JP2003328297A - Agent for making paper low density and method for producing low density paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agent for making paper low density by which a low density paper having the low density, opacity, excellent whiteness, high strength, high surface strength and small elongation by wetting can be easily produced, and to provide a method for producing the low density paper. <P>SOLUTION: The agent for making the paper low density contains a sulfosuccinic acid derivative represented by general formula [1], general formula [2], general formula [3] or general formula [4] (in the formulas, at least one of R<SP>1</SP>and R<SP>2</SP>, at least one of R<SP>4</SP>to R<SP>7</SP>, and at least one of R<SP>8</SP>to R<SP>10</SP>are each a 10-36C alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxyalkenyl group, or -(AO)nR<SP>3</SP>). The method for producing the low density paper involves adding the sulfosuccinic acid derivative represented by general formula [1], general formula [2], general formula [3] or general formula [4] by dispersing or dissolving the sulfonic acid derivative in water or an aqueous alkali solution at the papermaking process. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a low density agent for paper and a method for producing low density paper. More specifically, the present invention can easily produce low-density paper having excellent low density, opacity, and whiteness, high strength, high surface strength, and low water elongation without reducing the sizing degree. The present invention relates to a low density agent for paper and a method for producing low density paper.

[0002]

2. Description of the Related Art In recent years, efforts have been made to reduce the basis weight of paper products in order to suppress the amount of pulp used as much as possible due to lack of pulp resources, soaring pulp prices, and the need to protect the global environment. Newspaper, printing paper, recording paper,
By reducing the basis weight of paper products such as wrapping paper, wallpaper, fusuma stencil, and backing paper, it is believed that not only will costs be reduced, but forest resources will also be secured, which will have a great effect on solving global environmental problems. On the other hand, there is a demand for high-quality paper that is suitable for printing and has a sense of volume, and a paper having a high bulk and a low density is demanded. Conventionally, as a method of reducing the density of paper, a method of using crosslinked pulp, a method of mixing paper with synthetic fibers, and a method of filling pulp fibers with an inorganic substance have been performed. However, in the method using crosslinked pulp and the method using mixed paper with synthetic fibers,
It is difficult to recycle the paper, and the cost becomes high, and the method of filling the inorganic material has a drawback that the strength of the paper is significantly reduced. In order to solve these drawbacks, paper density reducing agents for reducing the density of paper by adding an organic compound at the time of papermaking have been studied. For example, as a bulking agent for paper that can obtain a bulky sheet without impairing the paper strength, JP-A No. 11-200283 discloses a fat / oil-based nonionic surfactant, a sugar alcohol-based nonionic surfactant or a sugar-based nonionic surfactant. A bulking agent for papers containing an ionic surfactant, Japanese Patent Laid-Open No. 11-200284 discloses a bulking agent for papers containing an alkylene oxide adduct of a higher fatty acid.
98/03730 proposes a bulking agent for paper containing an alkylene oxide adduct of a higher alcohol. Further, Japanese Patent Laid-Open No. 11-350380 discloses that
A polyhydric alcohol fatty acid ester compound having an oxyalkylene group has been proposed as a bulking agent for paper which can obtain a bulky sheet without impairing the effect of the sizing agent. In particular, although fatty acid ester compounds of polyhydric alcohols are widely marketed, these compounds have a drawback that the effect of lowering the density is low, and the strength, surface strength, sizing degree, etc. of paper are lowered. There is. In many paper products such as newsprint, printing paper, recording paper, wrapping paper, paperboard, wallpaper, fusuma paper and its backing paper, paper strength, surface strength, sizing degree, etc. are important characteristics. The deterioration of the characteristics is a big drawback.

[0003]

DISCLOSURE OF THE INVENTION The present invention makes it easy to produce a low density paper having excellent low density, opacity and whiteness, high strength and surface strength, and a low water elongation without reducing the size. The present invention has been made for the purpose of providing a low density agent for paper and a method for manufacturing low density paper.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor reduced the sizing degree by adding a sulfosuccinic acid derivative having a long-chain substituent to a papermaking process. It was found that a low-density paper excellent in opacity and whiteness and high in strength can be obtained without performing the above process, and the present invention has been completed based on this finding. That is, the present invention provides (1) a paper low-content paper containing a sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4]. Densifying agent,

[Chemical 7] (However, in the formula, one or both of R ¹ and R ² are an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group, or-.
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when only ^one of R ¹ and R ² is the above group, the other is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkali It is an earth metal, aluminum, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and X is hydrogen, ammonium, primary , Secondary, tertiary or quaternary ammonium, alkali metals, alkaline earth metals or aluminum. )

[Chemical 8] (In the formula, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-(AO) nR ³ And A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20. , R ⁴ ,
When R ⁵ , R ⁶ or R ⁷ is not the above group, hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms,
A hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, Y is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. is there. )

