JPS5820986B2 - Kogaku Teki Elephant Hakuzai - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for making a slurry of distilbene-type optical brighteners.

Distilbene-type optical brighteners are often used in the form of a dry powder made by transferring the wet filter cake to a plate and then drying it in an oven for several hours.

Because of the handling difficulties of dry powders and dust hazards, it is advantageous to use the brightener as an aqueous slurry.

In practice, attempts have been made to slurry the dry powder and mix the wet filter cake with water, but these result in slurries that are non-uniform and tend to settle out very quickly, resulting in whitening products. and has not been successful because it affects cold water stainability.

It is also difficult to turn dry powder into a slurry.

Through research, the inventors have determined that a homogeneous, thixotropic brightener slurry can be made by mixing a wet filter cake of brightener with a dispersant.

Such a slurry becomes a gel-like substance and is kept for a long time, e.g.
Since no significant precipitation occurs during static storage for two weeks, no noticeable precipitation occurs during storage.

In addition to the above-mentioned excellent properties with respect to settleability, this slurry has a viscosity that makes it easier to handle than in powdered form, since it can be removed from the storage tank by gravity or by pump, and the dust hazards that occur in powdered form are eliminated. It has characteristics.

Moreover, when combined with spray drying detergents, no deterioration in brightening products or cold water dyeability occurs.

The thixotropic slurry according to the present invention is as follows.

1. The viscosity at a constant shear rate, as measured by a Brookfield viscometer, decreases with time until equilibrium is reached.

This equilibrium usually reaches about a monomer, after which the viscosity remains constant.

2. Viscosity decreases as the shear rate increases.

The present invention is based on the general formula R-CH=
CH-X-CH=CH-R2(I) (in this formula, X is =C
an unsubstituted or substituted diphenylene residue bonded to the H-group in the 4- and 4′-positions;
R1 and R2 are each independently an unsubstituted or substituted phenyl group, an unsubstituted or substituted diphenyl group.

an unsubstituted or substituted naphthyl group or an unsubstituted or substituted pyridyl group, at least one of the ring members R1, R2 and X
thixotropy of compounds having preferably functionally modified sulfonic acid groups, sulfonic acid groups, preferably functionally modified carboxylic acid groups, nitrile groups, hydroxyl groups, mercapto groups or methyl groups) Regarding the production of slurry.

According to the present invention, in a method for preparing a thixotropic slurry containing 15 to 60% by weight based on the total weight of the slurry by mixing the compound represented by the general formula (1) with a dispersant, The wet filter cake and the resulting slurry are thixotropic.

Therefore, its tendency to seize during static storage is reduced.

The Brookfield viscosity of the slurry is 6r, p, m.

2,000 to 10,000 centipoise at 12 r, p, m, 1,000 to 3,50 centipoise
0 centipoise and up to 2.000 centipoise at 60 r, p, m, by mixing with an amount of dispersant to make the thixotropic slurry.

The wet filter cake can contain 20-80% solids depending on conditions, but typically contains 35-55% solids.

Compounds of formula (I) which are particularly valuable for making homogeneous thixotropic slurries are those of the general formula 1 in which R1 and R2 are phenyl groups, such as those of the general formula (in which Xl is a sulfonic acid group or an alkali metal group). is a salt, and X2 is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof, a halogen atom, or 1 to 4 carbon atoms.
or a carboxylic acid group or an alkali metal salt thereof, and X3 is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon atom an alkoxy group having 1 to 4 carbon atoms, a carboxylic acid group or an alkali metal salt thereof, a carbalkoxy group having 2 to 5 carbon atoms, or a cyano group, and X4 is a hydrogen atom, a sulfonic acid group or an alkali thereof; a metal salt, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, the group X2 is preferably a hydrogen atom or a chlorine atom, and X3 is preferably a is a sulfonic acid group or its salt, and X4 is preferably a hydrogen atom or a chlorine atom)
Compounds and general formulas (in this formula, A1 is an alkali metal sulfonate group, a halogen atom, or a hydrogen atom, and A2 is a 10-gen atom or a hydrogen atom, and the group A1 is preferably sodium sulfonic acid) or a chlorine atom, and the group A2 is preferably a hydrogen atom).

