CN1165606C - Fluorescent whitening agent formulation - Google Patents
Fluorescent whitening agent formulation Download PDFInfo
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- CN1165606C CN1165606C CNB971204411A CN97120441A CN1165606C CN 1165606 C CN1165606 C CN 1165606C CN B971204411 A CNB971204411 A CN B971204411A CN 97120441 A CN97120441 A CN 97120441A CN 1165606 C CN1165606 C CN 1165606C
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0063—Photo- activating compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Paper (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a liquid fluorescent whitening agent formulation which is a solution having a viscosity of 50 to 5000 mPas, and which comprises: (a)10-25%, preferably 15-20% by weight of an anionic fluorescent whitening agent, based on the total weight of the reformulation; (b) 15-35%, preferably 20-30% by weight of a polar solvent, based on the total weight of the formulation; and (c) 45-75%, preferably 50-70% by weight, based on the total weight of the formulation, of a nonionic surfactant having the formula, in which each radicle is defined in the specification.
Description
The present invention relates to fluorescent whitening agent formulation, relate in particular to and contain the liquid fluorescent whitening agent formulation that white dyes is dissolved in solution in the extraordinary nonionogenic tenside.
Traditionally, the solid detergent product of detergent manufacturer production is that the aqueous solution slurry that contains various detergent composition compositions (comprising white dyes) is made by spraying drying.For this reason, detergent manufacturer likes using the white dyes composition of liquid preparation form, wants in the spray-dired slurry to impel white dyes to infiltrate.As a result, the used white dyes of detergent manufacturer often is the water slurry form.But this water slurry generally contains big water gaging, should remove in spraying drying subsequently, and result in hand cramps, and as luming when the spraying drying, and easily deposits when storing.
Have been found that detergent manufacturer can be in the later stage of washing composition production process, in the mixture of spray-dired remaining detergent ingredients of granulous, add the liquid preparation of white dyes, with remarkable simplification washing composition production process.The white dyes of the liquid form of moisture content minimizing will be provided for this reason.And detergent manufacturer also is desirable to provide the homogeneous solution form, promptly avoids the in-problem white dyes of traditional water slurry.Another requirement is that the viscosity of said homogeneous solution should be enough low, makes it to carry out traditional pumping fluorescent whitening agent formulation.
In addition, what the liquid preparation of white dyes used is organic solvent, and water-free in fact.But these liquid preparations generally are full-bodied, need it could be blended in the detergent powder with special hybrid mode.
Find that unexpectedly anionic optical brighteners dissolves in the mixture that contains certain type a large amount of nonionogenic tensides and less water, forms stable low viscous limpid solution.
Therefore, the invention provides a kind of liquid fluorescent whitening agent formulation, this is that a kind of viscosity is 50-5000 milli handkerchief second (mPas), is preferably 100-3500 milli handkerchief second, especially be the 100-1000 solution of handkerchief second in the least, and these preparations contain:
A) account for the 10-25% of total formulation weight amount, the anionic optical brighteners of preferred 15-20% weight;
B) account for the 15-35% of total formulation weight amount, the polar solvent of preferred 20-30% weight; And
C) account for the 45-75% of total formulation weight amount, be preferably the nonionogenic tenside of the following general formula of 50-70% weight:
In the formula, m is 1,2,3 or 4, and when m was 1, R was C
8-C
18-alkyl residue or C
8-C
18-alkyl carboxyl residue; When m was 2, R was two C that hydroxyl has been removed
2-C
4The aklylene glycol residue; When m was 3, R was the three methanol-based propane residues that three hydroxyls have been removed, and when m was 4, R was the tetramethylolmethane residue that four hydroxyls have been removed; R
1Be hydrogen, methyl or ethyl; N is a numeral among the 1-40.
Preferred situation, m is 1,3 or 4, when m was 1, R was C
8-C
18-alkyl residue or C
8-C
18-alkyl carboxyl residue; When m is 3, R is a residue of having removed three methanol-based propane of three hydroxyls; When m was 4, R was a tetramethylolmethane residue of having removed four hydroxyls; R
1Be hydrogen, methyl or ethyl; N is a numeral among the 1-40.
The viscosity of liquid fluorescent whitening agent formulation of the present invention is 25 ℃ ± 1 ℃ following and 100/ second following mensuration of shearing force of temperature.
