JPS6197492A - High concentrated pulp digestion aid aqueous solution - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Objective "Field of industrial application" The present invention provides 1,4-Shihi I with substantially increased solubility.
I'Ayu'trahi1'-1'quinone (hereinafter referred to as 1,4-Nhydro:Janlrahi1'1'-1'N) is referred to as rDIIAIIQ
It's called J. ) type of dialkali metal salts, particularly disodium salts, as a main ingredient.

[Prior art j Anne 1 laquinones, 1,4,4a,9a-tetrahydroan 1:1. Nons, D II A II QEQ or GJ Using the cinalium salt, lignocellulose material is delignified into pulp in an alkaline cooking liquor such as soda cooking liquor, Graph 1 cooking liquor, or sulfite cooking liquor. The solution method is already known and has been put into practical use.
No. 5-1398, Special Publication No. 57-1923, etc.).

Practically speaking, 1,4 naph [quinone and butadiene are combined
-Russ-Alder-L4,4 obtained by reaction
a, 9a-i-l lahydroanthraquinone (rT
It's called ITAQJ. ) is dissolved in an aqueous solution of lithium hydroxide and used as an aqueous solution of D II A II Q salt in a bulb cooking system.

“The problem that the invention is trying to solve” D It
Aqueous solution of disodium salt of A II Q4. I. It is solid and liquid compared to water-insoluble quinone-based cooking aids such as anthraquinone, so it is easier to handle and feed into the cooking system, and moreover, it quickly transforms into lignocellulosic materials in the cooking system. Although it has the advantage of being able to permeate and exert its effects, it is usually transported to a place of use far from the place of manufacture, so it is necessary to avoid precipitation of crystals even under natural environmental conditions, and it is generally used as a disodium salt. It is handled as an aqueous solution of about 24χ, which has the disadvantage of increasing transportation costs per unit volume.

The present inventors have developed this D
A highly concentrated aqueous solution of an alkali metal salt such as a disodium salt of D II A II Q, which can substantially increase the concentration of the disodium salt aqueous solution of II A II Q and stably maintain the disodium salt solution without precipitating or causing crystals. We conducted extensive research with the aim of obtaining the following. As a result, this D
The present invention was completed by discovering that the above problems could be solved by incorporating the disodium salt of I-I A II Q into an aqueous solution.

(2) Structure of the invention ``Means and effects for solving the problems'' The present invention provides alkylene oxa-ide adducts of polyhydric alcohols,
Substantially enhanced solubility comprising one or more agents selected from the group of surface-active substances consisting of soluble alcohols, sulfosuccinate salts and anionic polymeric emulsifying dispersants. It is a highly concentrated pulp cooking aid aqueous solution whose main ingredient is a dialkali metal salt of 1,4-dihydroanthrahydequinone.

Examples of dialkali metal salts of D It A II Q used in the present invention include salts of sodium, potassium J1, and lithium, but thorium, which is inexpensive, is usually preferred.

The r)llAIIQs used in the present invention include DI
Substituted D I-1A substituted with IAIIQ or its lower argyl, lower)'lecone or 1.1ha')phosphorus
IIQ is an example.

Substitution D I-I A 1) As for 0, its 2nd and 3rd positions
Substituted compounds are preferred because they can be produced extremely easily. For example, 27thyl DI (AITQ, 2-ethyl D
it A II Q, 1 to 2,3-dimethyl Dll
) Q, 2-me1xyD II A II Q, 2chloroD It A II Q is 49%.

The above D II A II Q and substitution D! l A I
An aqueous alkali metal salt solution of IQ can generally be produced by the following method.

1.4-naphthoquinone and 1,3-butadiene or 1 substituted at the 2 and 3 positions corresponding to the above substituted DIIAIIQ
, 3-butanene in the presence or absence of a solvent according to the usual Diels-Alder reaction method, and the (J adduct (so-called T II A Q) is hydroxided. etc. in the absence of oxygen at 70 to 150°C, preferably 80 to 100°C, about 1
Dissolve for 0 minutes to 2 hours, usually under stirring. At this time, T
Hydrogens at positions 4a and 9a of 11AQs are isomerized to positions 9 and 10, and the dialkali metal salts of D II A II Qs are formed and dissolved. Of course, Tl1AQta is once isomerized to form DI-IATIQs, which is then converted into sodium hydroxide.
, etc. Caustic alkaline water? The number of liquids may be ambiguous.