If the concentration of the compound of formula (1) in the slurry is too high, the slurry will expand and solidify (dilatant).
This makes it difficult to pump the slurry.

This expansion and solidification (dilata-nc)
y) can be overcome by dilution with water or an aqueous electrolyte solution; however, if the concentration is too low, the precipitation stability will be weakened.

The desired proportion of the compound of formula (1) present in the slurry can be obtained by adding water, aqueous electrolyte solution, slurry or dry powder to the wet filter cake.

This water may be added together with a dispersant.

The proportion of the compound of formula (1) present in the slurry is advantageously from 20 to 60% by weight, preferably from 20 to 45% by weight, based on the weight of the slurry.

The slurry is then mixed with the dispersant until homogeneous.

Mixing can be carried out, for example, in a homogenizer.

A thixotropic slurry under static storage becomes a gel-like body and can be easily made fluid by stirring.

This reduces the viscosity and allows the slurry to be pumped or drained under its own weight.

Dispersants can be anionic, cationic or nonionic surfactants.

Suitable surfactants include:

Sodium salt of the condensation product of naphthalene sulfonic acid and formaldehyde.

Sodium salt of diptylnaphthalene sulfonic acid.

Condensation product of caprylic wax and ethylene oxide.

Mixture of cyclohexanol and stearamide.

Sodium salt of sulfonated oil.

Bis(2-hydroxyethyl)tallowamine oxide.

Monofatty acid ester or monoresin acid ester of polyoxyethylene glycol.

Amphoteric N-coco-α-aminobutyric acid.

Polymer of propylene oxide-ethylene oxide mixture.

Organic crystalline water-soluble wax or its hemi-sodium salt.

Non-ionic long chain polyoxyethylene ether condensate.

The amount of dispersant added to the wet filter cake is generally from 0.1 to 5% by weight relative to the wet filter cake, preferably the proportion of dispersant is 0.5% by weight relative to the wet filter cake.
-2% by weight.

If desired, a gelling agent can also be added to the slurry.

Examples of the gelling agent include carboxyvinyl polymer, highly penite magnesium silicate, magnesium montmorillonite, pure silicic acid fine powder or trade name Cal-0-511-M-
There is fumed silica commercially available in No. 5.

The amount of gelling agent added can vary, but is usually within the range of 0.1 to 2% by weight of the wet filter cake.
Preferably it is within the range of 0.1 to 1% by weight.

If desired, an electrolyte can be added to the slurry.

The electrolyte is sodium chloride, sodium sulfate, sodium carbonate or the corresponding potassium salt.

The amount of electrolyte is 4-25% by weight based on the total weight of the slurry.
, preferably around 5 to 20 weight.

Additionally, cold water dyeability can be improved by milling the slurry.

Cold water dyeability is determined by the surface area of the particles, the particle size being adjusted during the manufacture of the compound or obtained by milling the slurry.

Slurry viscosity is related to particle concentration and surface area.

The Brookfield viscosity is preferably 2,000 to 5,000 centipoise at 6r, p, m, and 6
0r, p, m, preferably 50 to 1.000
It is centipoise.

The homogeneous slurry thus produced can be diluted or thickened as desired.

The production of an aqueous slurry according to the invention has the advantage that the compound of formula (1) is produced in fewer steps and more quickly in a form suitable for immediate use than in the production of a dry powder, with correspondingly lower losses during production. It is advantageous.

Further, the slurry of the present invention can be used for several weeks, for example 12 weeks.

or longer during storage without significant precipitation and without disturbing properties when combined with cleaning agents.

Optionally, the wet filter cake of two or more compounds of formula (1) is mixed with a dispersant or the resulting 2
A slurry containing two or more types of compounds of formula (1) can be prepared by further mixing the slurry with an electrolyte if desired.

This slurry can then be mixed into the cleaning agent by weighing the required amount directly from the tank into the mixer containing the cleaning agent slurry just before spray drying.