Be used for preferred anionic surfactants white dyes of the present invention and have the structure of one of following general formula:
Or
In the formula, R
2And R
3Being independent of each other, respectively is OH, NH
2, O-C
1-C
4-alkyl, O-aryl, NH-C
1-C
4-alkyl, N (C
1-C
4-alkyl)
2, N (C
1-C
4-alkyl) (C
1-C
4-hydroxyalkyl), N (C
1-C
4-hydroxyalkyl)
2, NH-aryl, morpholino, S-C
1-C
4-alkyl (aryl), Cl or OH; R
4Be H, SO
3M, O-C
1-C
4Alkyl, CN, Cl, COO-C
1-C
4-alkyl, or CON (C
1-C
4-alkyl)
2M is H, Li, Na, K, Ca, Mg, ammonium, single-, two-three-or four-C
1-C
4-alkylammonium, single-, two-or three-C
1-C
4-hydroxyalkyl ammonium or two replaces or trisubstituted ammonium and C
1-C
4-alkyl and C
1-C
4The mixture of-hydroxyalkyl; P is 0 or 1.
In general formula (2) or (3) compound, C
1-C
4-alkyl is, for example, methyl, ethyl, just-propyl group, sec.-propyl and just-butyl, particularly methyl.Aryl is, for example, naphthyl or, phenyl particularly.
In the compound of preferred general formula (2), R
2And R
3Being independent of each other, respectively is methoxyl group, phenoxy group, NH
2, NH-methyl, N (methyl)
2, N (methyl) (hydroxyethyl), NH-ethyl, N (hydroxyethyl)
2, NH-phenyl, morpholino, S-methyl (phenyl), Cl or OH.
Have one of following general formula in the particular example of preferred general formula (2) compound:
With
R in the compound of preferred general formula (3)
4Be H or Cl, p is 1.
Preferred general formula (3) is changed and is contained one of following general formula in the particular example that contains thing:
With
Particularly preferably compound or its crystallized form of the general formula (10) of narration as in EP-A-0 577 557.
If desired, the mixture of two or more anionic optical brighteners can be as the composition of preparation of the present invention a).
Composition b in the preparation of the present invention) polar solvent water preferably.But if desired, water can use together with a kind of or various polarity secondary solvent.These secondary solvents for example are aklylene glycols, as ethylene glycol or 1, and 2-propylene glycol, or polyalkylene glycol, especially polyoxyethylene glycol or polypropylene glycol.The consumption preferable range of any secondary solvent is the 0-15% weight that accounts for the total formulation weight amount.
In the compound of general formula (1), when m was 1, R was derived from C
8-C
18-alkyl monocarbon alcohol.The example of these monohydroxy-alcohols comprises naturally occurring monohydroxy-alcohol, as lauryl alcohol, and myristyl alcohol, the pure and mild stearyl alcohol of hexadecyl, and synthol are as 2-Ethylhexyl Alcohol, 1,1,3,3-tetramethyl-butanols, suffering-2-alcohol, isononyl alcohol, trimethyl hexanol, Exxal 12, just-and decyl alcohol, C
9-C
13-oxo alcohol, tridecyl alcohol, isodecyl alcohol or C
8-C
18Straight chain primary alcohol.These C
8-C
18-straight chain primary alcohol can be buied with merchant's name Atfols on market, and typical example is Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol (16-18).Title " Alfol " is a registered trademark.
M is that 1 preferred embodiment comprises in general formula (1) compound, and for example, the oxyethane of 3-20 mole is with 1 mole of C
8-C
18-alkyl monocarbon alcohol add compound.Particularly importantly the 3-20 moles of ethylene oxide is with 1 mole C
11-C
13The oxyethane of adding compound and 8-20 mole of-oxo alcohol is with 1 mole of C
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) add compound.
M is in 2 the compound in general formula (1), R be derive own to removing the C of two hydroxyls
2-C
4Aklylene glycol.These C
2-C
4Aklylene glycol comprises ethylene glycol, positive butyleneglycol, especially propylene glycol.
M is that the preferred embodiment of 2 compound comprises that for example, the 2-20 moles of ethylene oxide is with 1 mole of C in general formula (1)
2-C
4Aklylene glycol add compound, be preferably the polyglycol ether of propylene glycol, especially have the compound of following general formula:
In the formula, x and y are 1-10 respectively, are preferably an integer among the 1-5, and the summation of x and y preferably is about 10.
M is that alkyl R is derived from three methanol-based propane in 3 the compound in general formula (1).
M is that preferred embodiment in 3 the compound comprises the add compound of 3-20 moles of ethylene oxide with 1 mole of three methanol-based propane in the general formula (1).The particularly important is the add compound of 7-20 oxyethane with 1 mole three methanol-based propane.
M is that alkyl R is from tetramethylolmethane in 4 the compound in general formula (1).
M is that the preferred embodiment of 4 compound comprises the add compound of 4-20 moles of ethylene oxide with 1 mole of pentaerythritol in general formula (1).The particularly important is the add compound of 5-20 moles of ethylene oxide with 1 mole of pentaerythritol.
The mixture of two or more general formulas (1) compound can be used as the composition c of preparation of the present invention).
