CN104726237A - Yellow-spot-removing dry cleaning agent - Google Patents
Yellow-spot-removing dry cleaning agent Download PDFInfo
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- CN104726237A CN104726237A CN201510092784.XA CN201510092784A CN104726237A CN 104726237 A CN104726237 A CN 104726237A CN 201510092784 A CN201510092784 A CN 201510092784A CN 104726237 A CN104726237 A CN 104726237A
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Abstract
The invention relates to a yellow-spot-removing dry cleaning agent which comprises the following components in parts by weight: 100 parts of first dry cleaning solvent, 2-100 parts of second dry cleaning solvent, 5-200 parts of water-in-oil emulsifier and 5-200 parts of nonionic surfactant with the HLB value of 12-16. The first dry cleaning solvent is selected from one or more of glycol ether solvents, glycol ether ester solvents and alcohol solvents; and the second dry cleaning solvent is a compound with at least 2 hydroxy groups and at least 1 carboxyl or sulfo group. The yellow-spot-removing dry cleaning agent has favorable yellow spot removal effect.
Description
Technical field
The present invention relates to de-etiolation spot dry cleaning composition, particularly particularly, relate to international Patent classificating number C11D7/00 mainly with the detergent composition that on-surface-active compound is base-material.
Background technology
White duds very easily forms macula lutea, especially at collar portion.In recent years, various collar cleaner releases one after another, and these products generally just have employed concentrated laundry liquid formulation technology, and detersive power is not strong; Even if add proteolytic enzyme, owing to only adopting the general stablizers such as calcium chloride, the detersive power of product to protein(aceous)soil after proteolytic enzyme inactivation, is caused to decline to a great extent; Or only adopt common alcoholic solvent, the rapid osmotic performance of product and the dissolving function to oily dirt can not be improved compared with conventional detergent, can not make zymin within the time that prewashing is shorter, give full play to Decomposition to protein(aceous)soil.
In addition, repeatedly dress and place's fabric such as washed collar very easily fluff, and the easier infiltrated fiber inside of dirt is increased and washs difficulty, and these enzyme-containing detergents of oiliness mixed dirt for some infiltrated fiber inside can not play soil-removing action effectively.Even if surface smut is cleaned, but still the spot vestige do not cleaned can be left.The vestige that the clothing of long-time dress wears because of gigging and shades, makes people think by mistake and does not clean.
Dry-cleaning industry experienced by the blank phase of previous decades in China, to today at the true development of China also with regard to the history of more than ten years, but go back imperfection comparatively speaking, make a general survey of the dry-cleaning development history of All Around The World, the part that it is lived as the house of people, passed by one section of marvellous road, dry-cleaning industry is for especially showing a dry-cleaning heat in China in the whole world.Along with the significantly raising of Consumption of China level, the requirement of each ages to dry-cleaning is also more and more higher, and people have regarded dry-cleaning as a part for life.
So de-etiolation spot dry cleaning composition is the technology that this area is badly in need of breaking through.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides de-etiolation spot dry cleaning composition, the nonionogenic tenside 5-200 weight part that described de-etiolation spot dry cleaning composition comprises the first dry cleaning solvent 100 weight part, the second dry cleaning solvent 2-100 weight part, water-in-oil type emulsifier 5-200 weight part, HLB value are 12-16, the first described dry cleaning solvent is selected from one or more in glycol ether solvent, glycol ether ester solvent, alcoholic solvent, and described second dry cleaning solvent is the compound with at least 2 hydroxyls and at least 1 carboxyl or sulfonic acid group.
The many sulfonic compounds of described poly-hydroxy are the benzene, naphthalene, anthracene, anthraquinone, the biphenyl that are at least connected to 2 oh groups and at least 2 sulfonic acid groups.
Described poly-hydroxy sulfonic compound is the benzene, naphthalene, anthracene, anthraquinone, the biphenyl that are at least connected to 2 oh groups and 1 sulfonic acid group.
Described multi-hydroxy multi-carboxy acid's compounds is ethane, propane, butane, Trimethylmethane, benzene, naphthalene, anthracene, anthraquinone, biphenyl, the compound of at least 2 oh groups and at least 2 hydroxy-acid groups.