[Chemical 9] (In the formula, at least one of R ⁸ , R ⁹ and R ¹⁰ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when R ⁸ is not the above group, hydrogen, ammonium, alkali metal, alkaline earth metal, alkyl group having 1 to 9 carbon atoms, 2 carbon atoms
To 9 alkenyl group, a hydroxy alkenyl group of a hydroxyalkyl group, or 3-9 carbon atoms, R ⁹ or R ¹⁰
Is a hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and Z is hydrogen or ammonium. , Primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. ), And (2)
The sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3], or the general formula [4] is dispersed or dissolved in water or an alkaline aqueous solution and added to the papermaking process. Characteristic low-density paper manufacturing method,

[Chemical 10] (However, in the formula, one or both of R ¹ and R ² are an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group, or-.
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when only ^one of R ¹ and R ² is the above group, the other is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkali It is an earth metal, aluminum, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and X is hydrogen, ammonium, primary , Secondary, tertiary or quaternary ammonium, alkali metals, alkaline earth metals or aluminum. )

[Chemical 11] (In the formula, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-(AO) nR ³ And A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20. , R ⁴ ,
When R ⁵ , R ⁶ or R ⁷ is not the above group, hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms,
A hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, Y is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. is there. )

[Chemical 12] (In the formula, at least one of R ⁸ , R ⁹ and R ¹⁰ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when R ⁸ is not the above group, hydrogen, ammonium, alkali metal, alkaline earth metal, alkyl group having 1 to 9 carbon atoms, 2 carbon atoms
To 9 alkenyl group, a hydroxy alkenyl group of a hydroxyalkyl group, or 3-9 carbon atoms, R ⁹ or R ¹⁰
Is a hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and Z is hydrogen or ammonium. , Primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. ), Is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The paper density reducing agent of the present invention contains a sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4]. To do. In the method for producing low-density paper of the present invention, the general formula [1],
The sulfosuccinic acid derivative represented by the general formula [2], the general formula [3] or the general formula [4] is dispersed or dissolved in water or an aqueous alkaline solution and added to the papermaking process.

[Chemical 13] However, in the general formula [1], one or both of R ¹ and R ² are an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group, or — (AO) nR ³ . Yes, A has 2 to 4 carbon atoms
R ³ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group, and n is 1 to 20.
When only ^one of R ¹ and R ² is the above group, the other is
Hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal, aluminum, alkyl group having 1 to 9 carbon atoms, alkenyl group having 2 to 9 carbon atoms, hydroxy It is an alkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms. X is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum.

In the general formula [2], R^Four, R^Five, R⁶Over
And R⁷At least one is an alkane having 10 to 36 carbon atoms.
Kill group, alkenyl group, hydroxylalkyl group, hydr
Roxyalkenyl group or-(AO) nR³And A is charcoal
R is an alkylene group having a prime number of 2 to 4,³Has 10 carbon atoms
~ 36 alkyl groups, alkenyl groups, hydroxyalkoxy
Is a hydroxyl group or a hydroxylalkenyl group, and n is 1 to 2
It is 0. R^Four, R^Five, R ⁶Or R⁷When is not the above group
Is hydrogen, an alkyl group having 1 to 9 carbon atoms, or an alkyl group having 2 to 9 carbon atoms
Alkenyl group, hydroxyalkyl group or C3-9
Is a hydroxyalkenyl group. Y is hydrogen, ammo
Nium, primary, secondary, tertiary or quaternary ammo
Ni, alkali metal, alkaline earth metal or aluminum
Umm. In the general formula [3], R⁸, R⁹And R^Ten
Is at least one alkyl having 10 to 36 carbon atoms.
Group, alkenyl group, hydroxylalkyl group, hydroxy
Cyalkenyl group or-(AO) nR³And A is the carbon number
2 to 4 alkylene groups, R³Has 10 to 3 carbon atoms
6 alkyl group, alkenyl group, hydroxyalkyl group
Or a hydroxylalkenyl group, n is 1 to 20
is there. R⁸When is not the above group, hydrogen, ammonium
Aluminum, alkali metal, alkaline earth metal, aluminum,
C1-C9 alkyl group, C2-C9 alkenyl
Group, hydroxyalkyl group or hydroxy group having 3 to 9 carbon atoms
A alkenyl group. R⁹Or R^TenIs not the above group
When, hydrogen, an alkyl group having 1 to 9 carbon atoms, and 2 to carbon atoms
9 alkenyl group, hydroxyalkyl group or 3 carbon atoms
~ 9 hydroxyalkenyl groups. Z is hydrogen,
MONMONIUM, first grade, second grade, third grade or fourth grade
Ammonium, alkali metal, alkaline earth metal or al
It is a minium.

