JP2003328287A - Cellulose pulp bleaching auxiliary and method of bleaching cellulose pulp - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching auxiliary having the effect of improving the bleaching degree of cellulose pulp as well as low foamability. <P>SOLUTION: The cellulose pulp bleaching auxiliary consists of a compound of general formula (1): R<SP>1</SP>-O-A<SP>1</SP>-SO<SB>3</SB>M<SP>1</SP>(wherein, R<SP>1</SP>is an alkyl or the like: A<SP>1</SP>is a polyoxyalkylene unit of specific structure; and M<SP>1</SP>is H, a monovalent metal atom or the like) or general formula (2): [R<SP>2</SP>-O-A<SP>2</SP>]<SB>x</SB>-PO-(OM<SP>2</SP>)<SB>3-x</SB>(wherein, R<SP>2</SP>and A<SP>2</SP>mean the same as R<SP>1</SP>and A<SP>1</SP>respectively; x is 1 or 2; and M<SP>2</SP>means the same as M<SP>1</SP>). A method of bleaching cellulose pulp using said bleaching auxiliary is also provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bleaching aid for cellulose pulp and a method for bleaching cellulose pulp.

[0002]

2. Description of the Related Art Cellulose pulp, which is a raw material for paper, contains coloring substances such as lignin on the surface and inside of pulp fibers. Therefore, these substances are removed or decomposed to improve the whiteness. I need to bleach it.
Various bleaching agents have been used for bleaching cellulose pulp. For example, chlorine, hypochlorite, oxygen, hydrogen peroxide, chlorine dioxide, etc. have been used, but the most effective bleaching agent is chlorine.

However, the use of chlorine as a bleaching agent for cellulose pulp imposes a heavy load on drainage. Further, since chlorine itself is a harmful substance and has been pointed out as a cause of dioxin formation in recent years, it has been strongly demanded to reduce the amount used as much as possible. To reduce the amount of chlorine used, it is conceivable to increase the bleaching efficiency of cellulose pulp by some method or use a bleaching agent other than chlorine.

Oxygen is being used as a bleaching agent for cellulose pulp, which replaces chlorine. Oxygen is harmless in itself and has less load on drainage, but oxygen has a weaker bleaching power than chlorine, so various efforts are made to improve the whiteness of cellulose pulp in oxygen bleaching. ing. In particular, as computerization of offices progresses and paper consumption increases, and papers with high whiteness are demanded, improvement of bleaching efficiency of cellulose pulp is urgently required. For example, Japanese Patent Application Laid-Open No. 2001-20192 discloses a technique of improving the bleaching efficiency by using a sulfate ester type and / or a phosphate ester type surfactant. JP 2001-32186 A, JP 2001
-32187 discloses a technique for improving bleaching efficiency by adding a polyoxyalkylene alkyl ether type nonionic surfactant.

[0005]

However, none of the bleaching auxiliaries listed above are practically useful because they have an insufficient effect of improving the bleaching degree of the cellulose pulp or have a remarkable foaming property. Met. Therefore, an object of the present invention is to provide a bleaching aid which has a low foaming property and an excellent effect of improving the bleaching degree of cellulose pulp.

[0006]