In the present invention, the Diels-Alder reaction adduct may contain, for example, about 0 to 30x of 1,4-dihydroan l-uquinone in which the (J adduct is partially oxidized), or Furthermore, even if several χ of oxidized anthraquinones are mixed in, there is no problem since all of them are dissolved in the aqueous caustic alkali solution and can be handled in the same manner as the aqueous pulp cooking aid solution of the present invention.

In this case, the amount of alkali metal hydroxide used is TIIAQ
or T) IIAIIQ or more, preferably 2.1 to 2.5 times the mole, more preferably 2.1 to 2.5 times the mole
2.4 times the mole is good. The concentration of the alkali metal hydroxide is selected from the range below the solubility of the alkali metal salt of D II A HQ at the operating temperature, but generally 1.
0 to 20 weight ■χ is adopted. The obtained D II A
The aqueous solution of the alkali metal salt of class II Q is the aqueous solution of the alkali metal salt of D
It can also be used after being diluted as necessary to achieve the desired concentration. The concentration of the aqueous alkali metal salt solution of D If A If Qt[i of the present invention is determined at the time of handling (for example,
Although it varies depending on the minimum holding temperature of the environment (transportation, storage, etc.) and the type and amount of the drug used, it generally ranges from around the concentration equivalent to its solubility to about 10 to about 20
You can choose from increased concentrations. For example, D It A
1) In the case of the disodium salt of Q, D II A
About 25% or more as disodium salt of IIQ, preferably about 26 to about 33χ, more preferably about 28 to about 3
It is 1χ.

The surfactant used in the present invention is one selected from the group of alkylene oxa-1' addition of polyhydric alcohol, poorly water-soluble alcohol, sulfosuccinate salt, and anionic polymer emulsifying dispersant; A surfactant consisting of two or more types of drugs. The surfactants of the present invention may be used alone or in combination of two or more, and there are cases where a synergistic effect is produced by mixing them.

Examples of the fullylene oxide adducts of polyhydric alcohols used in the present invention include the following.

As the polyhydric alcohol constituting the alkylene oxide adduct of polyhydric alcohol, those having 2 to 8 carbon atoms are preferable.

For example, ethylene glycol, diethylene glycol,
Propylene glycol, dipropylene glycol,
Examples include 4-butanol, 1,6-hegysandiol, glycerin, l-lyncholpropane, diglycerin, pentaerythryl, dipentaerythryl, sorbyl and the like.

Examples of alkylene oxides for polymerization to polyhydric alcohols include ethylene oxides, propylene oxides, propylene oxides, styrene oxides, styrene oxides, etc. Generally, ethylene oxa 4), IF, and propylene oxa I1 are used.

Examples of the (=J polymerization form) of the above-mentioned adducts include random addition polymerization of ethylene oxide, propylene oxide, etc., or random addition polymerization of two or more thereof, or block addition polymerization.

Moreover, when using ethylene oxide, Al4'-L/
D II A when the side-bonding of polyethylene oxide in the added molecular weight of polyethylene oxide exceeds 40 times Mχ
It tends to increase the viscosity of the aqueous alkali metal salts of Q class. Therefore, polyethylene fluoride 1- is 35 times heavy.
% or less is preferable.

The molecular weight of the adduct is preferably in the range of 100 to 3,000; if the molecular weight is less than 100, there is almost no stabilizing effect, and if it is more than 3°000, it becomes insoluble in water, so it becomes uniform. II A II Q An aqueous alkali metal salt solution of the same type cannot be obtained.

Examples include polypropylene glycol, polyol-12 dipropylene glyceryl ether ethylene polyoxypropylene brosoxypolymer, polyoxypropylene tulbyl ether, and the like.