R¹, R², R^Four, R^Five, R⁶, R⁷, R⁸, R⁹
Or R^TenAn alkyl group having 10 to 36 carbon atoms represented by
Lucenyl group, hydroxyalkyl group or hydroxyal
The alkenyl group may be linear or may have a side chain.
Yes. Examples of such an alkyl group include decyl
Group, lauryl group, myristyl group, cetyl group, stearyl
Group, icosyl group, behenyl group and the like.
It Examples of the hydroxyalkyl group include, for example, 12-hi
Droxylauryl group, 10-hydroxyoctadecyl group
And so on. Examples of alkenyl groups
For example, decenyl group, dodecenyl group, tetradecenyl group,
Hexadecenyl group, octadecenyl group, icosenyl group,
Examples thereof include a docosenyl group. Hydroxya
As the alkenyl group, for example, 12-hydroxy-cis
A -9-octadecenyl group etc. can be mentioned. R
¹, R², R^Four, R^Five, R⁶, R⁷, R⁸, R⁹Or R^TenRepresented by
Ru- (AO) nR³For example, polyoxyethylene
Alkyl ether group, polyoxypropylene alkyl
Ether group, polyoxyethylene alkenyl ether
Group, polyoxyethylene hydroxyalkyl ether
Group, polyoxyethylene hydroxyalkenyl ether
A group etc. can be mentioned. R¹, R², R^Four, R^Five, R
⁶, R⁷, R ⁸, R⁹Or R^TenAnd ammonium represented by
, Ammonium, monoethanol ammonium, di
Ethanol ammonium, triethanol ammonium
And so on. R¹, R², R^Four, R^Five,
R⁶, R⁷, R⁸, R⁹Or R^TenWith an alkali metal represented by
Examples include sodium and potassium.
You can R¹, R², R^Four, R^Five, R⁶, R⁷, R⁸, R⁹
Or R^TenFor example, the alkaline earth metal represented by
For example, calcium, magnesium, etc.
It Primary, secondary, tertiary or represented by X, Y or Z
Derived from alkanolamines to quaternary ammonium
Ammonium is included.

Both R ¹ and R ² in the general formula [1], all of R ⁴ , R ⁵ , R ⁶ and R ^{7 in} the general formula [2] are also the general formula [3] or the general formula [3]. 4] in R
^{When all of 8} , R ⁹ and R ¹⁰ are alkyl groups, alkenyl groups, hydroxyalkyl groups or hydroxyalkenyl groups having 9 or less carbon atoms, the density of the obtained paper may not be sufficiently reduced. In the general formula [1], one of R ¹ and R ² is replaced with R ⁴ , R ⁵ , and R ⁶ in the general formula [2].
And R ⁷ , and in the general formula [3] or the general formula [4], any of R ⁸ , R ⁹ and R ¹⁰ is an alkyl group, an alkenyl group, a hydroxyalkyl group having a carbon number of 37 or more, or When it is a hydroxyalkenyl group, it may be difficult to handle the paper density reducing agent. The method for producing the sulfosuccinic acid ester represented by the general formula [1] used in the present invention is not particularly limited, and examples thereof include ring-opening esterification reaction of maleic anhydride and a compound having a hydroxyl group, and the ring-opening esterification reaction. To the double bond of the ester compound obtained by the dehydration esterification reaction of the product of the above with a compound having a hydroxyl group, the dehydration esterification reaction of a maleic acid or fumaric acid with a compound having a hydroxyl group, bisulfite, pyro It can be produced by reacting a sulfite, a sulfur dioxide gas or the like to introduce a sulfonic acid group. The method for producing the sulfosuccinamide represented by the general formula [2] is not particularly limited, and examples thereof include ring-opening amidation reaction between maleic anhydride and a compound having an amino group or an imino group, and the ring-opening amidation reaction. Dehydrated amidation reaction of the product and a compound having an amino group or imino group, to the double bond of the amide compound obtained by dehydration amidation reaction of a maleic acid or fumaric acid and a compound having an amide group or an imino group, and the like, It can be produced by reacting bisulfite, pyrosulfite, sulfurous acid gas or the like to introduce a sulfonic acid group. The method for producing the sulfosuccinic acid ester amide represented by the general formula [3] or the general formula [4] is not particularly limited, and examples thereof include a ring-opening esterification reaction of maleic anhydride and a compound having a hydroxyl group, followed by an amino group. Or a dehydration amidation reaction with a compound having an imino group, a ring-opening amidation reaction between maleic anhydride and a compound having an amino group or an imino group, followed by a dehydration esterification reaction with a compound having a hydroxyl group, maleic acid or fumaric acid The double bond of the ester amide compound obtained by dehydration esterification amidation reaction of an acid and a compound having a hydroxyl group and a compound having an amino group or an imino group is reacted with hydrogen sulfite, pyrosulfite, sulfurous acid gas, etc. Can be produced by introducing a sulfonic acid group.

