CN1058764C - Photosensitive bleaching agent containing photosensitive compound and its preparing method - Google Patents
Photosensitive bleaching agent containing photosensitive compound and its preparing method Download PDFInfo
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- CN1058764C CN1058764C CN96104687A CN96104687A CN1058764C CN 1058764 C CN1058764 C CN 1058764C CN 96104687 A CN96104687 A CN 96104687A CN 96104687 A CN96104687 A CN 96104687A CN 1058764 C CN1058764 C CN 1058764C
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- bleaching agent
- porphines
- agent
- sodium
- photosensitive
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Abstract
The present invention provides a pohotosensitive bleaching agent containing photosensitive compounds and a preparing method thereof. The pohotosensitive bleaching agent containing photosensitive compounds comprises the following main components: a, monocyclic and dicyclic porphin derivative photosensitive compounds as base materials; b, inorganic salts, comprising sodium silicate, etc., enzyme, etc. as a blanching synergistic agent; c, surfactant, olefinic acid polymer, etc. as a wetting agent; d, foam stabilizer; e, a fluorescent whitening agent and essence. The present invention is characterized in that a, economy: natural solar light energy and oxygen in the air are used for decomposing pigment, worm marks and microorganism to obtain a purpose of whitening and sanitary; b, the pohotosensitive bleaching agent containing photosensitive compounds can simultaneously exert a dual vigor function of the enzyme and a bleaching agent. The pohotosensitive bleaching agent containing photosensitive compounds can be singly used as the bleaching agent and matched with various commodity washing agents to wash and blanch.
Description
The present invention relates to a kind of photosensitive bleaching agent that contains light-sensitive compound, be mainly used in the preparation laundry detergent compositions, it increases the bleaching washing function of washing agent.
Can both the abutment surface active power of not all dirt, wetting power, emulsifying ability, mechanical force, and physical force etc. washes, such as, tea, coffee, vegetable colours such as fruit juice must lean on chemical reaction power, as bleaching agent, pigment molecular is broken into colourless fragment remove.
Existing chlorine bleaches is typically clorox, although its bleaching power is strong, poor stability in processing and storage particularly has infringement to dyestuff and fabric when using.Chinese patent CN 1066465 has announced a kind of domestic bleaching water, is characterized in that hypochlorous sodium is a main component, adds Quadrafos, and metaphosphate, phosphate are as water softener, and NaOH is as stabilizing agent.Its principal component clorox is not very favourable to the dyestuff and the fiber of fabric.In oxygen-bearing bleaching agent, be typically SODIUM PERCARBONATE and sodium perborate.The former advantage is that discoloration is strong, and serviceability temperature is low, but stable non-constant.After water-soluble, one hour will be ineffective, and alkalescence is crossed also can cause its inefficacy by force.China is to the research of long-acting sodium percarbonate start to walk [liuYun, etc, 4
ThWorld Conference on Detergent (Strategy for 21
StCentury), Montrux, Switzerland, 1998.10].Although sodium perborate does not have destruction to fabric and dyestuff, serviceability temperature is only applicable to hot wash up to 90 ℃.The appearance of bleach-activating has reduced the serviceability temperature of sodium perborate, but generally still more than normal temperature.Because the loss of the active oxygen of peralcohol, the interpolation total amount of bleaching agent and activator is up to 20% (US 5415668).Trace meter can increase the activity of sodium perborate by catalysis, as iron, and molybdenum, tungsten, vanadium, manganese etc.But because the bleaching of sodium perborate is to realize by the hydrogen peroxide that produces, the metal ion that is added catalyzing hydrogen peroxide too decomposes, thereby must add stabilizing agent, as the magnesium silicate of abundant dispersion, or make itself and chelating agent form complex compound, reduce the side effect of heavy metal.The method of adding magnesium silicate is difficult actually to be realized.And the structure of the chelate of transition metal more complicated often has certain degree of difficulty in preparation.As 1,4 of manganese, 7-trimethyl-1,4, the dinuclear complex of 7-three nitrogen nonanes (U.S. Pat 5,280,117):
Mn(MeTACN)(OCH
3)
3(PF
6)
(ME-TACN:1,4,7-trimethyl-1,4,7-three nitrogen are appointed alkane)
The principal component of photosensitive bleaching agent involved in the present invention is monocycle porphines and dicyclo porphine derivative, and it absorbs abundant existence the in the Nature, and the sunlight energy of free supply, and it is passed to non-existent nowhere oxygen molecule in the air.Make it to be excited to excitation state, thereby oxidation pigment, spot and microorganism reach the purpose of pure white health from ground state.Therefore bleaching agent efficient is very high, contains one thousandth to ten thousand/just can reach the purpose of obvious bleaching in the treatment fluid, has saved cost greatly.Photosensitive bleaching agent can also kill fabric fibre surface and inner microorganism, makes fabric sanitation and hygiene more.