Next, water Ttt used as a surfactant of the present invention
1 Soluble alcohols are those that do not mix freely with water, and have a solubility in water (20°C) of 2.
5 fold N% or less, preferably QlO. It has a molecular weight of 01 to 10% and is selected from various alcohols and derivatives thereof. For example, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, n-amyl alcohol, i-amyl alcohol, sec-amyl alcohol, L-amyl alcohol, n-to''; sil alcohol, methyl amyl alcohol, 2-ethylbutyl alcohol, n-heptyl alcohol, 3-heptyl alcohol, n-octyl alcohol, 2-octyl alcohol,
Alcohol-like colors such as 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, cyclohexyl alcohol, hensyl alcohol, octyl alcohol, etc. Ethylene glycol diphthyl ether, propylene glycol monophthyl ether, glycerin isoamyl ether, diethylene glycol Examples include polyhydric alcohol ethers such as dibutyl ether.

Thirdly, the sulfosuccinate salt used as the surfactant of the present invention is represented by the following general formula (1) or (old).

CR is M, hydrogen or an alcohol or phenol residue having 4 to 18 carbon atoms, R is an alcohol or phenol residue having 4 to 18 carbon atoms, and M is selected from alkali metals and alkaline earth metals. represents a cation. ] In the above general formula, the alcohol or functional residue having 4 to 18 carbon atoms refers to, for example, those having a straight chain or an argyl, Schiff, alkyl, alkenyl, alkylaryl, or aral group having a side chain. Specifically, butyl, pendel, -, =1-Jl/. heptyl,
octyl, nonyl, decyl, undecyl, 1'decyl,
Examples include tridecyl, tetradenyl, pentadecyl, -, tridecyl, hebutadecylphenyl, octylphenyl, nonylphenyl, and 1-decylphenyl groups.

The alkali metals and alkaline earth metals represented by the above general formula include, for example, tritrium, potassium, lithium,
Calcium, barium, etc. may be used, but usually inexpensive minerals such as sodium chloride and barium are used.

Such sulfosuccinate salts include, for example, dibutyl sodium sulfosuccinate, cyamyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate,
Examples include dioctyl sodium sulfosuccinate, di-2-ethylhexyl sodium sulfosuccinate, ditridecyl sodium sulfosuccinate, dilauryl sodium sulfosuccinate, monolauryl sodium sulfosuccinate, and the like.

Fourthly, the anionic polymeric emulsifying and dispersing agent used as the surfactant of the present invention is preferably of the sulfonic acid type or carboxylic acid type obtained naturally or synthetically. for example,
Sulfonic acid types include natural polymers such as lignin sulfonate; aromatic sulfonates such as formalin condensates of naphthalene sulfonates, petroleum resin sulfonates, and melamine resin sulfonates; polystyrene sulfonates; Sulfonated products of high molecular compounds such as sulfonated products of styrene-maleic anhydride copolymer; styrene sulfonic acid $. Examples include copolymers of vinyl sulfonic acid monomers and unsaturated carboxylic acids, such as copolymers of hydromaleic acid.

Carboxylic acid types include polyacrylates; copolymers of olefins such as styrene, ethylene, isobutylene, and α-olefins and unsaturated carboxylic acids such as maleic anhydride, or water-soluble salts thereof; acrylic acid-fumaric acid; Examples include copolymers of vinyl monomers and unsaturated carboxylic acids, such as copolymers, and water-soluble salts thereof.

The molecular weight of this anionic polymer emulsifying dispersant is 1,000
~100.

000 is good.

Nonionic and cationic polymer emulsion content +13! The agent is
Since it has poor solubility in a highly concentrated aqueous caustic solution, when it is added to an aqueous alkali metal salt solution of D II A IIQi, a uniform aqueous solution cannot be obtained, which is not preferable.

In the present invention, Al-1- of the above polyhydric alcohol
Ren oxide additional salary, water H? It is sufficient to use at least one type of surfactant among the fj alcohol phosphosuccinate salt and the anionic polymer emulsifying dispersant, but a synergistic effect can be achieved by using two or more of these in combination. In some cases, the effects of these two methods can be synergistic.