Described multi-hydroxy carboxy acid's compounds is ethane, propane, butane, Trimethylmethane, benzene, naphthalene, anthracene, anthraquinone, biphenyl, the compound of at least 2 oh groups and 1 hydroxy-acid group.
The ethers emulsifying agent that described water-in-oil type emulsifier is selected from ester emulsifying agent that emulsifying agent, the polyether glycol with polysiloxane-hydrophilic group-alkyl molecule chain structure formed with its hydroxyl and lipid acid, polyether glycol is formed with its hydroxyl and fatty alcohol.
Described HLB value is the polyoxyethylene tensio-active agent that the nonionogenic tenside of 12-16 is selected from that molecular weight is 1000-8000.
Described de-etiolation spot dry cleaning composition also comprises the sulfonated polyimide resin of 5-30 weight part, described sulfonated polyimide resin is synthesized by tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines, and other components of described sulfonated polyimide and de-etiolation spot dry cleaning composition form dispersion.
Described tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines are symmetrical structure.
The sulfonation degree of described polyimide resin is lower than 75%.
The sulfonation degree of described sulfonated polyimide is 20%-75%.
The molecular-weight average of described sulfonated polyimide resin is 50000-250000.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
Second solvent of the present invention is liquid solvent under not only referring to normal temperature, also can be solid-state compound under normal temperature.
The nonionogenic tenside 5-200 weight part that de-etiolation spot dry cleaning composition comprises the first dry cleaning solvent 100 weight part, the second dry cleaning solvent 2-100 weight part, water-in-oil type emulsifier 5-200 weight part, HLB value are 12-16, the first described dry cleaning solvent is selected from one or more in glycol ether solvent, glycol ether ester solvent, alcoholic solvent, and described second dry cleaning solvent is the compound with at least 2 hydroxyls and at least 1 carboxyl or sulfonic acid group.
As one of embodiments of the invention, described glycol ether solvent can be methyl glycol ether, ethyl glycol ether, propyl glycol ether, butyl glycol ether and hexyl glycol ether etc.
As one of embodiments of the invention, glycol ether ester solvent can be ethylene glycol ether acetate, glycol methyl ether acetate, 2-Butoxyethyl acetate, glycol propyl ether acetic ester etc.
As one of embodiments of the invention, alcoholic solvent can be ethanol, hexylene glycol, butanols, propyl alcohol and amylalcohol etc.
As one of embodiments of the invention, the second described dry cleaning solvent is the many sulfonic compounds of poly-hydroxy and/or poly-hydroxy sulfonic compound, the many sulfonic compounds of described poly-hydroxy refer to the compound with at least 2 oh groups and at least 2 sulfonic acid groups, and described poly-hydroxy sulfonic compound refers to the compound with at least 2 oh groups and at least 1 sulfonic acid group.
As one of embodiments of the invention, the many sulfonic compounds of described poly-hydroxy are the benzene, naphthalene, anthracene, anthraquinone, the biphenyl that are at least connected to 2 oh groups and at least 2 sulfonic acid groups.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the benzene of at least 2 sulfonic acid groups can be 3,4-dihydroxy-benzene-1,2-disulfonic acid, 3,6-dihydroxy-benzene-1,2-disulfonic acid, 3,6-dihydroxy-benzene-1,2-disulfonic acid, 3,4,5-trihydroxybenzene-1,2-disulfonic acid, 3,4,6-trihydroxybenzene-1,2-disulfonic acid, 3,4,5,6-tetrahydroxy phenol-1,2-disulfonic acid.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the naphthalene of at least 2 sulfonic acid groups can be 4,5-dihydroxyl-2,7-naphthalene disulfonic acid, 3,6-dihydroxyl-2,7-naphthalene disulfonic acids, 5,6-dihydroxyl-2,3-naphthalene disulfonic acid, 5,7-dihydroxyl-2,4-naphthalene disulfonic acid, 1,8-dihydroxy naphthlene-3,6-disulfonic acid, 5,6-dihydroxyl-2,3,4-naphthalene trisulfonic acid.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the anthracene of at least 2 sulfonic acid groups are 1,4-dihydroxyanthraquinone-2,3-disulfonic acid, Isosorbide-5-Nitrae-dihydroxyanthraquinone-5,6-disulfonic acid, 1,4-dihydroxyanthraquinone-6,7-disulfonic acid, Isosorbide-5-Nitrae-dihydroxyanthraquinone-5,6,7-trisulfonic acid.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the biphenyl of at least 2 sulfonic acid groups are 2,2 '-dihydroxybiphenyl-4,4 '-disulfonic acid, 2,2 '-dihydroxybiphenyl-3,3 '-disulfonic acid, 2 ', 4 '-dihydroxybiphenyl-2,4-disulfonic acid.