Therefore, the present inventors have
As a result of examining compounds having various structures as a bleaching aid, a polyalkylene glycol derivative having a specific structure,
The inventors have found that there is an unprecedented effect of improving the bleaching degree of cellulose pulp, and have completed the present invention. That is, the present invention is a bleaching aid for cellulose pulp comprising a compound represented by the following general formula (1) or general formula (2). R ¹ —O—A ¹ —SO ₃ M ¹ (1) In the formula, R ¹ is a linear or branched alkyl group, alkenyl group, or 1 to 3 carbon atoms having 3 to 22 carbon atoms.
It is a cycloalkyl group which may be substituted with 16 alkyl groups. A ¹ is a polyoxyalkylene unit composed of an oxyethylene unit and an oxyalkylene unit having 3 or more carbon atoms and having a total number of units of 2 to 45.
M ¹ is hydrogen, a monovalent metal atom, ammonium or alkanol ammonium. During ^[R 2 ^{-O-A 2] _{x -PO- (OM 2) 3-}} x (2) ^type, R 2, ^{A 2} has the same meaning as ^R 1, ^{A 1,} respectively, x is 1 or 2 And M ² has the same meaning as M ¹ . The present invention is also a method for bleaching cellulose pulp, which comprises treating the cellulose pulp in the presence of a bleaching agent and the above bleaching aid.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (Compound of General Formula (1)) In the general formula (1), R ¹ is a linear or branched alkyl group, alkenyl group, or carbon atom having 3 to 22 carbon atoms. It represents a cycloalkyl group which may be substituted with an alkyl group of the formulas 1 to 16.

Examples of the alkyl group include propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tert-butyl group, pentyl group, isopentyl group, secondary pentyl group, neopentyl group, tert-pentyl group. , Hexyl group, secondary hexyl group, heptyl group,
Secondary heptyl group, octyl group, 2-ethylhexyl group,
Secondary octyl group, nonyl group, secondary nonyl group, decyl group,
Isodecyl group, secondary decyl group, undecyl group, secondary undecyl group, dodecyl group, secondary dodecyl group, tridecyl group, isotridecyl group, secondary tridecyl group, tetradecyl group, secondary tetradecyl group, hexadecyl group, secondary hexadecyl group , Stearyl group, icosyl group, docosyl group,
2-butyloctyl group, 2-butyldecyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-hexyldecyl group, 2-octyldodecyl group, monomethyl branched-isostearyl group, allyl Group, oleyl group and the like.

Examples of the alkenyl group include a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group and a nonenyl group.

Examples of the cycloalkyl group which may be substituted with an alkyl group having 1 to 16 carbon atoms include cyclohexyl group, methylcyclohexyl group and nonylcyclohexyl group.

Of these, as R ¹ , a linear or branched alkyl group having 4 to 12 carbon atoms has an excellent penetrating power into the cellulose pulp, and therefore exhibits the most excellent effect of improving the bleaching degree. be able to.

Usually, R ¹ is a residue obtained by removing a hydroxyl group from alcohol. Industrially, these alcohols are natural alcohols derived from natural fats and oils; or Ziegler alcohols (mainly a straight-chain primary alcohol) produced through a process of polymerizing ethylene by the Ziegler method, and olefins. Oxo alcohol produced by the oxo method of reacting carbon monoxide and hydrogen (main component is a linear primary alcohol and also mixed with branched primary alcohol), produced by air-oxidizing paraffin, and a hydroxyl group is a carbon chain It is produced as a single or mixed synthetic alcohol such as a secondary alcohol which is randomly bonded to other than the terminal, and any of these alcohols can be used.

In the general formula (1), A ¹ is composed of an oxyethylene unit and at least one kind of an oxyalkylene unit having 3 or more carbon atoms, and the total number of units is 2 to 2.
Represents 45 polyoxyalkylene units. Oxyethylene _{units, - (CH 2 -CH 2 -O} ) - represented by. The oxyalkylene group having 3 or more carbon atoms has the general formula-(A
_L -O) - represented by, as where A _L, propylene group, butylene group, a long-chain α- olefin group, and a styrene group, preferably a propylene group. Two or more kinds of alkylene groups having 3 or more carbon atoms can also be used. In that case, it is preferable that one kind is a propylene group. The average degree of polymerization of the polyoxyalkylene units represented by A ^1, that is, the average of the total number of oxyethylene units and oxyalkylene units having 3 or more carbon atoms is 2 to
45, preferably 2.1 to 22, more preferably 2.1.
~ 20. A ¹ is a random shape, a block shape, or a combination of a random shape portion and a block shape portion. Moreover, it is preferable that the weight ratio of the oxyethylene unit is preferably 30 to 90% by weight in the oxyethylene unit and the oxyalkylene unit having 3 or more carbon atoms in A ¹ .