° The amount of the drug of the present invention used is 0.0 parts by weight per 100 parts by weight of D II A HQ or T 1) A Q.
The range is 5 to 5 parts by weight, preferably 4:l:0.1 to 3 parts by weight. If the amount is less than 0.05 parts by weight, it will not be possible to obtain a long-term stable aqueous solution, and if it exceeds 5 parts by weight, a homogeneous aqueous solution may not be obtained or the stability of the aqueous solution may decrease, especially if the water soluble Alcohols and sulfosuccinic acid ester salts are undesirable because they cause the separation of unintended drugs.This use can be further reduced if two or more types of drugs are used to produce a synergistic effect.

In the present invention, examples of combinations in which two or more types of drugs are used are shown below.

(2) The poorly water-soluble alcohols can be used in combination with other surfactants and anionic polymer emulsifying and dispersing agents. Examples of surfactants include fatty acid salts and alkyl salts.
alkylaryl) sulfonates, sulfosuccinates, α-olefin sulfonates, alkyl (or alkylaryl) phosphates, alkyl sulfates, polyoxyal-1-lene alkyl (or alkylaryl) sulfates, etc. anionic surfactants,
Polyoxyalkylene alkyl (or alkylaryl) ether and polyoxyethylene polyoxybutylene 1) Non-ionic surfactants such as pyrene block copolymers, polyhydric alcohols such as polypropylene glycol, etc. Can be mentioned. Examples include anionic polymer emulsifying dispersant salts, styrene-maleic anhydride copolymers, polyacrylates, lignin sulfonates, and the like.

Among them, when used with alkylene oxa-ide adducts of polyhydric alcohols such as polypropylene glycol (1), the synergistic effect is remarkable.

Water tea Ij according to the present invention? When using M alcohols with other additives, the mixing ratio is as follows: 1) Soluble alcohols/other additives - 9,510
, 5 to 0.5/9.5 (weight ratio), and the total amount used may be within the above range.

■+a1 The sulfosuccinic acid ester salt used in the present invention is
It can be used alone or in combination with two or more solvents to enhance the effect. Examples of alcohol properties include lower alcohols such as methanol, ethanol, isopropylene glycol, alcohol, propylene glycol, xylene glycol,
Examples include polyhydric alcohols such as glycerin, aliphatic and aromatic hydrocarbons, and the like. The usage amount t of such a container
"Surbo 1...0 for 1 part of Risai ester salt
．． It is 1 to 10 parts by weight.

(h) Sulfosuccinic acid ester 1 has a synergistic effect with alkanediol or (J long alcohol, 1-renoh 1-lii F (-J separate substance and ino 1).Alkanediol , those having 5 to IO carbon atoms, such as 1,6-hexanol, octyl/Nguri: 1
-L, etc. @1jli Alu I-le's Alkylene Oni 1st issue (Self-help 1) As mentioned above, the ratio of Bolie J's:A-1-Kioid in the extra child is 3.
5% or less, and the number of molecular stars is preferably 100 to 3.00n, preferably 200 to 1,000. For example, polyoxypylene glycol, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene di-1-1-polymer, etc. are commonly used.
) Bilene glycol (historical ratio is sulpo succinic acid ester salt/alkanediol or polyhydric alcohol alkylene oxychloride)
~0°5/9.5 (weight ratio), especially when the blending ratio is 8
/2 to 27'8, the synergistic effect becomes significant. Further, when used in combination, 0.1 to 2.0 parts by weight of the drug C (compared to 100 parts by weight of D II A II Q) is sufficient.

(C) Also, the sulfosuccinic acid ester salt can be used in combination with other anionic surfactants and anionic polymer emulsifiers 1). As anionic and ionic surfactants,
Examples include fatty acid salts, alkyl (or alkylaryl) sulfonates, α-olefin sulfonates, alkyl sulfates, polyoxyalkylene al;1-l (or alkylaryl) sulfate salts, and anionic/ionic As the polymeric emulsifying and dispersing agent, the agent of the present invention is used, such as naphthalene sulfonate polymerine condensate, polystyrene sulfonate, styrene-maleic anhydride copolymer, polyacrylate, lignin sulfonate, etc. can be mentioned.