As one of embodiments of the invention, described poly-hydroxy sulfonic compound is the benzene, naphthalene, anthracene, anthraquinone, the biphenyl that are at least connected to 2 oh groups and 1 sulfonic acid group.
As one of embodiments of the invention, the benzene of at least 2 oh groups that can enumerate and 1 sulfonic acid group can be 3,5-dihydroxy benzenes sulfonic acid, 2,4-dihydroxy benzenes sulfonic acids, 2,5-dihydroxy benzenes sulfonic acid, 3,4,5-trihydroxybenzene sulfonic acid, 2,3,4-trihydroxybenzene sulfonic acid, 2,3,4,5-tetrahydroxy phenol sulfonic acid.
As one of embodiments of the invention, the anthracene of at least 2 oh groups that can enumerate and 1 sulfonic acid group can be 4,9-dihydroxyl-2-anthracene sulfonic acid, 5,8-dihydroxyl-2-anthracene sulfonic acids, 6,7-dihydroxyl-2-anthracene sulfonic acid, 3,4,5-trihydroxy--2-anthracene sulfonic acid, 3,5,8-trihydroxy--2-anthracene sulfonic acid, 4,5,8,9-tetrahydroxy-2-anthracene sulfonic acid.
As one of embodiments of the invention, the biphenyl of at least 2 oh groups that can enumerate and 1 sulfonic acid group can be 2,2 '-dihydroxybiphenyl-4-sulfonic acid, 2,2 '-dihydroxybiphenyl-3-sulfonic acid, 2 ', 4 '-dihydroxybiphenyl-2-sulfonic acid.
As one of embodiments of the invention, the naphthalene of at least 2 oh groups that can enumerate and 1 sulfonic acid group can be 2,3-dihydroxy naphthlene sulfonic acid, 2,4-dihydroxy naphthlene sulfonic acid, 4,5-dihydroxy naphthlene sulfonic acid, 2,6-dihydroxy naphthlene sulfonic acid, 3,5,7,8-tetrahydroxy naphthene sulfonic acid, 3,5,7-trihydroxynaphthalene sulfonic acid.
As one of embodiments of the invention, the second described dry cleaning solvent is multi-hydroxy multi-carboxy acid's compounds and/or multi-hydroxy carboxy acid's compounds, described multi-hydroxy multi-carboxy acid's compounds refers to the compound with at least 2 oh groups and at least 2 hydroxy-acid groups, and described multi-hydroxy carboxy acid's compounds refers to the compound with at least 2 oh groups and at least 1 hydroxy-acid group.