In the present invention, the compound having a hydroxyl group used for producing the sulfosuccinic acid derivative is
For example, lauryl alcohol, myristyl alcohol,
Examples thereof include cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol, 12-hydroxystearyl alcohol, dimerdiol and the like, and alkylene oxide adducts thereof. These compounds having a hydroxyl group can be used alone or in combination of two or more. In the present invention, examples of the compound having an amino group or an imino group used for producing a sulfosuccinic acid derivative include, for example, laurylamine, myristylamine, cetylamine, stearylamine, isostearylamine, oleylamine, behenylamine, and 12-hydroxy-cis-. 9-octadecenyl amine, distearyl amine, dilauryl amine, etc. can be mentioned. These compounds having an amino group or an imino group can be used alone or in combination of two or more. The sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4] used in the present invention has dispersibility in cold water or hot water,
It has good emulsifying and solubilizing properties, can be dispersed or dissolved in water without using a surfactant, and has almost no adverse effect on the sizing degree of the produced paper. Due to the hydrophilic nature of the sulfonate group, it can be self-dispersed, self-emulsified or self-solubilized in cold or hot water as it is,
Good handleability. Further, when it is fixed on paper, the strength and surface strength of the paper are hardly reduced. further,
By ionizing, the fixing property to paper is improved by adding a sulfuric acid band or a cationic compound, and the effect of lowering the density is improved. Fatty acid ester compounds of polyhydric alcohols that have been conventionally used as a density-reducing agent for paper have little compatibility with water, and a surfactant is added and dispersed in water. It is inevitable that the size of the paper will decrease. According to the paper density-reducing agent of the present invention, it is possible to reduce the density of paper without substantially reducing the sizing degree.

In the general formula [1], the general formula [2], the general formula [3] or the general formula [4], R ¹ , R ² , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ is an alkyl group having 9 or less carbon atoms, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group or a general formula — (AO) nR ³
When the sulfosuccinic acid derivative is a group represented by, the sulfosuccinic acid derivative is easily liquefied unless emulsified. The hydrophilicity of sulfosuccinic acid can be adjusted by appropriately combining an ethylene group, a propylene group and the like as A and selecting the value of n. When n exceeds 20, the effect of lowering the density and the size may be reduced. R ³ is an oleyl group, 12
A group having a double bond such as -hydroxy-cis-9-octadecenyl group, a group having a small number of carbon atoms such as a lauryl group,
A sulfosuccinic acid derivative having a branched group such as an isostearyl group or an isolauryl group is easily liquefied.
When R ³ is a linear group having a large number of carbon atoms such as stearyl group and behenyl group, the sulfosuccinic acid derivative is likely to be solid. In the method for producing low-density paper of the present invention, the sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4] is dispersed in water or an aqueous alkali solution. Alternatively, it is dissolved and added to the paper manufacturing process. The sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4] can be used alone or in combination of two or more kinds. It can also be used. The alkaline aqueous solution used is not particularly limited, and examples thereof include ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, monoethanolamine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, and isopropanolamine aqueous solution.

In the method of the present invention, the paper-making step of adding the sulfosuccinic acid derivative is not particularly limited, and examples thereof include a disaggregation step, a beating step, a preparation step of mixing chemicals and the like, and before papermaking. In the case of used paper, a recycling process or the like can be given. There is no particular limitation on the method of adding the density reducing agent for paper, and for example, it can be added as it is, or a small amount of a surfactant, water, a solvent, etc. may be added to self-emulsify in water or hot water. It can be added after being made into a formulation, and can also be added after being dissolved, dispersed or emulsified in water, a solvent and the like. In the method of the present invention, other chemicals can be added to the stock. Other chemicals include, for example, wet paper strength agents, dry paper strength agents, paper strength agents such as starch and polyvinyl alcohol, dryer release agents, pitch control agents, slime control agents, deinking agents, sizing agents, paper quality improving agents. , Fillers, pigments,
Examples thereof include dyes and defoaming agents. The paper of which the density is reduced by the method of the present invention is a thin layered product obtained by intertwining and sticking together plant fibers and / or other fibers. There is no particular limitation on the raw material such as pulp used, for example, wood pulp obtained from hardwood, conifer, etc., plant fiber such as bagasse, kenaf, bamboo pulp, synthetic polymer fiber such as rayon and polyester, fibrous inorganic material, etc. Can be mentioned. The present invention can also be applied to fiber materials such as pulp molds. The low-density paper produced by the method of the present invention is not particularly limited, and examples thereof include newsprint, printing paper, recording paper, wrapping paper, paperboard, liner, corrugated cardboard paper such as core, wallpaper, fusuma paper and its backing paper. Can be mentioned. By lowering the density of the paper, it is easy to turn, prints properly, and has a sense of volume.
It is possible to reduce the cost by improving the texture, the flexibility such as touch, the paper crack prevention property, the ease of delamination, the water absorption property, the oil absorption property, the resin absorption property and the opacity. According to the low density agent for paper and the method for producing low density paper of the present invention, not only can the density of the paper be lowered without lowering the sizing degree, but the opacity and whiteness of the paper can be improved, It is possible to reduce the water content elongation of.