When the sulfosuccinate salt is used in combination with the other drugs mentioned above, the mixing ratio is sulfosuccinate salt/other drugs -
The ratio is 9,510°5 to 0.5/9.5 (weight ratio), and the amount used in combination is 0.1 to 5 parts by weight per 100 parts by weight of DHA HQ.

■Is the anionic polymer emulsifying dispersant water ttl? B External alcohols When using nonionic compounds such as polyhydric alcohols alkylene oxides and It has a synergistic effect when used in combination with Sal.
"!-J addition may be as described above, but examples include polypropylene glycol, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene copolymer, etc. Generally, 200-1°000 polypropylene glycol anionic polymer emulsifying dispersant with a nonionic compound (J
When using l, the blending ratio is anionic polymer emulsifier 1)
agent/Jl ionic gold compound/1 to 1/9, preferably 8/2=2/8. The amount used in combination is D
0.05 to 3.0 parts by weight of the drug is sufficient for 100 parts by weight of Class II A IT Q.

The method of adding the drug used in the present invention is, for example, by adding a predetermined amount of the raw material T I (A QM or D II A II Q) into a caustic aqueous solution in advance.
＠Method of dissolving and then adding raw materials, method of adding a predetermined amount of drug to the above raw materials, or LJ:I')IIA
II Qli may be added to an aqueous alkali metal salt solution.

In the latter method, the temperature at which the drug is added and mixed is D II
Although there is no limitation as long as the alkali metal salt of A II Q class precipitates2, it is usually preferred to be at room temperature to 40°C or higher, especially about 50°C or higher.For example, when the above raw materials are dissolved in an aqueous caustic solution, Immediately after that, it is preferable to add the drug and stir at around 50° C. for 15 minutes to 1 hour while cooling.

Furthermore, when two or more types of additive agents are used, they may be added as a mixture or may be added separately at random, with the same effect.

The high concentration pulp cooking aid aqueous solution produced by the above method is
Cool immediately. It is preferable to keep the cooling temperature as low as possible in order to suppress the production of anthranol.
Considering the stability, a temperature of generally 60°C or lower and 10°C or higher, particularly 20 to 40°C is appropriate.

(3) Effects of the Invention The aqueous aqueous solution of an alkali metal salt of D II A HQ containing the drug of the present invention and having substantially increased solubility can be obtained even under conditions where crystals would normally precipitate. Since it is possible to stably maintain a homogeneous aqueous solution, it is possible to supply pulp cooking aid aqueous solutions with a higher concentration than before to pulp users who often live in relatively distant cold regions.
The effect is extremely significant.

The high-concentration pulp cooking aid aqueous solution of the present invention can be used in commonly practiced Lignohill 1 course monthly cooking such as Clara 1 cooking (sulfate cooking), soda cooking, sulfite cooking, vapor phase cooking, oxygen cooking, etc. can be used in a conventional manner as a cooking aid used to accelerate its cooking rate and improve pulp yield.

Hereinafter, the present invention will be further explained in detail with reference to Examples.

Example 1 In a four-bottomed flask equipped with a temperature control, a dropping funnel, a nitrogen inlet tube, and a stirring blade, t]adduct (T"1lAQ) obtained by the reaction of 1,4-nara-1quinone and butadiene was placed. , however, it contains 0.7χ of impurities of 1 than anthraginone ossification.Hereinafter,
This raw material is simply abbreviated as T II A Q. ) 80g and polypropylene glycol (molecule 1i400) 0.32g
, 0.64g, 0.96g and 1.6g respectively,
200g of 34.7g of sodium hydroxide under nitrogen atmosphere
of alkaline aqueous solution dissolved in water was added through the dropping funnel for 10 minutes.
It was added dropwise continuously over a period of minutes. After completing the dripping, warm your shoulders and
The mixture was stirred at 5° C. for 60 minutes to obtain a red aqueous solution of D II A II Q salt. Stir this solution 1
! 1゛Down straight 6. The long-term storage stability and homogeneity of each aqueous solution obtained after cooling to IQ in two chambers was evaluated using the following test method. The evaluation results are shown in Table-1.