M ¹ is hydrogen, a monovalent metal atom, ammonium or alkanolammonium. The monovalent metal atom is preferably an alkali metal atom, more preferably sodium or potassium. The ammonium includes alkylammonium.

The method for producing the compound represented by the general formula (1) is arbitrary. For example, an alcohol compound corresponding to R ¹ OH is subjected to an addition reaction with an alkylene oxide corresponding to A ¹ to obtain a polyether alcohol. , Sulfamic acid, chlorosulfonic acid, sulfur trioxide gas, and other known sulfating agents, and optionally M ¹ OH (in this case, M ¹ OH).
¹ can be obtained by neutralizing with a base corresponding to (not hydrogen). If not neutralized, M ¹ = hydrogen. Further, ^{M 1} by partial neutralization of the hydrogen and other ^{M 1}
It is also possible to use a mixture of compounds represented by the general formula (1) The degree of sulfuric acid esterification by the sulfating agent is not necessarily 100%, and the effect of the present invention can be obtained by reacting 0.1 mol or more as S atom with respect to 1 mol of polyether alcohol. Can
Preferably 0.1-0.5 mol, most preferably 0.1
~ 0.3 mol is good.

(Compound of the general formula (1-a)) The compound represented by the general formula (1) is preferably a compound represented by the following general formula (1-a). R ¹ -O- (PrO) _k -A ^3- (PrO) _n -SO ₃ M ¹ (1-a) In the formula, R ¹ and M ¹ are the same as those in formula (1), and Pr is a propylene group. is there. A ³ is composed of an oxyethylene unit and an oxyalkylene unit having 3 or more carbon atoms,
It represents a polyoxyalkylene unit having a total number of units of 2 to 30, preferably 2 to 15. A ³ has a random shape.
k and n represent the number of each oxyalkylene unit, and k is 0
<K ≦ 10, preferably 0.1 ≦ k ≦ 5, and more preferably 0.1 ≦ k ≦ 3. n is 0 ≦ n ≦
It is a number that satisfies 5, preferably 0 ≦ n ≦ 2.

The general formula (1-a) is included in the general formula (1), and the difference between the two is that the portion of the polyoxyalkylene unit represented by A ¹ in the general formula (1) is represented by the general formula (1). 1
-A) the ^{_{- (PrO) k -A 3 -}} (PrO) n - is a point that is the. To obtain such a structure, for example, propylene oxide is added to an alcohol compound corresponding to R ¹ OH, ethylene oxyside and an alkylene oxide having 3 or more carbon atoms are added at random, and then the desired compound is added. Therefore, propylene oxide may be further added.

(Compound of the general formula (2)) In the general formula (2), R ² has the same meaning as the above R ¹ , and A ² is the above A ^1.
And M ² has the same meaning as M ¹ . x is a number of 1 or 2.

Although the method for producing the compound represented by the general formula (2) is arbitrary, as an example, for example, an alcohol compound corresponding to R ² OH is added to an alkylene oxide corresponding to A ² O to obtain an alkylene oxide. It can be obtained by reacting the obtained polyether alcohol with a known phosphorylating agent such as phosphoric anhydride and, if desired, neutralizing with a base corresponding to M ² OH (in this case, M ² is not hydrogen). .
If not neutralized, M ² = hydrogen. It is also possible to M ² by partial neutralization is a mixture of the compound represented by hydrogen and the formula is other M ² (2).

The degree of phosphoric acid esterification by the phosphorylating agent does not necessarily have to be 100%.
As a P atom, 1 mole of polyether alcohol was used.
The effect of the present invention can be obtained by reacting 1 mol or more, preferably 0.1 to 0.5 mol, and most preferably 0.1 to 0.3 mol. Further, preferably, in the oxyethylene unit and the oxyalkylene unit having 3 or more carbon atoms in A ² , the weight ratio of the oxyethylene unit is 3
It is preferably from 0 to 90% by weight.