As one of embodiments of the invention, described multi-hydroxy multi-carboxy acid's compounds is ethane, propane, butane, Trimethylmethane, benzene, naphthalene, anthracene, anthraquinone, biphenyl, the compound of at least 2 oh groups and at least 2 hydroxy-acid groups.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the benzene of at least 2 hydroxy-acid groups can be 3,4-dihydroxy-benzene-1,2-dicarboxylic acid, 3,6-dihydroxy-benzene-1,2-dicarboxylic acid, 3,6-dihydroxy-benzene-1,2-dicarboxylic acid, 3,4,5-trihydroxybenzene-1,2-dicarboxylic acid, 3,4,6-trihydroxybenzene-1,2-dicarboxylic acid, 3,4,5,6-tetrahydroxy phenol-1,2-dicarboxylic acid.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the naphthalene of at least 2 hydroxy-acid groups can be 4,5-dihydroxyl-2,7-naphthalene dicarboxylic acids, 3,6-dihydroxyl-2,7-naphthalene dicarboxylic acids, 5,6-dihydroxyl-2,3-naphthalene dicarboxylic acids, 5,7-dihydroxyl-2,4-naphthalene dicarboxylic acids, 1,8-dihydroxy naphthlene-3,6-dicarboxylic acid, 5,6-dihydroxyl-2,3,4-naphthalene tricarboxylic acid.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the anthracene of at least 2 hydroxy-acid groups are 1,4-dihydroxyanthraquinone-2,3-dicarboxylic acid, Isosorbide-5-Nitrae-dihydroxyanthraquinone-5,6-dicarboxylic acid, 1,4-dihydroxyanthraquinone-6,7-dicarboxylic acid, Isosorbide-5-Nitrae-dihydroxyanthraquinone-5,6,7-tricarboxylic acid.
As one of embodiments of the invention, at least 2 oh groups that can enumerate and the biphenyl of at least 2 hydroxy-acid groups are 2,2 '-dihydroxybiphenyl-4,4 '-dicarboxylic acid, 2,2 '-dihydroxybiphenyl-3,3 '-dicarboxylic acid, 2 ', 4 '-dihydroxybiphenyl-2,4-dicarboxylic acid.
As one of embodiments of the invention, described multi-hydroxy carboxy acid's compounds is ethane, propane, butane, Trimethylmethane, benzene, naphthalene, anthracene, anthraquinone, biphenyl, the compound of at least 2 oh groups and 1 hydroxy-acid group.Hydroxy-acid group is the hydroxy-acid group of C1-C4, most preferably formic acid group.
As one of embodiments of the invention, the benzene of at least 2 oh groups that can enumerate and 1 hydroxy-acid group can be 3,5-resorcylic acid, 2,4-resorcylic acids, 2,5-resorcylic acid, 3,4,5-trihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,3,4,5-tetrahydroxy phenol formic acid.
As one of embodiments of the invention, the anthracene of at least 2 oh groups that can enumerate and 1 hydroxy-acid group can be 4,9-dihydroxyl-2-anthroic acid, 5,8-dihydroxyl-2-anthroic acids, 6,7-dihydroxyl-2-anthroic acid, 3,4,5-trihydroxy--2-anthroic acid, 3,5,8-trihydroxy--2-anthroic acid, 4,5,8,9-tetrahydroxy-2-anthroic acid.
As one of embodiments of the invention, the biphenyl of at least 2 oh groups that can enumerate and 1 hydroxy-acid group can be 2,2 '-dihydroxybiphenyl-4-formic acid, 2,2 '-dihydroxybiphenyl-3-formic acid, 2 ', 4 '-dihydroxybiphenyl-2-formic acid.
As one of embodiments of the invention, the naphthalene of at least 2 oh groups that can enumerate and 1 hydroxy-acid group can be 1,4-dihydroxy-2-naphthsaisyuoic acid, 1,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 1,6-dihydroxy-2-naphthoic acid, 1,7-dihydroxy-2-naphthoic acid.
As one of embodiments of the invention, in above-claimed cpd, most preferred is the compound containing at least 2 hydroxyls and 2 sulfonic acid groups or the naphthalene compound containing at least 2 hydroxyls and 2 hydroxy-acid groups, what have choosing most is 2 ', 4 ', 5 '-dihydroxyl-3,4-disulfonic acid, 3,7-dihydroxy-2-naphthoic acids.As preferred scheme, with 100 weight part first dry cleaning solvents for benchmark, 2 ', 4 ', 5 '-dihydroxyl-3,4-disulfonic acid, 3,7-dihydroxy-2-naphthoic acid consumptions are 1-5 weight part.
The ethane of at least 2 oh groups and at least 1 hydroxy-acid group, propane, butane, Trimethylmethane compound, what can select is the compound that dyhydrobutanedioic acid, dihydroxyl pentanedioic acid, dihydroxyl adipic acid etc. have α hydroxyl.