The amount of this slurry added is 0.1 based on the total weight of the cleaning agent.
~3.0% by weight.

The present invention also provides a cleaning composition prepared by adding the slurry prepared above to a cleaning agent, which can then be mixed and dried.

All parts in the following examples are parts by weight.

Example: 0.5 parts of the sodium salt of the condensation product of naphthalene sulfonic acid and formaldehyde, 0.7 parts of magnesium silicate commercially available under the trade name "Benaqua", 74.7 parts of water, and a compound represented by the formula 24.1 parts.

This is then first mixed by hand and then 5ilverson.
Homogenize with a mixer.

Brookfield viscosity is 6r, p, m, odor is 3,
520 centipoise, 60r, p, m, i, o
No significant precipitation was observed even after 12 weeks at less than 0.0 centipoise.

Although the present invention has been described in detail above, specific examples of the configuration of the present invention can be summarized as follows.

(1) General formula (In this formula, Xl is a sulfonic acid group or an alkali metal salt thereof, and X2 is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof, or a halogen atom.

X is an alkyl group or carboxylic acid group having 1 to 4 carbon atoms or an alkali metal salt thereof;

is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof,
a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxylic acid group or an alkali metal salt thereof, a carbalkoxy group having 2 to 5 carbon atoms, or a cyan group; , and X4 is a hydrogen atom, a sulfonic acid group, or an alkali metal salt thereof.

3. The method according to claim 2, wherein a compound of the following formula is used: a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

(2) X is a sulfonic acid group or its sodium salt, X2 is a hydrogen atom or a chlorine atom, X3 is a sulfonic acid group or its sodium salt, or a chlorine atom, and X4 is a hydrogen atom or a chlorine atom. It is an atom.

A compound of general formula (II) is used. The method described in the preceding section (1).

(3) The compound of formula (I) is a compound represented by the general formula (in this formula, Am is an alkali metal sulfonate group, a halogen atom or a hydrogen atom, and A2 is a halogen atom or a hydrogen atom).

The method described in the preceding section (2).

(4) In the above formula, the group AI is a sodium sulfonate group or a chlorine atom, and the group A2 is a hydrogen atom.

The method described in the preceding section (3). (5) The proportion of the compound of formula (I) present in the slurry is 20% by weight based on the weight of the slurry.
~45% by weight.

The method according to claim 2 and any one of the preceding claims (1) to (4).

(6) The dispersant is a sodium salt of a condensation product of naphthalene sulfonic acid and formaldehyde.

The method according to claim 2 and any one of the preceding claims (1) to (5).

(F) The amount of dispersant added to the filter cake is 0.1 to 5% by weight based on the wet filter cake.

The method according to claim 2 and any one of the preceding claims (1) to (6).

(8) Add gelling agent to slurry.

The method according to claim 2 or any one of the preceding claims (1) to (force).

(9) The method according to item (8) above, wherein the gelling agent is highly beneficent magnesium silicate.

(10) The gelling agent is 0.1 to 2.0% by weight based on the weight of the wet filter cake.

The method according to item (8) or (9) above.

A strong electrolyte is added to the slurry in an amount of 4-25% by weight based on the Uυ slurry.

The method according to claim 2 and any one of (1) to (lI) above.

(12) The electrolyte is sodium chloride.

The method described in the previous section 0υ.

Claim 2, wherein the α9 slurry is subjected to a grinding process.
The method according to any one of Items 1 and 1 to 12 above.

α 2,000 to 5,000 centipoise at Brookfield viscosity of 6r, p, m, 60r, p,
m.

It is 50 to 1,0007 inch poise.

The method according to claim 2 and any one of items (1) to 03).

α General formula (In this formula, Xl is a sulfonic acid group or an alkali metal salt thereof, and X2 is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or A carboxylic acid group or an alkali metal salt thereof.

X3 is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxylic acid group or an alkali metal salt thereof, a carbon atom a carbalkoxy group or cyano group having 2 to 5 atoms, and X4 is a hydrogen atom, a sulfonic acid group or an alkali metal salt thereof,
It is characterized by containing an optical brightener represented by a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

The thixotropic slurry according to claim 1.