The bleaching mechanism of monocycle porphines that this photosensitive bleaching agent is related and dicyclo porphines light-sensitive compound is:
At first, light-sensitive compound absorbs solar energy becomes excitation state:
1、
This excitation state light-sensitive compound passes to airborne oxygen molecule with energy, makes it to become excitation state:
2、
The oxygen molecule of this excitation state has very high energy, immediately with spot and pigment, and microbial action, making it becomes colourless fragment, thereby makes fabric bleaching and sterilization:
3、
In addition, known enzyme is to remove protein, effective washing agent additive of fat type soil, but because itself is lived protein, so the above is all kinds of chloride, oxygen-bearing bleaching agent all has in various degree lethal effect to enzyme, so just limited in the past bleaching agent and the common use of enzyme.And this photosensitive bleaching agent does not only have lethal effect to enzyme, and also has certain synergy when coexisting with enzyme sometimes.
The object of the present invention is to provide a kind of photosensitive bleaching agent that contains light-sensitive compound, can improve the detergent bleach function of washing agent.It can use separately, also can cooperate commercially available detergent to use, so that according to the character of washings, makes full use of the energy of sunshine.
This photosensitive bleaching agent is characterized in that having following composition:
A, base-material: monocycle porphines and dicyclo porphines light-sensitive compound, its feature such as structural formula I:
X in the formula be (N=) or (=CY-); Y is H, alkyl, cycloalkyl, aralkyl, aryl, or heterocycle; Each R is H, or alkyl, cycloalkyl, and aralkyl, aryl, or heterocycle, and adjacent group can link to each other; A is two H atoms, or Cd (II), Mg (II), Ca (II), A1 (III), Sc (III), Cu (II), Zn (II), Sn (IV); B is an anion in the formula, CATION, nonionic or amphion; M be the B group counter ion; S is the number of solubility group in the formula; N among the formula II is 1,2,3.
If B is a CATION, then M is an anion; If B is an anion, then M is sun.
If B is an anion, then be sulfonic group, sulfate, phosphate, carboxylic acid group, or the polyoxyethylene ether of sulfonic acid or sulfuric acid replacement, its counter ion M is alkali-metal salt, ammonium ion or alkyl phosphate ion; If B is a CATION, then be ammonium ion or alkyl phosphate ion, its counter ion M is halogen ion or p-methyl benzenesulfonic acid base.
If B is a nonionic, then B is polyoxyethylene groups, sulfuric acid single ethanol amide, sulfuric acid diglycollic amide, sulfonic acid single ethanol amide, sulfonic acid diglycollic amide, polyethylene glycol dicarboxylic acid monoesters etc.
The synthetic route of some monocycle porphines light-sensitive compound that this photosensitive bleaching agent is related is as follows:
The synthetic route of the dicyclo porphines light-sensitive compound that this photosensitive bleaching agent is related is as follows:
B, bleach boosters: inorganic salts such as silicate, Quadrafos, citrate, sulfate, sulphite, 4A zeolite, boron-moisten soil, perborate, carbonate, Bio-sil and enzyme etc.Powdery and liquid detergent can be used as bleach boosters.
C, wetting agent: anion surfactant, non-ionic surface active agent, ethylenic unsaturated acid copolymer etc., super absorbent resin ester etc.
If anion surfactant then is an alkylbenzenesulfonate, fatty alcohol polyoxyethylene ether sulfate, aliphatic alcohol polyethenoxy ether carboxylate, α-Xi Jihuangsuanyan etc.; If non-ionic surface active agent then is a fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, glyceryl monostearate, sorbitan fatty acid esters, sucrose fatty ester etc.; The ethylenic unsaturated acid copolymer is maleic anhydride and polymerizing acrylic acid thing (molecular weight 2,000-20,000) etc.