The compound of general formula (2)-(12) is known, and the preparation of available currently known methods.
The optional adjuvants that can add in preparation of the present invention comprises the stablizer of adjustable restraining agent flowability, foam reducing composition, and alkali reagent, fabric softener, anti redeposition agent, oxidation inhibitor, washing assistant is as polyacrylic acid and spices.
The example of these stablizers comprises, kaolin for example, Mg/Al silicate, especially wilkinite, polynite, the silicic acid of zeolite or high dispersing.
The preparation of preparation of the present invention can be by with white dyes, and the compound of solvent and general formula (1) is mixed together with optional adjuvants, and preferably at high temperature, as under 40-100 ℃ with the gained mixture homogenization.Mix usually and realize by suitable whipping appts.
Resulting preparation generally is limpid and stable solution.But, also may need sometimes preparation is filtered, to remove a spot of insoluble composition.
Preparation of the present invention is specially adapted to sneak in the dry detergent composition, and method is to be added in the dry detergent composition preparation of the present invention of aequum and the resulting mixture of homogenizing simply.Yet, be added in the liquid detergent composition by preparation of the present invention aequum, then with resulting mixture homogenization, also preparation of the present invention can be used to produce liquid washing agent.
Following implementation column further specifies the present invention.Unless otherwise indicated, part and the percentage shown in it is meant weight.Used in an embodiment viscosity data is with milli. handkerchief. second. expression, its measured quantity is carried out under 25 ℃ ± 1 ℃ of shearing force 100/ second and temperature.
Embodiment 1
Following material is packed in 1 liter the flask:
The deionized water of 100 grams;
1 part of C of 600 grams
13-oxo alcohol is with the adducts of 9 parts of oxyethane; And
The fluorescence with following general formula of 300 grams increases the wet cake (active substance that contains 50% weight) of agent:
To obtain suspension under agitation is heated to internal temperature and reaches 70-80 ℃.After 4-5 hour, obtain almost limpid solution, contain not solvent components in the solution less than 1% weight.This solution is as cold as 40-50 ℃, filters then.The yellow clear solution that obtains contains the active substance of 15% weight, and the water of 25% weight and viscosity were 462 milli handkerchief seconds.
Embodiment 2-7
With the method for narration among the embodiment 1, change the amount of each composition and/or change the umber of oxyethane in the condensation product, the pharmaceutical solutions of preparation general formula (10) compound.The results are shown in following table.
Table
| Embodiment | Compound (10) filter cake % weight | Water % weight | Oxyethane umber in the adducts | Adducts % weight | Product appearance in the time of 25 ℃ | Viscosity milli handkerchief second |
| 2 3 4 5 6 7 | 30 30 30 30 40 40 | 10 15 0 10 0 0 | 8 9 10 10 15 20 | 60 55 70 60 60 60 | Limpid limpid limpid limpid of the slight slight lacteous of lacteous | 397 505 1060 575 1880 3263 |
Embodiment 8
Following material is packed in 1 liter of flask:
1 part of C of 600 grams
13-oxo alcohol is with the adducts of 10 parts of oxyethane;
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams; And
1 of 100 grams, the 2-propylene glycol.
Method with narration among the embodiment 1 obtains liquid preparation, at 25 ℃ be-clear solution, and viscosity was 702 handkerchief seconds in the least.
Embodiment 9
Following material is packed in 1 liter the flask:
The deionized water of 100 grams;
1 part of C of 600 grams
11-oxo alcohol is 11 parts ethylene oxide adduct together; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
Be used among the embodiment 1 method of narration, obtain liquid preparation, 25 ℃ be limpid solution, and viscosity was 397 handkerchief seconds in the least.
Embodiment 10
Following material is packed in 1 liter of flask:
The deionized water of 100 grams;
1 part of C of 420 grams
13-hydroxyl synthol is with the adducts of 8 parts of oxyethane;
1 part of C of 180 grams
13-hydroxyl synthol is with the adducts of 15 parts of oxyethane; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
Be used among the embodiment 1 method of narration, obtain liquid preparation, be clear solution down at 25 ℃, viscosity was 434 milli handkerchief seconds.
Embodiment 11
Following material is packed in 1 liter of flask:
The deionized water of 150 grams;
1 part of C of 385 grams
13-oxo alcohol is with the adducts of 8 parts of oxyethane;
1 part of C of 165 grams
13-oxo alcohol is with the adducts of 15 parts of oxyethane; And
The white dyes wet cake with general formula (10) (active substance that contains 50% weight) of 300 grams.
Being used among the embodiment 1 method of narration, obtaining liquid preparation, be limpid solution at 25 ℃, and viscosity was 550 handkerchief seconds in the least.