(Compound of the general formula (2-a)) The compound represented by the general formula (2) is preferably a compound represented by the following general formula (2-a). _{^{[R 2 -O- (PrO) q -A}} 4 - (PrO) t ] ^{_{x -PO- (OM 2) 3-}} x in (2-a) ^formula, R ^{2, M 2,} x has the formula (2) And Pr is a propylene group. A ⁴ is an oxyethylene unit,
It is composed of an oxyalkylene unit having 3 or more carbon atoms and represents a polyoxyalkylene unit having a total number of units of 2 to 30, preferably 2 to 15. A ⁴ has a random shape. q and t represent the number of each oxyalkylene unit, and q
Is a number satisfying 0 <q ≦ 10, preferably 0.1 ≦ q ≦ 5, and more preferably 0.1 ≦ q ≦ 3. t is 0 ≦
It is a number that satisfies t ≦ 5, preferably 0 ≦ n ≦ 2.

The general formula (2-a) is included in the general formula (2), but the difference between the ^two is that the polyoxyalkylene chain portion represented by A ² in the general formula (2) is represented by the general formula (2). 2-
a) In _- ^(PrO) q -A 4 _- is a point that is the - _{(PrO) t.} To make such a structure, for example,
After adding propylene oxide to an alcohol compound corresponding to R ² OH, ethylene oxyside and an alkylene oxide having 3 or more carbon atoms are randomly added, and then propylene oxide may be further added if desired.

(Aspect of Bleaching Aid) The bleaching auxiliary for cellulose pulp of the present invention is a compound represented by the general formula (1), preferably the general formula (1-a), or the general formula (2), preferably the general formula (2). Is a compound represented by the general formula (2-a). As a specific embodiment, the general formula (1), preferably the general formula (1-
There is an embodiment consisting of one kind of the compound represented by a) and an embodiment consisting of one kind of the compound represented by the general formula (2), preferably the general formula (2-a). Further, a composition containing two or more compounds represented by the general formula (1), preferably the general formula (1-a) can be mentioned. Further, a composition containing two or more compounds represented by the general formula (2), preferably the general formula (2-a) can be mentioned. Furthermore, one or more compounds represented by general formula (1), preferably general formula (1-a), and general formula (2), preferably general formula (2-
Compositions containing one or more of the compounds represented by a) are mentioned.

(Bleaching Method) The present invention includes a method for bleaching cellulose pulp, which comprises treating the cellulose pulp in the presence of a bleaching agent and the above bleaching auxiliary.

The amount used as a bleaching aid varies depending on the conditions such as the type of cellulose pulp to be bleached, the bleaching agent to be used, the target whiteness, etc. As the amount, preferably 0.0
It is about 05 to 3% by weight, more preferably about 0.01 to 2% by weight.

The type of cellulose pulp to be bleached is not particularly limited, but examples include kraft pulp and
Chemical pulp such as chemiground pulp, semi-chemical pulp, sulfite pulp, and alkali pulp; mechanical pulp such as ground wood pulp, refiner mechanical pulp, thermomechanical pulp, and the like, and the bleaching aid of the present invention includes wood pulp or non-powder. The effect of improving the bleaching degree is demonstrated with any of the wood pulps.

The bleaching aid of the present invention exhibits the effect of improving the bleaching degree with respect to any bleaching agent. The bleaching agent used for bleaching cellulose pulp, for example, chlorine, hypochlorite, chlorine dioxide, oxygen, ozone, hydrogen peroxide,
Peracetic acid (salt), percarbonate (salt), perboric acid (salt), etc. are mentioned. Among these, oxygen-based bleaching agents that are desirable in terms of load on drainage and safety, such as oxygen, ozone, hydrogen peroxide, peracetic acid (salt), percarbonic acid (salt), perboric acid (salt), etc. When used together with a bleaching agent, the bleaching degree improving effect is remarkable, and the bleaching aid of the present invention is particularly effective.