The second organic solvent coordinated with the first dry cleaning solvent that the present invention selects has more hydroxyl, effectively can obtain the protein macula lutea that cleaning fabric deposits, because protein macula lutea is attached on fabric very securely, even form comparatively firmly chemical bond with the fluorescent agent on fabric, possible mechanism is, multi-hydroxy multi-carboxy acid of the present invention or the many sulfoacid compounds of poly-hydroxy have stronger acidity and steric effect, hydroxyl simultaneously on phenyl ring or α hydroxyl have higher activity, instability absorption can be formed at fabric fibre, under external force, by the fiber surface generation mechanico-chemical reaction that alcohol ether solvent soaks, thus the protein macula lutea of fabric face can be removed at normal temperatures.
The present invention can also select part to common are machine acid, as oxysuccinic acid, fumaric acid, toxilic acid, citric acid equal aforesaid second organic solvent and be used in combination.
As one of embodiments of the invention, the ethers emulsifying agent that described water-in-oil type emulsifier is selected from ester emulsifying agent that emulsifying agent, the polyether glycol with polysiloxane-hydrophilic group-alkyl molecule chain structure formed with its hydroxyl and lipid acid, polyether glycol is formed with its hydroxyl and fatty alcohol.
As one of embodiments of the invention, the ethers emulsifying agent that described water-in-oil type emulsifier is selected from ester emulsifying agent that emulsifying agent, the polyether glycol with polysiloxane-hydrophilic group-alkyl molecule chain structure formed with its hydroxyl and lipid acid, polyether glycol is formed with its hydroxyl and fatty alcohol.
As one of embodiments of the invention, there is the emulsifying agent of polysiloxane+hydrophilic group+alkyl molecule chain structure, comprise the block copolymer emulsif iotaer that polysiloxane, polyether glycol and fat alkane are connected with covalent linkage, with polysiloxane be main chain, polyether glycol and fatty alkyl for side base is respectively with the emulsifying agent that covalent linkage is connected with polysiloxane chain, and be main chain with polysiloxane, the emulsifying agent that is connected with polysiloxane chain with covalent linkage for side base of polyether glycol modified of fatty alkyl; The polyoxyethylene polydimethylsiloxane of preferred C6-C20 alkyl copolymerization, more preferably hexadecyl PEG/PPG-10/1 polydimethylsiloxane (Degussa EM90);
There is the emulsifying agent of polysiloxane+hydrophilic group molecular chain structure, comprise the block copolymer emulsif iotaer that polysiloxane is connected with covalent linkage with polyether glycol, take polysiloxane as main chain, emulsifying agent that polyether glycol is connected with polysiloxane backbone with covalent linkage for side base; Preferred polyoxyethylene polydimethylsiloxane, Polyglycerine polydimethylsiloxane, more preferably two-PEG/PPG-14/14 polydimethylsiloxane (Degussa EM97);
As one of embodiments of the invention, the ester emulsifying agent that the polyether glycol of non-linear structure or linear structure is formed with its hydroxyl and lipid acid, or the ethers emulsifying agent that polyether glycol is formed with its hydroxyl and fatty alcohol, comprise polyoxyethylene fatty acid ester, Voranol EP 2001, list or polyglycerol fatty acid ester, list or polyglycerol alkyl ether, preferably two isostearoyl base Polyglycerine-3 linoleic acid dimers ester (Degussa PDI), Polyglycerine-4 diisopstearate/poly-oxystearic acid sebate (Degussa GPS), polyoxyethylene sorbitan fatty acid ester.
As one of embodiments of the invention, described HLB value is the polyoxyethylene tensio-active agent that the nonionogenic tenside of 12-16 is selected from that molecular weight is 1000-8000.
HLB value=7+11.7log (MW/MO),
Mw: the molecular weight of tensio-active agent hydrophilic segment,
Mo: the molecular weight of tensio-active agent oleophilic moiety,
As one of embodiments of the invention, be the nonionic surface active agent of 14 ~ 18 as HLB, polyoxyethylene glycerol fatty acid esters can be enumerated, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol sorbitan-fatty acid ester, polyoxyethylenated castor oil, polyoxyethylene hardened castor oil (the average addition mole number of oxyethane: 60 ~ 100), glycol fatty acid ester, 12 ~ 150) polyoxyethylene glycol mono fatty acid ester (the average addition mole number of oxyethane: the cithrol such as, alkyl glycerylether, Voranol EP 2001, Voranol EP 2001 fatty acid ester etc.These can be used alone a kind of or appropriately combined two or morely to use.