Embodiment 12
Following material is packed in 1 liter of flask:
The deionized water of 50 grams;
1 part of C of 455 grams
13-oxo alcohol is with 8 parts of ethylene oxide adducts;
1 part of C of 195 grams
13-oxo alcohol is with 15 parts of ethylene oxide adducts; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
Being used among the embodiment 1 method of narration, obtaining liquid preparation, be limpid solution at 25 ℃, and viscosity was 540 handkerchief seconds in the least.
Embodiment 13-16
Following material is packed in 1 liter of flask:
The deionized water of 100 grams;
1 part of C of 600 grams
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is with the adducts of 15 parts of oxyethane; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
Be used among the embodiment 1 method of narration, obtain liquid preparation (embodiment 13), preparation be limpid solution at 25 ℃, and viscosity was 1600 handkerchief seconds in the least.
With 1 part of C
12-C
14(embodiment 14 for the adducts of the same 20 parts of oxyethane of-Fatty Alcohol(C12-C14 and C12-C18); Viscosity 3261 milli handkerchief second); Or with 1 part of C
12-C
14(embodiment 15 for the adducts of the same 8 parts of oxyethane of Fatty Alcohol(C12-C14 and C12-C18); Viscosity 829 milli handkerchief second) replaces 1 part of C
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is with the adducts of 15 parts of oxyethane, or the amount that will have the wet cake (active substance that contains 50% weight) of the white dyes of general formula (10) without deionized water increases to 400 grams, and (embodiment 16; Viscosity 2417 milli handkerchief second) time, all obtains similar good result.
Embodiment 17 and 18
Following material is packed in 1 liter of flask:
100 gram deionized waters;
1 part of C of 420 grams
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is with the adducts of 8 parts of oxyethane;
1 part of C of 180 grams
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is with the adducts of 15 parts of oxyethane; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
The method that is used among the embodiment 1 narration makes liquid preparation (embodiment 17), and after filtering, preparation be limpid solution at 25 ℃, and viscosity 732 is handkerchief second in the least.
As 1 part of C
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is reduced to 300 grams with the adducts amount of 8 parts of oxyethane, and 1 part of C
12-C
14When-Fatty Alcohol(C12-C14 and C12-C18) increases to 300 grams (embodiment 18, viscosity 893 milli handkerchief seconds) with the adducts amount of 15 parts of oxyethane, also can obtain similar good result.
Embodiment 19 and 20
Following material is packed in 1 liter of flask:
The deionized water of 150 grams;
1 part of C of 385 grams
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is with the adducts of 8 parts of oxyethane;
1 part of C of 165 grams
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is with the adducts of 15 parts of oxyethane; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
The method that is used in narration among the embodiment 1 makes liquid preparation, and (embodiment 19; Viscosity 807 milli handkerchief second), after filtering, be limpid solution at 25 ℃.
As 1 part of C
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) is reduced to 275 grams with the adducts amount of 8 parts oxyethane, and 1 part C
12-C
14The adducts amount of the same 15 parts of oxyethane of-Fatty Alcohol(C12-C14 and C12-C18) increases to 275 grams, and (embodiment 20; Viscosity 913 milli handkerchief second) time, can obtain similar good result.
Embodiment 21-23
Following material is packed in 1 liter of flask:
1 part of tetramethylolmethane of 600 grams is with the adducts of 5 parts of oxyethane; With
The white dyes wet cake with general formula (10) (active substance that contains 50% weight) of 400 grams.
(embodiment 21 to make liquid preparation with the method for embodiment 1 narration; Viscosity was lower than for 500 milli handkerchief seconds), preparation is limpid solution at 25 ℃.
(embodiment 22 with the adducts of the same 7 parts of oxyethane of 1 part of three methanol-based propane with the adducts of 5 parts of oxyethane when 1 part of tetramethylolmethane; Viscosity 446 milli handkerchief second) or with the adducts of the same 20 parts of oxyethane of 1 part of three methanol-based propane (embodiment 23; Viscosity 558 milli handkerchief second) when replacing, obtains similar good result.
Embodiment 24-26
Following material is packed in 1 liter the flask:
The deionized water of 100 grams;
1 part of tetramethylolmethane of 600 grams is with the adducts of 5 parts of oxyethane; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
The method that is used in narration among the embodiment 1 makes liquid preparation, and (embodiment 24; Viscosity was lower than for 500 milli handkerchief seconds), preparation is limpid solution at 25 ℃.
(embodiment 25 when the adducts with 1 part of trihydroxymethyl propane, 7 parts of oxyethane together; Viscosity 101 milli handkerchief second); Or with 1 part of three methanol-based propane (embodiment 26 with the adducts of 20 parts of oxyethane; When viscosity 206 milli handkerchief second) replacing 1 part of tetramethylolmethane, obtain similar good result with the adducts of 5 parts of oxyethane.