[0012]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, the test paper was evaluated by the following method. (1) Density Measured according to JIS P 8118. (2) Opacity According to JIS P 8138, COLORIMATE
R [Murakami Color Research Laboratory, CM-53D] is used for measurement. (3) Whiteness According to JIS P 8123, the color is measured using a colorimeter [Minolta Co., Ltd. CM-3700d]. (4) Specific burst strength Measured according to JIS P 8112. (5) Surface strength Measured according to the method using JIS P 8129 2.1 wax. (6) Size Degree Measured according to JIS P 8122. (7) Water content elongation Test paper pretreated according to JIS P 8111,
Draw a solid line with a length of 15 cm at 5 points with a pencil, measure the length of the solid line after immersing in water at 20 ° C. for 15 minutes, and calculate the average value of the water content elongation.

Example 1 98 g (1 mol) of maleic anhydride and 270 g (1 mol) of stearyl alcohol were charged into a four-necked flask equipped with a thermometer and a nitrogen gas-blowing tube, and 80 to 100 while blowing nitrogen gas. The reaction was carried out at 0 ° C. for 2 hours to obtain maleic acid monostearyl ester. This maleic acid monostearyl ester was charged into a glass autoclave, and 50 g of water and 114 g of sodium bisulfite (1.
1 mol) was added and sealed, and when the pressure became 98 kPa or more, degassing was performed to raise the temperature while lowering the pressure to 49 kPa, and the reaction was carried out at 80 to 120 ° C. for 5 hours to obtain sulfosuccinic acid monostearyl ester. Was obtained. This compound was neutralized with triethanolamine to obtain a sodium salt triethanolamine salt of sulfosuccinic acid monostearyl ester. The obtained salt was dispersed in hot water at 80 ° C. to obtain a dispersion liquid containing 5% by weight of sodium salt triethanolamine salt of sulfosuccinic acid monostearyl ester. A hardwood bleached kraft pulp and a softwood bleached kraft pulp were mixed in a weight ratio of 70/30 and beaten to a Canadian standard freeness of 420 mL to prepare a pulp slurry. While stirring this pulp slurry using a Chemistrer, the above dispersion liquid was added so that the addition amount of sodium salt triethanolamine salt of sulfosuccinic acid monostearyl ester was 0.40% by weight with respect to the pulp. After 5 minutes, 0.4% by weight of dry paper strength agent [Harima Kasei Co., Ltd., Hermide C-10, anionic] was added to the pulp, and 5 minutes later, the pH was adjusted to 4. with a sulfuric acid band.
It was adjusted to 5, and 5 minutes after that, an emulsion sizing agent [Japan PMC Corporation, AL-120F] was added to the pulp in an amount of 1% by weight. Then, the stirring was continued for 10 minutes to complete the preparation of the stock. This paper material was made into a paper having a basis weight of 80 g / m ² using a square sheet machine for test. Then, using a press machine, press for 5 minutes at 700 kPa, and then use a Yankee dryer for testing at 105 ° C. for 3 minutes.
Minute drying was performed to obtain a test paper. The obtained test paper has a density of 0.
608 g / cm ³ , opacity 90.2%, whiteness 75.8,
The specific burst strength was 1.94 kPa / (g / m ² ), the surface strength was 6 A, the size degree was 37 seconds, and the water content elongation was 1.05%.

Example 2 4 equipped with a dehydration pipe, a thermometer and a nitrogen gas blowing pipe
A one-necked flask was charged with 116 g (1 mol) of maleic acid, 486 g (1.8 mol) of stearyl alcohol, 54 g (0.2 mol) of oleyl alcohol and 0.6 g of p-toluenesulfonic acid, while blowing nitrogen gas, 1
A dehydration reaction was performed at 80 to 240 ° C. for 5 hours to obtain maleic acid stearyl / oleyl (9/1) ester. This stearyl maleate / oleyl (9/1) maleate was washed with water to remove p-toluenesulfonic acid, then charged into a glass autoclave, and 50 g of water and 114 g (1.1 mol) of sodium hydrogen sulfite were added to carry out. Reaction as in Example 1 to give stearyl sulfosuccinate / oleyl (9 /
1) The sodium salt of the ester was obtained. The salt obtained is 80
Dispersion in hot water at 0 ° C. yielded a dispersion containing 5% by weight of the sodium salt of stearyl sulfosuccinate / oleyl (9/1) ester. This dispersion was tested in the same manner as in Example 1 except that the sodium salt of stearyl sulfosuccinate / oleyl (9/1) ester was added in an amount of 0.40% by weight based on the pulp. Paper was prepared and evaluated. Example 3 A four-necked flask similar to that used in Example 2 was charged with maleic acid 116.
g (1 mol), stearyl alcohol 54 g (0.2 mol), oleyl alcohol 482 g (1.8 mol) and p-paratoluenesulfonic acid 0.6 g were charged, and nitrogen gas was blown thereinto at 180 to 240 ° C. for 5 hours. A dehydration reaction was carried out for an hour to obtain stearyl maleate / oleyl (1/9) ester. This stearyl maleate / oleyl
After washing the (1/9) ester with water to remove p-toluenesulfonic acid, 50 g of water and 1 part of sodium hydrogen sulfite were added.
14 g (1.1 mol) was added and reacted in the same manner as in Example 1 to obtain a sodium salt of stearyl sulfosuccinate / oleyl (1/9) ester. The obtained salt was dispersed in warm water at 50 ° C., and stearyl sulfosuccinate / oleyl (1 /
9) A dispersion was obtained containing 5% by weight of the sodium salt of the ester. This dispersion was tested in the same manner as in Example 1 except that the sodium salt of stearyl sulfosuccinate / oleyl (1/9) ester was added to the pulp in an amount of 0.40% by weight. Paper was prepared and evaluated.