Particularly, HLB14-18 can enumerate, polyethyleneglycol dodecanoate (12EO), polyethylene glycol mono stearate (20EO), four oleic acid POE (60) sorbyl alcohols, POE (60) hardened castor oil, single tetradecanoic acid ten glyceryl ester, POE (25) stearyl ether etc.As HLB15, polyethylene glycol stearate (30EO), POE (80) hardened castor oil, POE (100) hardened castor oil, POE (20) sorbitan list isostearate, POE (20) sorbitan monooleate, POE (25) isocetyl ether, POE (20) lauryl ether, POE (30) octadecyl ether, polyoxyethylene glycerol isostearate (30EO) etc.As HLB16, polyethylene glycol mono stearate (40EO), POE (15) oily ether, POE (40) octadecyl ether, polyoxyethylene glycerol Unimac 5680 (50EO) etc. can be enumerated.HLB18 can enumerate polyethylene glycol mono stearate (150EO) etc.Wherein, from more effectively playing raising storage stability, the nonionic surface active agent of preferred more than HLB15, the more preferably polyethylene glycol mono stearate (150EO) of HLB18.Wherein, EO is oxyethane, and POE is polyoxyethylene.
As one of embodiments of the invention, described de-etiolation spot dry cleaning composition also comprises the sulfonated polyimide resin of 5-30 weight part, described sulfonated polyimide resin is synthesized by tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines, described tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines are symmetrical structure, the sulfonation degree of described polyimide resin is lower than 75%, and other components of described sulfonated polyimide and de-etiolation spot dry cleaning composition form dispersion.
As one of embodiments of the invention, the molecular-weight average of described sulfonated polyimide is 20%-75%.
As one of embodiments of the invention, the molecular-weight average of described sulfonated polyimide resin is 50000-250000.
As one of embodiments of the invention, described de-etiolation spot dry cleaning composition also comprises the polyimide resin of 5-30 weight part, the molecular-weight average of described polyimide resin is for being not less than 50000, and other components of described polyimide and de-etiolation spot dry cleaning composition form dispersion.Pole is used to be insoluble in the polyimide of organic solvent of the present invention, polyimide is crushed to certain particle diameter, and make polyimide be scattered in organic solvent in the mode of dispersion, polyimide particle shell small portion occurs swelling, and the polyimide of inner hard outer softness can remove protein macula lutea well.The present invention found through experiments, molecular-weight average is selected to be that 50000-250000 can realize object of the present invention effectively, lower than 50000 molecular weight, then the generation of polyimide particle major part is swelling, particle deliquescing possibly cannot adsorb glue or the coating of more colloidal sol, even can be adsorbed on fabric, and higher than 250000 molecular weight, then molecular weight cannot occur too greatly swelling, effect reduces.So as preferred technical scheme, the molecular-weight average of polyimide resin of the present invention is 50000-250000.The molecular weight of polyimide is obtained by viscosimetry.
As one of embodiments of the invention, as preferred technical scheme, being synthesized by tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines of described polyimide, described tetracarboxylic dianhydride, aromatic diamines are symmetrical structure.Tetracarboxylic dianhydride, non-sulfonated aromatic diamines can structure as described in the prior art, is not repeated herein.
As one of embodiments of the invention, sulfonated aromatic diamine of the present invention can be following structure:
Its preparation method is as follows: under nitrogen atmosphere, tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated diamines, phenylformic acid, triethylamine are added in meta-cresol, be warming up to 80 degrees Celsius of stirring reaction 3-10 hour, rise to 180 degrees Celsius of reaction 5-10 hour again, use washing with acetone dry after cooling, the sulfonated polyimide material obtained is ground to powder again.