The test method is as follows.

Stability: Test 1'l water? '4 liquid] 00ml 2.5c in diameter
When the sample was placed in a glass test tube with a height of 22 cm and stored at a specified temperature under a nitrogen atmosphere, evaluation was made based on the elapsed time at which crystals precipitate at the bottom of the test tube.

Uniformity/quality: For sample aqueous solutions stored at 20 to 40°C for 2 months, 1t)l outside the solution was visually determined. Also,
Collect 10+nl each from the top, middle, and bottom of the test tube, oxidize each aqueous alkali salt solution of anlaquinone (DIIAIIQ) with hydrogen peroxide, and determine the precipitated ara-1-one. .) The concentration was measured.

○: No foreign matter was observed in the aqueous solution, and
△: There are two parts of aqueous solution or a small number of figurines on the glass wall ×: Crystal precipitation Comparative Example 1 D II A was prepared in the same manner as in Example 1 using 1.6 g of a nonionic surfactant.
A water-cooled solution of the disodium salt of IIQ was prepared.

The stability and homogeneity of the obtained aqueous solution were evaluated using the same test method as in Example 1. The evaluation results are shown in Table-1.

Comparative Example 2 In Example 1, D I without any additive drug was used.
An aqueous solution of the disodium salt of I A II Q was prepared.

The resulting water? The stability and uniformity of the 8 liquids were evaluated using the same test method as in Example 1. The evaluation results are shown in Table-1.

Note: (Il# symbol, F(;J additive) of secondary alcohol having 12 to 14 carbon atoms. (f does not indicate the average degree of condensation.) (2) The aqueous solution thickens.

Example 2 and Comparative Example 3 An aqueous disodium salt solution of DIIAIIQ was prepared in the same manner as in Example 1, except that 0.96 g of boriso 1) pyrene glycol Xl-ol with a different concentration of 7-■ was used in Example 1. . Next, the stability and homogeneity of the aqueous solution were evaluated using the same test method as in Example 1. The evaluation IJi results are shown in Table-2.

Table 2 Example 3 and Comparative Example 4 Example 1 except that 1.6 g of various polyoxyethylene polyoxypropylene brosoxycopolymers shown in Table 3 was used instead of polypropylene glycol. An aqueous solution of the disodium salt of DIT A II Q was prepared in the same manner as in Example 1. Next, the stability, uniformity, and properties of the aqueous solution were evaluated using the same test method as in Example 1. The evaluation results are shown in Table-3.

Note: The mark * indicates the content of ethylene oxa-I1 in the total molecular weight, χ.

Example 4 In Example 1, 1.6 g of polyvalent July 1-bar alkylene ol 1-4J 1).j lamp body shown in Table 4 was used instead of polypropylene glycol 1-1. An aqueous solution of dinatrium 1 and salt of D It A II Q was prepared in the same manner as in Example 1, except for the following. Next, the stability and uniformity of the aqueous solution were evaluated using the same test method as in Example 1. The evaluation results are shown in Table-4.

Table-4 Example 5 Temperature 81. Connect the dripping port-l, nitrogen introduction pipe, and stirring blade (=t
In a four-loaf flask, add T” I (A Q 8h to 1
”: Contains, under nitrogen atmosphere, 34.7 g of sodium hydroxide
78 liquid 4 of alkaline water dissolved in 200 g of water was continuously added dropwise from the dropping funnel over a period of 10 minutes. After completion of the dropwise addition, the mixture was brought to ambient temperature and stirred at 85°C for 60 minutes.
II Q's China 1. A red aqueous solution of IJium salt was obtained.

To this, n-hexyl alcohol 0°32.1.6.3
．． After adding 2 g, the solution was cooled to room temperature while stirring.

The long-term storage stability and uniformity of each of the obtained aqueous solutions were evaluated using the same test methods as in Example 1. The evaluation results are shown in Table 5.

Comparative Example 5 In Example 5, D)I was prepared without using any additive drug.
An aqueous solution of the disodium salt of AHQ was prepared.