Example 4 A four-necked flask similar to that used in Example 2 was charged with maleic acid 116.
g (1 mol), behenyl alcohol 652 g (2 mol)
And 0.6 g of p-toluenesulfonic acid were charged, and dehydration reaction was carried out at 180 to 240 ° C. for 5 hours while blowing nitrogen gas to obtain maleic acid dibehenyl ester. This maleic acid dibehenyl ester was washed with water to remove p-toluenesulfonic acid, and then charged into a glass autoclave to obtain 50 g of water and 114 g of sodium bisulfite.
(1.1 mol) was added and the reaction was carried out in the same manner as in Example 1 to obtain a sodium salt of dibehenyl sulfosuccinate. The obtained salt was dispersed in hot water at 80 ° C. to obtain a dispersion liquid containing 5% by weight of sodium salt of dibehenyl sulfosuccinate. Example 1 except that this dispersion was added such that the addition amount of the sodium salt of dibehenyl sulfosuccinate was 0.40% by weight with respect to the pulp.
A test paper was prepared and evaluated in the same manner as in. Example 5 Maleic acid 116 was placed in a four-necked flask similar to Example 2.
g (1 mol), 268 g (1 mol) of oleyl alcohol, 358 g (1 mol) of stearyl alcohol ethylene oxide 2 mol adduct and 0.6 g of p-toluenesulfonic acid were charged, and while blowing nitrogen gas, 180
A dehydration reaction was carried out at ˜240 ° C. for 5 hours to obtain maleic acid oleyl (stearyloxyethyloxyethyl) (1/1) ester. This maleic acid diester compound was washed with water to remove p-toluenesulfonic acid, then charged into a glass autoclave, 50 g of water and 132 g (1.1 mol) of potassium hydrogen sulfite were added, and the reaction was carried out in the same manner as in Example 1. The potassium salt of sulfosuccinic acid diester was obtained.
The obtained salt was dispersed in warm water of 40 ° C. to obtain a dispersion liquid containing 5% by weight of potassium salt of sulfosuccinic acid diester. This dispersion was prepared in the same manner as in Example 1 except that the potassium salt of oleyl sulfosuccinate (stearyloxyethyloxyethyl) (1/1) ester was added in an amount of 0.40% by weight based on the pulp. Similarly, a test paper was produced and evaluated.

Example 6 A four-necked flask similar to that of Example 1 was charged with 269 g (1 mol) of stearylamine and heated at 60 ° C. while being blown with nitrogen gas to dissolve it.
8 g (1 mol) was added slowly. Then 60 to 10
The reaction was carried out at 0 ° C. for 2 hours to obtain maleic acid monostearyl amide. The obtained maleic acid monostearylamide was placed in a glass autoclave, 50 g of water and 114 g (1.1 mol) of sodium hydrogen sulfite were added, and the reaction was carried out in the same manner as in Example 1 to obtain a sodium salt of sulfosuccinic acid monostearylamide. It was This compound was further neutralized with sodium hydroxide to obtain the disodium salt of sulfosuccinic acid monostearylamide. The obtained disodium salt was dispersed in hot water at 80 ° C. to obtain a dispersion liquid containing 5% by weight of the disodium salt of sulfosuccinic acid monostearylamide. The amount of the disodium salt of sulfosuccinic acid monostearylamide added to this dispersion was 0.40 with respect to the pulp.
A test paper was prepared and evaluated in the same manner as in Example 1 except that it was added so as to be added by weight%. Example 7 In a four-necked flask similar to that of Example 1, 404 g (1.5 mol) of stearylamine was charged, heated to 60 ° C. while being blown with nitrogen gas to dissolve, and then 98 g (1 mol of maleic anhydride). ) Was gradually added. Then, 60-
The reaction was carried out at 200 ° C. for 3 hours to obtain maleic acid sesquistearylamide. The obtained sesquistearyl amide maleate was charged into a glass autoclave, and 50 g of water and 114 g (1.1 mol) of sodium bisulfite were added,
The reaction was carried out in the same manner as in Example 1 to obtain the sodium salt of sesquistearylamide sulfosuccinate. This compound was further neutralized with triethanolamine to obtain a sodium salt of sulfosuccinic acid sesquistearylamide triethanolamine salt. The obtained salt was dispersed in hot water at 80 ° C. to obtain a dispersion liquid containing 5% by weight of sodium salt triethanolamine salt of sesquistearylamide sulfosuccinate. A test paper was prepared in the same manner as in Example 1 except that this dispersion was added so that the addition amount of the sodium salt of sulfosuccinic acid sesquistearylamide triethanolamine salt was 0.40% by weight based on the pulp. It was produced and evaluated.

