malonates |
| CN106928766A (en) * | 2015-12-31 | 2017-07-07 | 广东华润涂料有限公司 | water-soluble formaldehyde scavenger |
| CN112661646A (en) * | 2020-12-11 | 2021-04-16 | 江苏长能节能新材料科技有限公司 | Active methylene type aldehyde remover and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2010749A6 (en) | 1989-12-01 |
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