Each of the obtained aqueous solutions was evaluated for long-term storage stability, uniformity, and properties using the same test methods as in Example 1. The evaluation results are shown in Table-5.

Example 6 D II A HQ was prepared in the same manner as in Example 5, except that 1.6 g of each of the poorly water-soluble alcohols shown in Table 6 was used instead of n-hexyl alcohol.
An aqueous solution of the disodium salt of was prepared.

Stability of the obtained aqueous solution - 1) FuH plan
It was evaluated using the same method. The evaluation results are shown in Table-6.

Comparative Example 6 D II A II was prepared in the same manner as in Example 5, except that 1.6 g of each of the water-soluble alcohols shown in Table 6 was used instead of n-hexyl alcohol.
An aqueous solution of the disodium salt of Q was prepared. For alcohols with a boiling point lower than 85°C, DTI A
It was added when the temperature of the disodium salt aqueous solution of I(Q) reached 60°C.

The stability and uniformity of the obtained aqueous solution were evaluated using the same test method as in Example 1. The evaluation results are shown in Table-6.

(Left below) Table 6 Example 7 Addition method of drug: DIIAIIQ salt water? Before preparing the 8 liquid, a mixture of the drugs shown in Table 7 and polypropylene glycol was added to T HAQ, and then an aqueous sodium hydroxide solution was added dropwise to obtain an aqueous solution of the sul-lium salt of D HA IIQ. .

Addition ■: 0.32 g (OJχ vs. T If A Q) How to use the drug: Below is the slightly water-soluble alcohol cheek/Vorip D pyrene glycol (MW400) L/1 (weight ratio) Table 7 Example 8 Temperature 51, dropwise addition 1. Under a nitrogen atmosphere with r, I-l, nitrogen inlet tube, and stirring blade installed, 1. lJum34.
An alkaline water-cooled solution prepared by dissolving 7 g in 200 g of water was continuously dropped from dropping row F over 10 minutes. After completing the dropwise addition, warm the plate and stir at 85°C for 60 minutes to dissolve DllA.
A red aqueous solution of the disodium salt of IIQ was obtained. This solution was immediately cooled to room temperature while stirring.

The long-term storage stability and uniformity of each of the obtained aqueous solutions were evaluated using the same test methods as in Example 1. The evaluation results are shown in Table-8.

Example 9 DNA HQ was produced in the same manner as in Example 8, except that a mixture of dioctyl sodium sulfosuccinate and polypropylene glycol (Mw 400) was used instead of dioctyl sodium sulfosuccinate.
An aqueous solution of the disodium salt of was prepared.

The stability, uniformity, and properties of the obtained aqueous solution were evaluated using the same test methods as in Example 1. The evaluation results are shown in Table-8.

Comparative Example 7 In Example 8, D H was prepared without using any additive drug.
An aqueous solution of the disodium salt of A II Q was prepared.

The long-term storage stability and uniformity of each of the obtained aqueous solutions were evaluated using the same test methods as in Example 1. The evaluation results are shown in Table-8.

(Margin below) Table 8 Notes: (1) In the table, PPG represents polypropylene glycol.

Example 10, Comparative Example 8 In Example 8, instead of dioctyl sodium sulfosuccinate, 0.32 g of an equal amount mixture of the compound shown in Table 9 and dioctyl sodium sulfosuccinate was used. Similarly to 8, D II A II
An aqueous solution of the disodium salt of Q was prepared.

The stability, uniformity, and properties of the obtained aqueous solution were evaluated using the same test methods as in Example 1. The evaluation results are shown in Table-9.

Table 9 Note: Two marks indicate alkylene oxalyl'-i' additives of secondary alcohols having 12 to 14 carbon atoms (blank below).
Example 1 Using the additives shown in Table IO instead of
An aqueous solution of the cinalium salt of D II A II Q was prepared in the same manner as in Example 7.

The stability and uniformity of the obtained aqueous solution were evaluated using the same test method as in Example 1, and the results are shown in Table 10.