(16) In the above formula (I), Xl is a sulfonic acid group or its sodium salt, X2 is a hydrogen atom or a chlorine atom, X3 is a sulfonic acid group or its sodium salt, or a chlorine atom, and X4 is hydrogen The thixotropic slurry αη according to the preceding paragraph (15), characterized in that it contains an optical brightener of the general formula (II), which is an atom or a chlorine atom (in this formula, A1 is an alkali metal sulfonate) Base.

It is characterized by containing an optical brightener represented by the following formula: halogen atom or hydrogen atom, A2 is /'% halogen atom or hydrogen atom.

The thixotropic slurry according to claim 1.

0al In the above formula (III), the group Al is a sulfonic acid) l) The above item α characterized in that it contains an optical brightener of the general formula (If) where the group A2 is a ram group or a chlorine atom and the group A2 is a hydrogen atom. ′? thixotropic slurry described in ).

α-U Optical brightener is added at 20 to 4% based on the total weight of the slurry.
It is characterized by containing 5% by weight.

The thixotropic slurry according to claim 1.

(20) The dispersant is a salt of a condensation product of naphthalene sulfonic acid and formaldehyde.

The thixotropic slurry according to claim 1 has a Brookfield viscosity of 6r, p, m, 2.000 to 5,000 centipoise in odor, 60r,
p.m.

50 to 1,000 centipoise.

The thixotropic slurry according to claim 1 0 (22) The amount of the gelling agent is 0.1 to 0.1 to
It is characterized by containing 2.0% by weight.

The thixotropic slurry according to claim 1.

(23) The gelling agent is highly beneficent magnesium silicate.

The thixotropic slurry described in the preceding section (22). (To) The slurry is characterized by containing 4 to 25% by weight of a strong electrolyte based on the total weight of the slurry.

The thixotropic slurry according to claim 1.

Claims (1)

[Claims] 1 B) General formula % formula % () (in this formula, X is an unsubstituted or substituted diphenylene group bonded to the -CH= group at the 4- and 4'-positions) and Ro and R2 are each unsubstituted or substituted phenyl group, unsubstituted or substituted diphenyl group. Unsubstituted or substituted naphthyl group or unsubstituted or substituted pyridyl group, at least one of the ring systems R1, R2 and X
(optionally functionally modified sulfonic acid groups, sulfonic acid groups, optionally functionally modified carboxylic acid groups, nitrile groups, hydroxyl groups, mercapto groups or methyl groups) 15 to 60% by weight of the slurry based on the total weight of the slurry. (0) The amount of dispersant is 0.1 based on the total weight of the slurry.
Contains ~5% by weight, and has a Brookfield viscosity of 2,000 to 10,000 centipoise at 6r, p, m, and 60
It is characterized by up to 2,000 centipoise in r, p, and m. Thixotropic slurry. 2 General formula % Formula % (1) (In this formula, X is an unsubstituted or substituted diphenylene group bonded to the -CH= group at the 4- and 4'-positions, and R1 and R2 are Independently of each other, unsubstituted or substituted phenyl, unsubstituted or substituted diphenyl, unsubstituted or substituted naphthyl or unsubstituted or or a substituted pyridyl group, in which at least one of the ring systems R1, R2 and X is an optionally functionally modified sulfonic acid group,
A suspension containing 15 to 60% by weight of a compound having a sulfonic group, an optionally functionally modified carboxylic acid group, a nitrile group, a hydroxyl group, a mercapto group or a methyl group, based on the total weight of the slurry. The preparation of the modified slurry consists of mixing the wet filter cake obtained during the preparation of this compound with a dispersant. It is thixotropic and therefore has a low tendency to settle during its static storage and has a Brookfield viscosity of 6 r,p,m. 2,000 to 10,000 centipoise at 12 r, p, m, 1,000 to 3,500
centipoise and 2 at 60 r, p, m,
,000 centipoise. A method for producing the thixotropic slurry.