D, foam stabilizer: higher aliphatic (C
10-C
22), higher fatty acids (C
10-C
22) and fatty acid amide (C
10-C
22) etc.;
E, fluorescent whitening agent and essence.
Fluorescent whitening agent: talan biphenyl sulfonate type, as CBS[4,4 '-two (2-sulfonic acid styrene) biphenyl], or the talan sulfonate type, as VBL[4,4 '-two (4-hydroxyethylamines-6-anilino--1,3,5-triazine-2 base) amino-talan-2,2 '-sodium disulfonate], BST[4,4 '-two (2,5-disulfobenzene amido)-4-morpholinyls-1,3,5-triazine-2-base is amino] talan-2,2 ' sodium disulfonate etc.
This photosensitive bleaching agent contains following component:
Weight ratio is the light-sensitive compound of 0.01-60%;
Weight ratio is the bleach boosters of 1-99.9%;
Weight ratio is the wetting agent of 0-40%;
Weight ratio is the foam stabilizer (when anion surfactant was 0, foam stabilizer was 0) of 0-8%;
Fluorescent whitening agent, colorant, preservative agent and the essence of trace convention amount.
Wherein this photosensitive bleaching agent comprises liquid photosensitive bleaching agent and solid photosensitive bleaching agent.The liquid photosensitive bleaching agent contains:
Weight ratio is the light-sensitive compound of 0.01-30%;
Weight ratio is the bleach boosters of 1-40%;
Weight ratio is the wetting agent of 0-40%;
Weight ratio is the foam stabilizer (when anion surfactant was 0, foam stabilizer was 0) of 0-5%;
Fluorescent whitening agent, colorant, preservative agent and the essence of trace convention amount.
The solid photosensitive bleaching agent, contain:
Weight ratio is the light-sensitive compound of 0.01-60%;
Weight ratio is the bleach boosters of 40-99.9%;
Weight ratio is the wetting agent of 0-40%;
Weight ratio is the foam stabilizer (when anion surfactant was 0, foam stabilizer was 0) of 0-8%;
Fluorescent whitening agent, preservative agent, colorant and the essence of trace convention amount.
The preparation method of liquid photosensitive bleaching agent carries out by the following method:
At first that light-sensitive compound is soluble in water at 20-50 ℃, stirred 20-60 minute, add Quadrafos, sulfate, silicate, Quadrafos, citrate, sulfate, sulphite, sodium alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether sulfate, salts substances such as aliphatic alcohol polyethenoxy ether carboxylate, stirred 1-2.5 hour, and made abundant dissolving, this is a solution A; Then with fluorescent whitening agent, non-ionic surface active agent, materials such as polymer add the aqueous solution at 50-80 ℃, stir 30-70 minute, and this is a solution B; A and two kinds of solution mixing of B stirring were cooled to below 45 ℃ after 50-70 minute, add essence, last, add water to predetermined.
The preparation method of the photosensitive fabric bleaching agent of solid carries out by the following method:
1, at first light-sensitive compound is pulverized with ball mill, this is component A;
2, again with Quadrafos, sulfate, salts substances such as silicate, Quadrafos, citrate, sulfate, sulphite, sodium alkyl benzene sulfonate are pulverized in ball mill, and this is a B component;
3,30-80 ℃ of dissolving, this is component C with usefulness low amounts of water such as the wetting agent of non-salt, foam stabilizer, fluorescent whitening agent (be no more than gross weight 6%);
4, small powders such as essence are made a spot of ethanol water, this is component D;
5, with component A, B, C, D mix in rotary drum and are finished product.Also can be processed into particle with kneader.
If adopt the 4A zeolite during preparation solid photosensitive bleaching agent, Bio-sil, fluffy profit soil, or washing powder is the prescription of bleach boosters, then at first with light-sensitive compound at the 20-50 ℃ of aqueous solution of making 1%-10%, mix the back with zeolite etc. and in thin film evaporator, steam and remove moisture, mix in rotary drum with other components again, or be sprayed on other the component, or directly in rotary drum, mix.
This photosensitive bleaching agent can add running water separately fabric is bleached, also can cooperate any washing agent to use, also can when making washing agent, join in the conventional prescription, handling bath raio (ratio of light-sensitive compound and bleaching liquid or cleaning solution) is 1: 2,000-1: 100,000, can receive tangible bleaching effect.