Embodiment 27 and 28
Following material is packed in 1 liter the flask:
The deionized water of 100 grams;
1 part of Viscotrol C of 600 grams is with the adducts of 40 parts of oxyethane; And
300 grams have the wet cake (active substance that contains 50% weight) of the white dyes of general formula (10).
The suspension that obtains under agitation is heated to internal temperature reaches 70-80 ℃.After 4-5 hour, obtain almost limpid solution, wherein contain the not solvent components that is lower than 1% weight.This solution is cooled to 50-60 ℃ and filter, obtains yellow transparent solution, wherein contain the active substance of 15% weight, the water of 25% weight, viscosity was 3000 milli handkerchief seconds.After leaving standstill two days, it is limpid that solution keeps.
When the adducts with the same 11 parts of oxyethane of 1 part of Viscotrol C replaces the adducts of the same 40 parts of oxyethane of 1 part of Viscotrol C, obtain similar result.
Embodiment 29
Following material is packed in 1 liter the flask:
The C of 1132 grams
10-C
12The alkylpolyglycosides that-alkyl alcohol is made (53%); And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
The suspension that obtains under agitation is heated to internal temperature reaches 70-80 ℃.The water that separates evaporation.After 4-5 hour, obtain almost limpid solution, wherein contain the undissolved composition that is lower than 1% weight.Solution is chilled to 50-60 ℃, and filters.Obtain limpid dark brown solution.The active substance that contains 12% weight, the water of 42% weight, viscosity was 3500 milli handkerchief seconds.
Embodiment 30 and 31
Following material is packed in 1 liter of flask:
The molecular-weight average of 600 grams is 300 polyoxyethylene glycol; With
The white dyes wet cake with general formula (10) (active substance that contains 50% weight) of 400 grams.
The suspension that obtains under agitation is heated to internal temperature reaches 70-80 ℃.After 4-5 hour, obtain almost limpid solution, wherein contain the not solvent components that is lower than 1% weight.This solution is as cold as 50-60 ℃, and filters.Obtain limpid yellow solution, wherein contain the active substance of 20% weight and the water of 20% weight.After leaving standstill 2 hours, it is limpid that solution keeps.
When the mixture of the wet cake (active substance that contains 50% weight) of the white dyess of the deionized waters of 200 grams being used instead the deionized waters of 100 grams and 300 grams with the mixture of wet cake (active substance that contains 50% weight) of the white dyess with general formula (10) of 200 grams, then obtain similar result with general formula (10).
Embodiment 32
Following material is packed in 1 liter of flask:
The deionized water of 100 grams;
1 part of sorbitol monooleate of 600 grams is with the adducts of 20 parts of oxyethane; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
The suspension that obtains under agitation is heated to internal temperature reaches 70-80 ℃.After 4-5 hour, obtain almost limpid solution, wherein contain the not solvent components that is lower than 1% weight.This solution is as cold as 50-60 ℃, and filters.Obtain yellow clear solution, wherein contain the active substance of 15% weight, the water of 25% weight, viscosity was 3300 milli handkerchief seconds.After leaving standstill two days, it is limpid that solution keeps.
Embodiment 33
Following material is packed in 1 liter the flask:
The deionized water of 100 grams;
The lauric acid Polyglycerine alcohol ester of 1 part of ethoxylation of 600 grams; And
The wet cake (active substance that contains 50% weight) of the white dyes with general formula (10) of 300 grams.
The suspension that obtains under agitation is heated to interior humidity reaches 70-80 ℃.After 4-5 hour, obtain clear solution, wherein contain the not solvent components that is lower than 1% weight.This solution is as cold as 50-60 ℃, and filters.Obtain yellow clear solution, wherein contain the active substance of 15% weight, the water of 25% weight, viscosity was 517 milli handkerchief seconds.After leaving standstill 6 days, it is limpid that solution keeps.