The amount of the bleaching agent used varies greatly depending on the type of the bleaching agent, the type of the bleached cellulose pulp, the target whiteness, the bleaching conditions such as the temperature, etc. Is 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and most preferably 1 to 5% by weight.

The bleaching aid of the present invention is used in the bleaching step of cellulose pulp, for example, other components such as alkali such as sodium hydroxide, magnesium salt such as magnesium sulfate, chelating agent, defoaming agent and peroxide stabilizing. It can be used in combination with agents and the like.

The bleaching aid of the present invention can be used in combination with other surfactants. Other surfactants include
For example, fatty acid soap, alkyl sulfonate, alkylbenzene sulfonate, higher alcohol sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, dialkyl sulfosuccinate salt, higher alcohol phosphate ester Anionic surfactants such as salts, alkylbenzene phosphonates, aliphatic amide phosphonates, alkylnaphthalene sulfonate formalin condensates; polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan Examples thereof include nonionic surfactants such as alkyl esters and polyoxyethylene sorbitan alkyl esters. Among these, particularly preferred are polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, dialkyl sulfosuccinate salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and the like.

The bleaching of the cellulose pulp is generally carried out by crushing the wood-based or non-wood-based pulp as a raw material, digesting the pulp, and adding about 50 to 20 to the obtained cellulose pulp slurry.
Bleaching is performed by adding a bleaching agent at 0 ° C. The bleaching aid of the present invention has only to be added to the system in this bleaching step, and may be during or after the cooking of the cellulose pulp.

The bleaching aid of the present invention has a low concentration (less than 10% by weight), a medium concentration (10 to 20% by weight) or a high concentration (20% by weight or more) of the concentration of the cellulose pulp slurry in the bleaching step. It can be used even if there is. Among these, an example of the bleaching conditions of the cellulose pulp at a medium concentration is shown below.

(A) In the case of oxygen bleaching Pulp concentration: 10 to 15% by weight Oxygen concentration: 10 to 30 kg / pulp t Alkaline medium: 20 to 30 kg / pulp t Magnesium sulfate: 0 to 3 kg / pulp t Treatment temperature: 80 to 130 ° C Processing time: 0.5-2 hours Top internal pressure: 3-6 kg / cm ² G

(B) In case of ozone bleaching Pulp concentration: 10 to 15% by weight Ozone concentration: 0.1-3% by weight Processing temperature: 10-80 ° C Processing time: 1-60 minutes

(C) In the case of hydrogen peroxide bleaching Pulp concentration: 10 to 20% by weight Hydrogen peroxide concentration: 0.1 to 3% by weight Treatment temperature: 50 to 90 ° C. Treatment time: 1 to 5 hours Before or after the bleaching step, chlorine bleaching with chlorine, hypochlorite, chlorine dioxide or the like may be performed.

[0036]

The present invention will be described in more detail with reference to the following examples. In the following examples, parts and% are based on weight unless otherwise specified. Example 1 [Production Example of Sulfate Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
Propylene oxide 58 at 120 to 130 ° C.
g (1 mol) was added, and then 352 g (8 mol) of ethylene oxide and 58 g (1 mol of propylene oxide).
(Mol) was added to add alkylene oxide to obtain 598 g of a reaction product. Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 23.4 g (0.2 mol) of chlorosulfonic acid was added at 20 ° C. for reaction. This reaction product was used as a bleaching aid (1-1).