Table-10 Note: *marks indicate vs. T1) ΔΩχ Example 12, Minhuania+1)! In Example 8, 33.2 g of F hydroxide dissolved in 200 g of water was used as the liquid, and dioctyl sulfosuccinate was used as the additive agent. An aqueous solution of the disodium salt of D II A II Q was prepared in the same manner as in Example 8, except that 1.6 g of the anionic surfactant shown in Table 1) (Comparative Example 8) was used.

The stability and uniformity of the obtained aqueous solution were evaluated using the same test method as in Example 1, and the results are shown in Table 1).

In addition, a case in which no drug was added was shown as Comparative Example 9.

Table 1) Example 13 In a fourth flask equipped with a thermometer, dropping funnel, nitrogen inlet tube, and stirring blade, 80 g of TIIAQ and Iliurium polyacrylic acid (molecules! 8,000) 0.32.0 .96.
Add 1.6 g of each and add sodium hydroxide under nitrogen atmosphere.
．． An alkaline aqueous solution prepared by dissolving 34.7 g in 200 g of water was continuously added dropwise from the dropping funnel over a period of 10 minutes. After dropping, warm the mixture and stir at 85°C for 60 minutes.
A red aqueous solution of dilinolium salt of IIAHQ was obtained. The solution was immediately cooled to room temperature while stirring.

Each water obtained? The long-term storage stability and uniformity of the 8 liquids were evaluated using the same test method as in Example 1. The evaluation results are shown in Table-12.

Example 14 In Example 13, instead of 1 lithium polyacrylate, 1 lithium polyacrylate, (molecular tt 8,00
An aqueous solution of the cinallium salt of D II A II Q was prepared in the same manner as in Example 13, except that 0.32 g of a mixture of equal amounts of 0) and polypropylene glycol (h400) was used.

The stability and uniformity of the obtained aqueous solution were evaluated using the same test method as in Example 1. The evaluation results are shown in Table 12.

Comparative Example 10゜ In Example 13, D I without using any additive drug.
An aqueous solution of the disodium salt of I A HQ was prepared.

Each of the obtained aqueous solutions was evaluated for long-term storage stability, uniformity, and properties using the same test methods as in Example 1. The evaluation results are shown in Table-12.

Table 12 Examples 15 to 23, Comparative Example 1) In Example 13, various high porosity emulsifying dispersants and dispersants shown in Table 13 were used instead of monolium polyacrylate (molecular fft 8°000). Example 1 except that a mixture of a polymeric emulsifying dispersant and polypropylene glycol was used.
An aqueous disodium salt solution of D It A 1) Q was prepared in the same manner as in Example 3.

The stability and uniformity of the obtained aqueous solution were evaluated using the same test method as in Example 1, and the results are shown in Table 13.

Table-13 Note: In the table, Na/sodium, NP=naphthalene, 5O
3Na=sodium sulfonate, ST/styrene, MA
N-maleic anhydride, PPG-represents polypropylene glycol.

Claims (6)

[Claims] (1) alkylene oxide adduct of polyhydric alcohol,
It contains one or more drugs selected from the group of surface-active substances consisting of poorly water-soluble alcohols, sulfosuccinic acid ester salts, and anionic/ionic polymer emulsifying dispersants. A highly concentrated pulp cooking aid aqueous solution containing dialkali metal salts of 1,4-dihydroanthrahydroquinones as a main ingredient. (2) The aqueous solution according to claim 1, wherein the alkylene oxide adduct of polyhydric alcohol has a molecular weight of 100 to 3,000. (3) The sulfosuccinic acid ester salt has the following general formula (I
) or (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [R is M, hydrogen or alcohol with 4 to 18 carbon atoms, or phenol residue The group R' represents an alcohol or phenol residue having 4 to 18 carbon atoms, and M represents a cation selected from alkali metals and alkaline earth metals. ] (4) The molecular weight of the anionic polymer emulsifying dispersant is 1,00
The aqueous solution according to claim 1, which has a molecular weight of 0 to 100,000. (5) The aqueous solution according to claim 1 or 2, wherein the surface-active substance comprises a sulfosuccinate salt and an alkylene oxide adduct of an alkanediol or a polyhydric alcohol. (6) The aqueous solution according to claim 1, wherein the alkali metal salt is a sodium salt.