Example 8 Into a four-necked flask similar to that of Example 1, 521 g (1 mol) of distearylamine was charged, heated to 80 ° C. while being blown with nitrogen gas to dissolve, and then 98 g of maleic anhydride ( 1 mol) was gradually added. Then 80-1
The reaction was carried out at 00 ° C for 2 hours to obtain maleic acid mono (distearylamide). The obtained maleic acid mono (distearyl amide) was charged into a glass autoclave, and water 50
g and 114 g (1.1 mol) of sodium hydrogen sulfite were added and reacted in the same manner as in Example 1 to give sulfosuccinic acid mono
A sodium salt of (distearylamide) was obtained. This compound was neutralized with monoethanolamine to obtain a sodium salt monoethanolamine salt of sulfosuccinic acid mono (distearylamide). Disperse the obtained salt in hot water at 80 ° C,
A dispersion containing 5% by weight of the sodium salt monoethanolamine salt of sulfosuccinic acid mono (distearylamide) was obtained. This dispersion was prepared in the same manner as in Example 1 except that the sodium salt monoethanolamine salt of sulfosuccinic acid mono (distearylamide) was added in an amount of 0.40% by weight based on the pulp. Make a test paper,
An evaluation was made. Example 9 A four-necked flask similar to that of Example 2 was charged with laurylamine 1
39 g (0.75 mol) and oleylamine 200 g (0.75 mol).
(75 mol), and while blowing nitrogen gas, 60
After heating to ℃ to dissolve, 98g of maleic anhydride (1
Mol) was gradually added. Then 3 at 60-200 ° C
A dehydration reaction was carried out for an hour to obtain lauryl maleate / oleyl amide. The obtained lauryl maleate / oleyl amide was charged into a glass autoclave, and 50 g of water and 114 g (1.1 mol) of sodium hydrogen sulfite were added and reacted in the same manner as in Example 1 to give the sodium salt of lauryl sulfosuccinate / oleyl amide. Got This compound was neutralized with triethanolamine to obtain sodium lauryl sulfosuccinate / oleylamide salt triethanolamine salt. The obtained salt was dispersed in warm water at 50 ° C. to obtain a dispersion liquid containing 5% by weight of sodium salt of lauryl sulfosuccinate / oleylamide triethanolamine salt. This dispersion was added so that the amount of lauryl sulfosuccinate / oleylamide sodium salt triethanolamine salt added was 0.40% by weight based on the pulp.
Test paper was prepared and evaluated in the same manner as in Example 1.

Example 10 A four-necked flask similar to that of Example 2 was charged with 270 g (1 mol) of stearyl alcohol, heated to 60 ° C. while being blown with nitrogen gas and dissolved, and then 98 g of maleic anhydride (1 mol). Mol) was gradually added and reacted at 80 to 100 ° C. for 2 hours to obtain maleic acid monostearyl ester. Then 269 g (1 mol) of stearylamine
Was gradually added, and dehydration reaction was performed at 60 to 200 ° C. for 3 hours to obtain maleic acid stearyl ester stearyl amide. The obtained maleic acid stearyl ester stearyl amide was charged into a glass autoclave, and 50 g of water and 114 g (1.1 mol) of sodium bisulfite were added,
Reaction was carried out in the same manner as in Example 1 to obtain a sodium salt of sulfosuccinic acid stearyl ester stearylamide. The obtained salt was dispersed in hot water at 80 ° C. to give 5% by weight of sodium salt of sulfosuccinic acid stearyl ester stearylamide.
A dispersion liquid containing was obtained. A test paper was prepared in the same manner as in Example 1 except that this dispersion was added so that the added amount of sodium salt of sulfosuccinic acid stearyl ester stearylamide was 0.40% by weight based on the pulp. An evaluation was made.