Example 2 [Production Example of Sulfate Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
Propylene oxide 1 at 120 to 130 ° C.
7.4 g (0.3 mol) was added, and then alkylene oxide obtained by mixing 352 g (8 mol) of ethylene oxide and 29 g (0.5 mol) of propylene oxide was added. Then, 29 g of propylene oxide
(0.5 mol) was added. Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 35.1 g (0.3 mol) of chlorosulfonic acid was added at 20 ° C. for reaction. This reaction product was used as a bleaching aid (1-2).

Example 3 Production Example of Sulfate Type Compound The bleaching aid (1-1) was neutralized with sodium hydroxide. This reaction product was used as a bleaching aid (1-3).

Example 4 [Production Example of Sulfate Ester-Type Compound] The bleaching aid (1-2) was neutralized with sodium hydroxide, and this reaction product was used as a bleaching aid (1-4).

Example 5 [Production Example of Sulfate Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
Propylene oxide 58 at 120 to 130 ° C.
g (1 mol) was added, and then 352 g (8 mol) of ethylene oxide and 58 g (1 mol of propylene oxide).
(Mol) was added to add alkylene oxide to obtain 598 g of a reaction product. Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 19.4 g (0.2 mol) of sulfamic acid was added at 120 ° C. for reaction. This reaction product was used as a bleaching aid (1-5).

Example 6 [Production Example 6 of sulfuric acid ester type compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol was added with 1 g of potassium hydroxide as a catalyst.
Propylene oxide 1 at 120 to 130 ° C.
7.4 g (0.3 mol) was added, and then alkylene oxide obtained by mixing 352 g (8 mol) of ethylene oxide and 29 g (0.5 mol) of propylene oxide was added. Then, 29 g of propylene oxide
(0.5 mol) was added. Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 29.1 g (0.3 mol) of sulfamic acid was added at 120 ° C. for reaction. This reaction product was used as a bleaching aid (1-6).

Examples 7 to 20 [Production Example of Sulfate Ester-Type Compound] Starting materials, types of each alkylene oxide, number of moles added, number of moles of sulfating agent, presence / absence of neutralizing agent, and types are shown in Table 1. Bleaching auxiliaries (1-7) to (1-2) in the same manner as in Examples 1 to 5 of the sulfuric acid ester type compound except that the above changes.
0) was obtained.

Comparative Examples 1 to 4 For comparison, the starting material, the type of each alkylene oxide, the number of moles of addition, the number of moles of the sulfating agent, the presence or absence of the neutralizing agent, and the type were changed as shown in Table 2. Is a comparative bleaching aid (1
-1) to (1-4) were obtained.

Example 21 [Production Example of Sulfate Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
And ethylene oxide 39 at 120 to 130 ° C.
An alkylene oxide obtained by mixing 6 g (9 mol) and 116 g (2 mol) of propylene oxide was added.
Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 19.4 g (0.2
Mol) was added at 120 ° C. to react. This reaction product was used as a bleaching aid (1-21).

Example 22 [Production Example of Sulfate Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
Propylene oxide 58 at 120 to 130 ° C.
g (1 mol) was added, followed by 352 g (8 mol) of ethylene oxide. Then, 58 g (1 mol) of propylene oxide was added. Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 19.4 g (0.2 mol) of sulfamic acid was added at 120 ° C. for reaction. This reaction product was used as a bleaching aid (1-22).

[0046]

[Table 1]

[0047]

[Table 2]

Example 23 [Production Example of Phosphate Ester-Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol was added with 1 g of potassium hydroxide as a catalyst.
Propylene oxide 58 at 120 to 130 ° C.
g (1 mol) was added, and then 352 g (8 mol) of ethylene oxide and 58 g (1 mol of propylene oxide).
(Mol) was added to add alkylene oxide to obtain 598 g of a reaction product. Next, the whole amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 14.2 g (0.1 mol) of phosphoric anhydride was reacted at 50 ° C. for 1 hour, and then 2 g (0.1 mol). Mol) of water was added, and the mixture was kept at 40 ° C. for 1 hour, then heated to 80 ° C. and kept at 80 ° C. for 2 hours to cause a hydrolysis reaction to obtain 626.4 g of a reaction product. This reaction product was used as a bleaching aid (2-1).