As one of embodiments of the invention, preferred scheme is the sulfonated aromatic diamine using symmetrical structure, obtains the sulfonated polyimide that degree of crystallinity is higher, improves the intensity of particle, can obtain and better dry-clean effect, more obstinate protein macula lutea can be cleaned.
De-etiolation spot dry cleaning composition of the present invention, selects aforesaid component and weight part, first drops into the first dry cleaning solvent in a reservoir, successively adds the second organic solvent, tensio-active agent, emulsifying agent, finally add polyimide under fully stirring.Stable emulsification system (at least 6 months) is obtained under high-speed stirring.During use, as there is layering because of unusual long storage time, slightly mixing and can use.
Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiments are only illustrative and nonrestrictive.If do not have other to illustrate, raw materials used is all commercially available.
The present invention is described in detail referring to several example.
A1 Virahol
A2 glycol ether
B1 dihydroxyl hexanodioic acid
B2 1,8-dihydroxy naphthlene-3,6-disulfonic acid
B3 3,4,5-trihydroxybenzene sulfonic acid
B4 4,5,8,9-tetrahydroxy-2-anthracene sulfonic acid
B5 1,8-dihydroxy naphthlene-3,6-dicarboxylic acid
B6 Gallic Acid
B7 2 ', 4 ', 5 '-dihydroxybiphenyl-3,4-disulfonic acid
B8 3,7-dihydroxy-2-naphthoic acid
C1 hexadecyl PEG/PPG-10/1 polydimethylsiloxane (Degussa EM90)
Two-PEG/PPG-14/14 the polydimethylsiloxane (Degussa EM97) of C2
C3 Polyglycerine-4 diisopstearate/poly-oxystearic acid sebate (Degussa GPS)
D1 polyethylene glycol mono stearate (150EO)
D2POE (20) sorbitan list isostearate
D3 polyoxyethylene hardened castor oil (the average addition mole number of oxyethane: 60 ~ 100)
The special SG200P of alliance is moulded in E1 polyimide Hangzhou, is ground to median size 1 micron.
The preparation of E2 sulfonated polyimide
Its preparation method is as follows: under nitrogen atmosphere, by 2,3,2', 3' bibenzene tetracarboxylic dianhydride, 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane (molar percentage of sulfonated aromatic diamine is 33.3%), phenylformic acid, triethylamine are added in meta-cresol, be warming up to 80 degrees Celsius of stirring reaction 3-10 hour, rise to 180 degrees Celsius of reaction 5-10 hour again, use washing with acetone dry after cooling, the sulfonated polyimide material obtained is ground to powder average particle size 1000 nanometer again.
The preparation of E3 sulfonated polyimide
Its preparation method is as follows: under nitrogen atmosphere, by 2,3,2', 3' bibenzene tetracarboxylic dianhydride, 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane (molar percentage of sulfonated aromatic diamine is 66.6%), phenylformic acid, triethylamine are added in meta-cresol, be warming up to 80 degrees Celsius of stirring reaction 3-10 hour, rise to 180 degrees Celsius of reaction 5-10 hour again, use washing with acetone dry after cooling, the sulfonated polyimide material obtained is ground to powder average particle size 1000 nanometer again.
The preparation of E4 sulfonated polyimide
Its preparation method is as follows: under nitrogen atmosphere, by 2,3,2', 3' bibenzene tetracarboxylic dianhydride, 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane (molar percentage of sulfonated aromatic diamine is 80%), phenylformic acid, triethylamine are added in meta-cresol, be warming up to 80 degrees Celsius of stirring reaction 3-10 hour, rise to 180 degrees Celsius of reaction 5-10 hour again, use washing with acetone dry after cooling, the sulfonated polyimide material obtained is ground to powder average particle size 1000 nanometer again.
Evaluation method:
Dry-cleaning test: the keg making 2 liter capacity sizes, keg is fixed on the equipment of similar cylinder rotation, simulation drum wash mode carries out detergency ability test, use EMPA116 international standard calico (artificially soiled cloth), and be cut into the disk that diameter is 60mm, the decontamination difference DELTA R(compared before and after artificially soiled cloth dry-cleaning calculates according to GB/T13174).Blancometer uses the full-automatic blancometer of WSD-3C type, Beijing Kang Guang Instrument Ltd..