Claims (35)
1. liquid fluorescent whitening agent formulation, this preparation are the viscosity 50-5000 milli handkerchief solution of second, and contain:
A) account for the following formula anionic optical brighteners of total formulation weight amount 10-25%
Or
In the formula, R
2And R
3Being independent of each other, respectively is OH, NH
2, O-C
1-C
4-alkyl, O-aryl, NH-C
1-C
4-alkyl, N (C
1-C
4-alkyl)
2, N (C
1-C
4-alkyl) (C
1-C
4-hydroxyalkyl), N (C
1-C
4-hydroxyalkyl)
2, NH-aryl, morpholino, S-C
1-C
4-alkyl, S-C
1-C
4-aryl, Cl or OH; R
4Be H, SO
3M, O-C
1-C
4-alkyl, CN, Cl, COO-C
1-C
4-alkyl, or CON (C
1-C
4-alkyl)
2M is H, Li, and Na, K, Ca, Mg, ammonium, single-, two-, three-or four-C
1-C
4-alkylammonium, single-, two-or three-C
1-C
4-hydroxyalkyl ammonium or by C
1-C
4-alkyl and C
1-C
4The ammonium of-hydroxyalkyl mixture two-or three-replace; And p is 0 or 1;
B) account for the water of total formulation weight amount 15-35%; And
C) account for the nonionogenic tenside of total formulation weight amount 45-75%, its general formula is:
In the formula, m is 1,2,3 or 4, and when m was 1, R was C
8-C
18-alkyl residue or C
8-C
18-alkyl carboxyl residue; When m was 2, R was the C that has removed two hydroxyls
2-C
4The aklylene glycol residue; When m was 3, R was a residue of having removed three methanol-based propane of three hydroxyls; When m was 4, R was a tetramethylolmethane residue of having removed four hydroxyls, R
1Be hydrogen, methyl or ethyl; N is a numeral among the 1-40.
2. the preparation of claim 1, wherein, m is 1,3 or 4, when m is 1, R is C
8-C
18-alkyl residue or C
8-C
18-alkyl carboxyl residue, when m was 3, R was three methanol-based propane residues of having removed three hydroxyls, when m was 4, R was a tetramethylolmethane residue of having removed four hydroxyls; R
1Be hydrogen, methyl or ethyl; N is a numeral among the 1-40.
3. the preparation of claim 1, the viscosity of preparation are 100-3500 milli handkerchief second.
4. the preparation of claim 3, the viscosity of preparation are 100-1000 milli handkerchief second.
5. the preparation of claim 1 wherein contains the anionic optical brighteners that accounts for total formulation weight amount 15-20% weight.
6. the preparation of claim 1 wherein contains the water that accounts for total formulation weight amount 20-30% weight.
7. the preparation of claim 1 wherein contains the nonionogenic tenside with general formula (1) that accounts for total formulation weight amount 50-70% weight.
8. the preparation of claim 1, wherein, R
2And R
3Being independent of each other, respectively is methoxyl group, phenoxy group, NH
2, NH-methyl, N (methyl)
2, N (methyl) (hydroxyethyl), NH-ethyl, N (hydroxyethyl)
2, NH-phenyl, morpholino, S-methyl, S-phenyl, Cl or OH.
9. the preparation of claim 1, its formula of (2) compound one of have in the following structural:
Or
10. the preparation of claim 1, wherein, in general formula (3) compound, R
4Be H or Cl, p is 1.
11. the preparation of claim 1, wherein, general formula (3) compound has one of following structural:
Or
12. the preparation of claim 11, wherein, general formula (3) compound is compound or its crystallized form of general formula (10).
13. the preparation of claim 1, wherein, the mixture of two or more anionic optical brighteners as the composition of preparation a).
14. the preparation of claim 1, wherein, water uses together with one or more aklylene glycols or polyalkylene glycol.
15. the preparation of claim 14, wherein, aklylene glycol is ethylene glycol or 1, the 2-propylene glycol.
16. the preparation of claim 14, wherein, polyalkylene glycol is polyoxyethylene glycol or polypropylene glycol.
17. each preparation among the claim 14-16, wherein, the consumption of aklylene glycol or polyalkylene glycol accounts for the 0-15% of total formulation weight amount.
18. aforesaid right requires each preparation of 1-16, wherein, in general formula (1) compound, m is 1, and compound is that the oxyethane of 3-20 mole is with 1 mole of C
8-C
18-alkyl monocarbon alcohol add compound.
19. the preparation of claim 18, wherein, adding compound is same 1 mole of C of oxyethane of 3-20 mole
11-C
13The oxyethane of adding compound or 8-20 mole of-oxo alcohol is 1 mole C together
12-C
14-Fatty Alcohol(C12-C14 and C12-C18) add compound.
20. each preparation among the claim 1-16, wherein, in the compound of general formula (1), m is 2, and compound is that the oxyethane of 2-20 mole is with 1 mole C
2-C
4-aklylene glycol add compound.
21. the preparation of claim 20, wherein, C
2-C
4Aklylene glycol is ethylene glycol or positive butylidene glycol.
22. the preparation of claim 20, wherein, C
2-C
4Aklylene glycol is a propylene glycol.
23. the preparation of claim 22, wherein, general formula below in the compound of general formula (1), having:
In the formula, x and y respectively are integer among the 1-10.
24. the preparation of claim 23, wherein, x and y respectively are an integer among the 1-5.
25. the preparation of claim 24, wherein, the summation of x and y is 10.
26. each preparation among the claim 1-16, wherein, in the compound of general formula (1), m is 3, and compound is the add compound of the oxyethane of 3-20 mole with 1 mole of three methanol-based propane.