Washing methods can soak fabric in the sun, also airing in the sun.The bleaching degree and sunny degree weather and the length of airing time, and the degree of polluting is relevant.Sunlight is sufficient more, and the airing time is long more, and it is serious more that fabric pollutes, and clean result is remarkable more.
Example I-V: the composition of photosensitive bleaching agent
The listed prescription of following table is % by weight:
| Raw material | I | II | III | IV | V |
| Two porphines 5,10,15-three (4-sulphenyl)-20-[4-[3-[4-[10,15,20-three (4-sulphenyl)-5-porphines base] phenoxy group] propoxyl group] phenyl] porphines sodium sulfonate (DTPPS 6) (light-sensitive compound A) | 2.0 | ||||
| 5,10,15,20-four (front three aminophenyl) porphines paratoluenesulfonic acid ammonium salt (light-sensitive compound B) | 1.0 | 3.0 | |||
| 5,10,15,20-four p-hydroxybenzene porphines, four polyethylene glycol succinates (light-sensitive compound C) | 3.0 | ||||
| The blue or green zinc four sulfo group diglycollic amides (light-sensitive compound D) of phthalein | 2.0 | ||||
| Dodecanol polyoxyethylene ether carboxylic acid sodium (EO 3) | 11.0 | ||||
| Neopelex | 30.0 | 20.0 | |||
| The dodecyl alcohol polyoxyethylene ether sodium sulfate | 15.0 | ||||
| Dodecanol polyoxyethylene ether (EO 6-9) | 5.0 | 20.0 | |||
| The glycerol monostearate | 5.0 | ||||
| I-octadecanol polyoxyethylene ten pentaethers | 2.0 | 5.0 | |||
| Sodium sulphate | 10.0 | Surplus |
| Sodium phosphate trimer | 18.0 | 30.0 | |||
| Sodium metasilicate | 5.0 | 10.0 | 8.0 | ||
| The 4A zeolite | 30.0 | 22.0 | |||
| Sodium sulfite | 5.0 | ||||
| Sodium carboxymethylcellulose | 5.0 | ||||
| Granulated detergent | 47.0 | ||||
| Acrylic acid/copolymer-maleic anhydride | 0.8 | 5.0 | |||
| High hydroscopic resin | 0.3 | ||||
| Protease | 2.5 | 5.0 | |||
| Lipase | 2.5 | ||||
| Fluorescent whitening agent, preservative agent, essence, colorant | Trace | Trace | Trace | Trace | Trace |
| Water | 8.0 | Surplus | Surplus | 7.0 | 6.0 |
Example VI: application examples (bleach merely and cooperate commodity washing powder detergent bleach)
Be equipped with in the basin of one liter of running water in bleaching agent shown in 0.25ml (1) the formula I I is added, place under the outdoor sunlight, put into 60 * 60cm
2The coffee soiled cotton, a same in addition soiled cotton is put into the running water of the same volume of no bleaching agent, thing was rinsed two cloth specimens well after 120 minutes with running water in contrast, pressed driedly, or soaked airing in the sun after 30 minutes.The cloth specimen that soaks in bleaching agent compares with the whiteness (sweet thatch whiteness) of contrast cloth specimen, and whiteness obviously increases, and Δ Δ R is 2.7-7.2 (Δ Δ R is that range estimation in 1.5 o'clock has notable difference).
Be applied to be added with the running water of 3g/l panda brand washing powder with quadrat method, the cloth specimen that soaks in being added with the washing powder water of photosensitive bleaching agent is apparently higher than the person that only is added with washing powder.
Be applied to two kinds with quadrat method and be added with the super running water of imitating concentrated detergent powder of 1g/l, Δ Δ R is 3.0-6.3.
The difference of bleaching degree and fine degree and the length of airing time, and the degree of polluting is relevant.
Example VII A: application examples (synergy of photosensitive bleaching agent and enzyme)
Prescription 1 and every liter of running water of formula I II add photosensitive bleaching agent and are respectively 0.125g and 0.085g, bleach and add the detergent bleach of washing powder merely by the example VI same procedure.Tester is the same prescription that does not contain the same prescription of enzyme and do not contain photosensitive bleaching agent.
Result is 3.82-7.20 (A value) for the Δ Δ R value that promptly contains enzyme and contain the prescription of light-sensitive compound again, and do not contain enzyme, the prescription Δ Δ R value that only contains light-sensitive compound is 2.5-6.20 (B value), only contains enzyme but the Δ Δ R value that do not contain light-sensitive compound is 0.81-3.71 (C value).