Example 24 [Production Example of Phosphate Ester Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
Propylene oxide 1 at 120 to 130 ° C.
7.4 g (0.3 mol) was added, and then alkylene oxide obtained by mixing 352 g (8 mol) of ethylene oxide and 29 g (0.5 mol) of propylene oxide was added. Then, 29 g of propylene oxide
(0.5 mol) was added. Next, the entire amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 21.3 g (0.15 mol) of phosphoric anhydride was reacted at 50 ° C. for 1 hour, and then 3 g (0.16 mol). Mol) water, 40 ° C
After that, the temperature was raised to 80 ° C., and the temperature was kept at 80 ° C. for 2 hours for hydrolysis reaction. This reaction product was used as a bleaching aid (2-2).

Example 25 [Production Example of Phosphate Ester Compound] The bleaching aid (2-1) was neutralized with sodium hydroxide. This reaction product was used as a bleaching aid (2-3).

Example 26 [Production Example of Phosphate Ester-Type Compound] The bleaching aid (2-2) was neutralized with sodium hydroxide, and this reaction product was used as a bleaching aid (2-4).

Examples 27 to 41 [Production Example of Phosphate Ester-Type Compound] Table 3 shows starting materials, types of each alkylene oxide, number of moles added, number of moles of phosphoric anhydride, presence / absence of a neutralizing agent, and types. The same procedure as in Production Examples 23 to 25 of the phosphoric acid ester type compound except that the bleaching aid (2-5) to
(2-19) was obtained.

Comparative Examples 5 to 8 For comparison, starting materials, kinds of alkylene oxides, number of moles of addition, number of moles of phosphoric anhydride, presence or absence of a neutralizing agent,
Comparative bleaching aids (2-1) to (2-4) were obtained in the same manner as in Production Examples 23 to 25 of phosphoric acid ester type compound except that the kind was changed as shown in Table 4.

Example 42 [Production Example of Phosphate Ester-Type Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol was added with 1 g of potassium hydroxide as a catalyst.
And ethylene oxide 39 at 120 to 130 ° C.
An alkylene oxide obtained by mixing 6 g (9 mol) and 116 g (2 mol) of propylene oxide was added.
Next, the entire amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 14.2 g (0.1 mol) of phosphoric anhydride was reacted at 50 ° C for 1 hour, and then at 100 ° C for 4 hours. It was made to react and neutralized with sodium hydroxide. This reaction product was used as a bleaching aid (2-20).

Example 43 [Production Example of Phosphate Ester Compound] Using an autoclave, 130 g (1 mol) of 2-ethylhexyl alcohol and 1 g of potassium hydroxide as a catalyst.
Propylene oxide 58 at 120 to 130 ° C.
g (1 mol) was added, followed by 352 g (8 mol) of ethylene oxide. Then, 58 g (1 mol) of propylene oxide was added. Next, the entire amount of this reaction product was charged into a four-necked flask equipped with a thermometer and a stirrer, and 14.2 g (0.1 mol) of phosphoric anhydride was added to 50 ml.
After reacting at ℃ for 1 hour, then at 100 ℃ for 4 hours,
Neutralized with sodium hydroxide. This reaction product was used as a bleaching aid (2-21).

[0056]

[Table 3]

[0057]

[Table 4]

In Tables 1 to 4, the number of moles of alkylene oxide added is an average number. EO is an oxyethylene group, PrO is an oxypropylene group, and BO
Represents an oxybutylene group, and StO represents an oxystyrene group. (EO) / (PrO) represents random polymerization,
(PrO)-(EO)-(PrO) represents block polymerization.