27. the preparation of claim 26, wherein, compound is the add compound of the oxyethane of 7-20 mole with 1 mole of three methanol-based propane.
28. each preparation among the claim 1-16, wherein, in the compound of general formula (1), m is 4, and compound is the add compound of the oxyethane of 4-20 mole with 1 mole of pentaerythritol.
29. the preparation of claim 28, wherein, compound is the add compound of the oxyethane of 5-20 mole with 1 mole of pentaerythritol.
30. aforesaid right requires each preparation of 1-16, wherein, the mixture of the compound of two or more general formulas (1) is as the composition c of preparation).
31. aforesaid right requires each preparation of 1-16, wherein, also has one or more auxiliarys, these auxiliarys are selected from can effectively regulate the stablizer of the flowability of preparation, foam reducing composition, alkali reagent, fabric softener, anti redeposition agent, antioxidant, washing assistant and spices.
32. the production method of claim 1 preparation, this method comprise the anionic optical brighteners with general formula (2) or (3), water and general formula (1) compound, and with the mixture homogenization that obtains.
33. the method for claim 32 is wherein also mixed auxiliary, described auxiliary is selected from can effectively regulate the stablizer of the flowability of preparation, foam reducing composition, alkali reagent, fabric softener, anti redeposition agent, antioxidant, washing assistant and spices.
34. the method for claim 32, wherein, this method is to carry out at temperature 40-100 ℃.
35. produce the method for washing composition, this method is included in the preparation that adds the claim 1 of aequum in the detergent composition, then with the mixture homogenization that obtains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9621421A GB2318360A (en) | 1996-10-15 | 1996-10-15 | Fluorescent whitening agent formulation |
| GB9621421.8 | 1996-10-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1179466A CN1179466A (en) | 1998-04-22 |
| CN1165606C true CN1165606C (en) | 2004-09-08 |
Family
ID=10801404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971204411A Expired - Fee Related CN1165606C (en) | 1996-10-15 | 1997-10-14 | Fluorescent whitening agent formulation |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0837124B1 (en) |
| JP (1) | JPH10152695A (en) |
| KR (1) | KR100503774B1 (en) |
| CN (1) | CN1165606C (en) |
| AU (1) | AU732991B2 (en) |
| BR (1) | BR9705030A (en) |
| DE (1) | DE69726544T2 (en) |
| ES (1) | ES2210486T3 (en) |
| GB (1) | GB2318360A (en) |
| ID (1) | ID18528A (en) |
| MX (1) | MX9707800A (en) |
| TW (1) | TW400379B (en) |
| ZA (1) | ZA979178B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238099A (en) * | 2015-10-12 | 2016-01-13 | 山西青山化工有限公司 | Liquid fluorescent whitening agent for whitening soup and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167787C (en) | 1999-08-16 | 2004-09-22 | 西巴特殊化学品控股有限公司 | Liquid fluorescent whitening agent formulation |
| JP4567975B2 (en) * | 2002-02-25 | 2010-10-27 | チバ ホールディング インコーポレーテッド | Method of processing fiber material |
| RU2368655C2 (en) * | 2003-09-19 | 2009-09-27 | Циба Спешиалти Кэмикэлз Холдинг Инк. | Aqueous solutions of fluorescent optical bleaching agents |
| KR100689260B1 (en) * | 2005-05-24 | 2007-03-02 | 삼원산업주식회사 | Fluorescent Whitening Agent of stilbene type having property of preventing oxidation and Process of producing thereof |
| KR101421622B1 (en) * | 2012-06-29 | 2014-07-23 | 삼원산업주식회사 | Fluorescent Whitening Agent of stilbene type havingproperty of preventing oxidation and Process ofproducing thereof |
| CA2936149A1 (en) * | 2014-01-20 | 2015-07-23 | The Procter & Gamble Company | Fluorescent brightener premix |
| CN104862120A (en) * | 2015-04-09 | 2015-08-26 | 广州立白企业集团有限公司 | Preparation method of fluorescent brightener water solution for detergent |
| CN106087384A (en) * | 2016-06-21 | 2016-11-09 | 太仓市东明化工有限公司 | A kind of fabric water-resistant type fluorescent whitening agent |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953380A (en) * | 1970-10-28 | 1976-04-27 | Colgate-Palmolive Company | Liquid detergent |