For every group of test, always have A greater than B and A greater than C; General A is not less than B+C, and A is greater than (B+C) 2 more than the whiteness value sometimes.
Claims (4)
1. photosensitive bleaching agent that contains light-sensitive compound, it is characterized in that containing light-sensitive compound, bleach boosters and wetting agent, and selective foam stabilizer, wherein said light-sensitive compound is selected from two porphines 5,10,15-three (4-sulphenyl)-20-[4-[3-[4-[10,15,20-three (4-sulphenyl)-5-porphines base] phenoxy group] propoxyl group] phenyl] porphines sodium sulfonate, 5,10,15,20-four (front three aminophenyl) porphines paratoluenesulfonic acid ammonium salt, 5,10,15,20-four p-hydroxybenzene porphines four polyethylene glycol succinates;
Bleach boosters is selected from inorganic salts such as silicate, Quadrafos, citrate, sulfate, sulphite, 4A zeolite, boron-moisten soil, perborate, carbonate, Bio-sil and enzyme etc.Powdery and liquid detergent can be used as bleach boosters;
Photosensitive bleaching agent contains following each composition, is benchmark with the percentage by weight:
Light-sensitive compound 0.01-60%
Bleach boosters 1-99.9%
Wetting agent 0-40%
Weight ratio is the foam stabilizer of 0-8%;
2. the described photosensitive bleaching agent of claim 1 is characterized in that it contains following each composition, is benchmark with the percentage by weight:
Two porphines 5,10,15-three (4-sulphenyl)-20-[4-[3-[4-[10,15,20-three
(4-sulphenyl)-5-porphines base] phenoxy group] propoxyl group] phenyl]
Porphines sodium sulfonate 2.0%
Glycerol monostearate 5.0%
4A zeolite 30.0%
Granulated detergent 47.0%
3. photosensitive bleaching agent as claimed in claim 1 is characterized in that, it contains following each composition, is benchmark with the percentage by weight:
5,10,15,20-four (front three aminophenyl) porphines paratoluenesulfonic acid ammonium salt 1.0%
Dodecanol polyoxyethylene ether carboxylic acid sodium (EO
3) 11.0%
I-octadecanol polyoxyethylene ten pentaethers 2.0%
Sodium sulphate 10.0%
Acrylic acid/copolymer-maleic anhydride 0.8%
High hydroscopic resin 0.3%
Sodium sulfite 5.0%
4. photosensitive bleaching agent as claimed in claim 1 is characterized in that containing following each composition, is benchmark with the percentage by weight:
5,10,15,20-four p-hydroxybenzene porphines, four polyethylene glycol succinates 3.0%
Dodecyl alcohol polyoxyethylene ether sodium sulfate 15.0
Dodecanol polyoxyethylene ether (EO
6-9) 5.0
I-octadecanol polyoxyethylene ten pentaethers 5.0
Sodium metasilicate 5.0
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104687A CN1058764C (en) | 1996-04-22 | 1996-04-22 | Photosensitive bleaching agent containing photosensitive compound and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104687A CN1058764C (en) | 1996-04-22 | 1996-04-22 | Photosensitive bleaching agent containing photosensitive compound and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1137591A CN1137591A (en) | 1996-12-11 |
| CN1058764C true CN1058764C (en) | 2000-11-22 |
Family
ID=5118452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96104687A Expired - Fee Related CN1058764C (en) | 1996-04-22 | 1996-04-22 | Photosensitive bleaching agent containing photosensitive compound and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1058764C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277337B1 (en) * | 1998-07-21 | 2001-08-21 | Gambro, Inc. | Method and apparatus for inactivation of biological contaminants using photosensitizers |
| CN103695192A (en) * | 2013-11-28 | 2014-04-02 | 南通市通州区大达麻纺织有限公司 | Bactericidal disinfectant for sheet and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045124A (en) * | 1989-02-22 | 1990-09-05 | 普罗格特-甘布尔公司 | The stable liquid detergent compositions that contains SYNTHETIC OPTICAL WHITNER |
-
1996
- 1996-04-22 CN CN96104687A patent/CN1058764C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045124A (en) * | 1989-02-22 | 1990-09-05 | 普罗格特-甘布尔公司 | The stable liquid detergent compositions that contains SYNTHETIC OPTICAL WHITNER |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1137591A (en) | 1996-12-11 |
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