Example 44 [Example of bleaching] The unbleached pulp of Akamatsu produced in North America was bleached under the following bleaching conditions using each of the bleaching aids shown in Tables 1 to 4 and oxygen as the bleaching agent. It was <Bleaching conditions> Pulp: North American red pine unbleached pulp (Kappa value: 2)
1.3) Pulp concentration: 13 wt% (in slurry) Oxygen concentration: 1.5 wt% (vs dry pulp) Alkali concentration: 2.0 wt% (sodium hydroxide NaO
₂ conversion, relative to absolute dry pulp) Bleaching aid concentration: 0.07 wt% (versus absolute dry pulp) Reaction temperature: 110 ° C ± 5 ° C Reaction pressure: 5.5 kg / cm ² G Treatment time: 1 hour Reaction vessel: Autoclave

The obtained bleached pulp was thoroughly washed with water and dried, and the Kappa value, which is an index of the bleaching degree of each pulp, was measured according to JIS-P-8221. The results are shown in Tables 5 and 6. Further, the squeezing liquid (250 ml) of the pulp slurry after oxygen bleaching was placed in a glass cylindrical container having an inner diameter of 11 cm, and air was introduced for 10 minutes through a glass ball filter at a liquid temperature of 90 ° C. (4 liter / liter).
And the foam height immediately after that was evaluated. Table 3 shows those that are practically preferable as ◯, those that have practical problems as Δ, and those that cannot be used as x.

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

EFFECTS OF THE INVENTION According to the present invention, a bleaching aid having a low foaming property and an excellent effect of improving the bleaching degree of cellulose pulp is provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H003 AB31 AB33 AB39 DA12 EE03                       FA19 FA42                 4L055 AD17 AD20 BB17 FA05

Claims (4)

[Claims] 1. A bleaching aid for cellulose pulp comprising a compound represented by the following general formula (1) or (2). R ¹ -O-A ¹ -SO ₃ M ¹ (1) (In the formula, R ¹ is a linear or branched alkyl group, alkenyl group, or C ¹ having 3 to 22 carbon atoms.
A cycloalkyl group which may be substituted with an alkyl group having 1 to 16 carbon atoms, A ¹ is composed of an oxyethylene unit and an oxyalkylene unit having 3 or more carbon atoms, and has a total number of units of 2 to 45; Represents an oxyalkylene unit, M ¹ is hydrogen, a monovalent metal atom, ammonium or alkanolammonium) [R ² -O-A ² ] _x- PO- (OM ² ) _3-x (2) (wherein , R ² and A ² are synonymous with R ¹ and A ¹ , respectively, x is 1 or 2 and M ² is synonymous with M ^1. ) 2. The bleaching aid for cellulose pulp according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1-a). R ¹ -O- (PrO) _k -A ^3- (PrO) _n -SO ₃ M ¹ (1-a) (In the formula, R ¹ and M ¹ are the same as formula (1), and Pr is a propylene group. And A ³ is a random polyoxyalkylene unit composed of an oxyethylene unit and an oxyalkylene unit having 3 or more carbon atoms, and the total number of units is 2 to 30, and k and n are 0 < k ≦ 10, 0 ≦ n ≦
It is a number that satisfies 5. ) 3. The bleaching aid for cellulose pulp according to claim 1, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2-a). _{^{[R 2 -O- (PrO) q -A}} 4 - (PrO) t ] _{^{x -PO- (OM 2) 3-}} x (2-a) ( ^wherein, R ^{2, M 2,} x has the formula (2 ), And Pr
Is a propylene group, A ⁴ is a random polyoxyalkylene unit composed of an oxyethylene unit and an oxyalkylene unit having 3 or more carbon atoms, and the total number of units is 2 to 30, and q and t are , 0 <q ≦ 10, 0 ≦
It is a number that satisfies t ≦ 5. ) 4. A method for bleaching cellulose pulp, which comprises treating the cellulose pulp in the presence of a bleaching agent and the bleaching auxiliary according to any one of claims 1 to 3.