| US4298490A (en) * | 1978-12-22 | 1981-11-03 | Ciba-Geigy Corporation | Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents |
| US4661287A (en) * | 1983-10-05 | 1987-04-28 | Colgate-Palmolive Company | Stable soil release promoting enzymatic liquid detergent composition |
| US4764302A (en) * | 1986-10-21 | 1988-08-16 | The Clorox Company | Thickening system for incorporating fluorescent whitening agents |
| EP0323399B1 (en) * | 1987-11-27 | 1993-02-17 | Ciba-Geigy Ag | Optical brightener dispersion |
| US5149463A (en) * | 1989-04-21 | 1992-09-22 | The Clorox Company | Thickened acidic liquid composition with sulfonate fwa useful as a bleaching agent vehicle |
| EP0427670A1 (en) * | 1989-11-07 | 1991-05-15 | Ciba-Geigy Ag | Liquid detergent |
| IT1237754B (en) * | 1989-11-08 | 1993-06-17 | Sigma Prodotti Chimici Srl | OPTICAL BLEACH LIQUID COMPOSITION. |
| CH682748A5 (en) * | 1991-11-07 | 1993-11-15 | Ciba Geigy Ag | A storage-stable formulation of optical brightener. |
| KR0161894B1 (en) * | 1991-11-08 | 1999-01-15 | 구자홍 | A scroll compressor |
| MY109837A (en) * | 1992-06-30 | 1997-08-30 | Ciba Specialty Chemicals Holding Inc | Hydrates of the disodium salt or dipotassium salt of 4, 4''-bis (2-sulfostyryl)bipheny] |
| CH686959A5 (en) * | 1992-12-22 | 1996-08-15 | Ciba Geigy Ag | A storage-stable formulation of optical brighteners. |
| US5425898A (en) * | 1993-09-27 | 1995-06-20 | The Clorox Company | Thickening system for incorporating fluorescent whitening agents |
| GB9323250D0 (en) * | 1993-11-11 | 1994-01-05 | Unilever Plc | Process for the production of a detergent composition |
| JPH07286198A (en) * | 1994-04-15 | 1995-10-31 | Lion Corp | Method for producing granular nonionic detergent composition |
| IT1270004B (en) * | 1994-09-23 | 1997-04-16 | 3V Sigma Spa | "FORMULATIONS OF OPTICAL BLEACHERS" |
| GB9509291D0 (en) * | 1995-05-06 | 1995-06-28 | Ciba Geigy Ag | Formulations |
-
1996
- 1996-10-15 GB GB9621421A patent/GB2318360A/en not_active Withdrawn
-
1997
- 1997-08-30 TW TW086112472A patent/TW400379B/en not_active IP Right Cessation
- 1997-10-06 ES ES97810741T patent/ES2210486T3/en not_active Expired - Lifetime
- 1997-10-06 DE DE69726544T patent/DE69726544T2/en not_active Expired - Fee Related
- 1997-10-06 EP EP97810741A patent/EP0837124B1/en not_active Expired - Lifetime
- 1997-10-10 MX MX9707800A patent/MX9707800A/en active IP Right Grant
- 1997-10-14 AU AU41000/97A patent/AU732991B2/en not_active Ceased
- 1997-10-14 CN CNB971204411A patent/CN1165606C/en not_active Expired - Fee Related
- 1997-10-14 BR BR9705030A patent/BR9705030A/en not_active IP Right Cessation
- 1997-10-14 ZA ZA9709178A patent/ZA979178B/en unknown
- 1997-10-14 KR KR1019970052433A patent/KR100503774B1/en not_active IP Right Cessation
- 1997-10-14 ID IDP973434A patent/ID18528A/en unknown
- 1997-10-15 JP JP9280987A patent/JPH10152695A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238099A (en) * | 2015-10-12 | 2016-01-13 | 山西青山化工有限公司 | Liquid fluorescent whitening agent for whitening soup and preparation method thereof |
| CN105238099B (en) * | 2015-10-12 | 2017-07-07 | 山西青山化工有限公司 | One kind brightens soap liquid fluorescent whitening agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9705030A (en) | 1999-06-15 |
| TW400379B (en) | 2000-08-01 |
| KR19980032785A (en) | 1998-07-25 |
| EP0837124A3 (en) | 1999-01-20 |
| AU732991B2 (en) | 2001-05-03 |
| EP0837124A2 (en) | 1998-04-22 |
| ID18528A (en) | 1998-04-16 |
| KR100503774B1 (en) | 2005-10-13 |
| ES2210486T3 (en) | 2004-07-01 |
| EP0837124B1 (en) | 2003-12-03 |
| MX9707800A (en) | 1998-04-30 |
| AU4100097A (en) | 1998-04-23 |
| DE69726544T2 (en) | 2004-09-30 |
| DE69726544D1 (en) | 2004-01-15 |
| JPH10152695A (en) | 1998-06-09 |
| GB2318360A (en) | 1998-04-22 |
| CN1179466A (en) | 1998-04-22 |
| GB9621421D0 (en) | 1996-12-04 |
| ZA979178B (en) | 1998-04-15 |
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