Embodiment 1-4, comparative example 1-2
Embodiment 5-9
Can be found by above-mentioned experiment, the first dry cleaning solvent of the present invention achieves good cooperation with the second dry cleaning solvent, achieves at normal temperatures and dry-cleans effect preferably.The present invention lists 8 kinds of dissimilar many sulfonic acid of poly-hydroxy or multi-carboxylic acid compounds, and visible, the compound with at least 2 hydroxyls and at least 1 carboxyl or sulfonic acid group can realize good de-etiolation spot effect.In addition, polyimide, as dry-cleaning additive, effectively achieves the cleaning performance removing protein macula lutea at normal temperatures.
Claims (10)
1. de-etiolation spot dry cleaning composition, it is characterized in that, the nonionogenic tenside 5-200 weight part that described de-etiolation spot dry cleaning composition comprises the first dry cleaning solvent 100 weight part, the second dry cleaning solvent 2-100 weight part, water-in-oil type emulsifier 5-200 weight part, HLB value are 12-16, the first described dry cleaning solvent is selected from one or more in glycol ether solvent, glycol ether ester solvent, alcoholic solvent, and described second dry cleaning solvent is the compound with at least 2 hydroxyls and at least 1 carboxyl or sulfonic acid group.
2. macula lutea dry cleaning composition according to claim 1, is characterized in that, the many sulfonic compounds of described poly-hydroxy are benzene, naphthalene, anthracene, anthraquinone, the biphenyl with at least 2 oh groups and at least 2 sulfonic acid groups.
3. macula lutea dry cleaning composition according to claim 1, is characterized in that, described poly-hydroxy sulfonic compound is benzene, naphthalene, anthracene, anthraquinone, the biphenyl with at least 2 oh groups and 1 sulfonic acid group.
4. macula lutea dry cleaning composition according to claim 1, it is characterized in that, described multi-hydroxy multi-carboxy acid's compounds is ethane, propane, butane, Trimethylmethane, benzene, naphthalene, anthracene, anthraquinone, the biphenol compound with at least 2 oh groups and at least 2 hydroxy-acid groups.
5. macula lutea dry cleaning composition according to claim 1, is characterized in that, described multi-hydroxy carboxy acid's compounds is ethane, propane, butane, Trimethylmethane, benzene, naphthalene, anthracene, anthraquinone, the biphenol compound with at least 2 oh groups and 1 hydroxy-acid group.
6. macula lutea dry cleaning composition according to claim 1, it is characterized in that, described water-in-oil type emulsifier is selected from ester emulsifying agent that emulsifying agent, the polyether glycol with polysiloxane-hydrophilic group-alkyl molecule chain structure formed with its hydroxyl and lipid acid, ethers emulsifying agent that polyether glycol is formed with its hydroxyl and fatty alcohol.
7. macula lutea dry cleaning composition according to claim 1, is characterized in that, described HLB value is the non-ionic polyoxyethylene class tensio-active agent of 12-16.
8. macula lutea dry cleaning composition according to claim 1, it is characterized in that, described de-etiolation spot dry cleaning composition also comprises the sulfonated polyimide resin of 5-30 weight part, described sulfonated polyimide resin is synthesized by tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines, and other components of described sulfonated polyimide and de-etiolation spot dry cleaning composition form dispersion.
9. macula lutea dry cleaning composition according to claim 8, is characterized in that, described tetracarboxylic dianhydride, sulfonated aromatic diamine, non-sulfonated aromatic diamines are symmetrical structure, and the molecular-weight average of described sulfonated polyimide resin is 50000-250000.
10. macula lutea dry cleaning composition according to claim 8, is characterized in that, the sulfonation degree of described polyimide resin is lower than 75%.
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| CN201510092784.XA CN104726237A (en) | 2015-03-03 | 2015-03-03 | Yellow-spot-removing dry cleaning agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105647709A (en) * | 2016-02-01 | 2016-06-08 | 东莞品派实业投资有限公司 | Dry cleaning agent for removing yellow spots on clothes and preparation method thereof |
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