Comparative Example 1 Sodium stearate was dispersed in hot water at 80 ° C. to obtain a dispersion containing 5% by weight of sodium stearate.
A test paper was prepared in the same manner as in Example 1 except that the sodium stearate dispersion was added to the pulp slurry so that the amount of sodium stearate added was 0.40% by weight based on the pulp. It was made. The obtained test paper had a density of 0.641 g / cm ³ , opacity of 88.6%, whiteness of 75.3, specific burst strength of 2.20 kPa / (g / m ² ), surface strength of 7 A, and size of 41 seconds. The water elongation was 1.12%. Comparative Example 2 A stearyl alcohol 2 mol adduct of ethylene oxide was emulsified and dispersed in water at 50 ° C. to obtain an emulsion dispersion containing 5 wt% of a stearyl alcohol 2 mol adduct of ethylene oxide. To the pulp slurry, the above emulsion dispersion,
A test paper was prepared and evaluated in the same manner as in Example 1 except that the addition amount of the ethylene oxide 2 mol adduct of stearyl alcohol was 0.40% by weight based on the pulp. Comparative Example 3 5 mol of stearic acid ethylene oxide / 5 mol propylene oxide random adduct was emulsified and dispersed in water at 25 ° C., and an emulsified dispersion liquid containing 5 wt% of ethylene oxide 5 mol / propylene oxide 5 mol adduct was added. Obtained. The above emulsion dispersion was added to the pulp slurry, and the addition amount of the ethylene oxide 5 mol / propylene oxide 5 mol random adduct of stearic acid was 0.1 to the pulp.
A test paper was prepared and evaluated in the same manner as in Example 1 except that 40% by weight was added.

Comparative Example 4 Pentaerythritol stearate triester 10
2 parts by weight of fatty acid esterified product of ethylene oxide adduct of sorbitol was added to 0 part by weight, and emulsified and dispersed while gradually adding hot water to obtain an emulsion dispersion containing 10% by weight of stearic acid triester of pentaerythritol. It was A test paper was prepared in the same manner as in Example 1 except that the above emulsion dispersion was added to the pulp slurry such that the amount of pentaerythritol stearate triester added was 0.40% by weight based on the pulp. Was prepared and evaluated. Comparative Example 5 An emulsion dispersion was prepared and a test paper was prepared and evaluated in the same manner as in Comparative Example 4 except that beef tallow was used instead of pentaerythritol stearate triester. Comparative Example 6 A test paper was prepared and evaluated in the same manner as in Example 1 except that the low density agent was not added. The structures of the compounds represented by the general formula [1], the general formula [2], the general formula [3], or the general formula [4] synthesized in Examples 1 to 10 are shown in Table 1, and in Comparative Examples 1 to 6. Table 2 shows the paper density-reducing agents used.
The results of No. 10 and Comparative Examples 1 to 6 are shown in Table 3.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

Example 1 prepared using a paper density-reducing agent containing a sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4].
The test papers of No. 10 to 10 have a relatively small decrease in sizing degree, a high specific burst strength and a high surface strength, a low density, an opacity,
High whiteness and low water content elongation. Of the five types of paper density-reducing agents used in Comparative Examples, sodium stearate of Comparative Example 1 was dispersed in hot water, and the test paper produced using this was
The specific burst strength, surface strength, and size are large, but other properties are inferior. The stearyl alcohol ethylene oxide adduct of Comparative Example 2 and the ethylene oxide propylene oxide stearate adduct of Comparative Example 3 were dispersed in water, and the test paper prepared using these had good surface strength, but other performances. Is inferior, and especially the sizing degree is extremely low. The compounds used in Comparative Examples 4 to 5 require the combined use of an emulsifier in order to disperse them in water, so that not only the size degree is lowered, but also other properties are generally inferior.

[0025]

EFFECTS OF THE INVENTION According to the density-reducing agent for low density and the method for producing low-density paper of the present invention, not only the density of the paper can be reduced by suppressing the decrease in size, but also the opacity and whiteness of the paper can be reduced. And the water content elongation can be reduced. As a result, it is possible to reduce the amount of pulp raw material used, improve productivity, and reduce raw material costs. In addition, it is possible to manufacture high-quality paper that is suitable for printing and has a sense of volume. Further, by improving the opacity, it is possible to reduce the amount of the pulp raw material, the inorganic filler and the like used, and it is possible to produce high quality paper with high whiteness.

Claims (2)

[Claims] 1. A paper density-reducing agent containing a sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4]. [Chemical 1] (However, in the formula, one or both of R ¹ and R ² are an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group, or-.
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when only ^one of R ¹ and R ² is the above group, the other is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkali It is an earth metal, aluminum, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and X is hydrogen, ammonium, primary , Secondary, tertiary or quaternary ammonium, alkali metals, alkaline earth metals or aluminum. ) [Chemical 2] (In the formula, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-(AO) nR ³ And A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20. , R ⁴ ,
When R ⁵ , R ⁶ or R ⁷ is not the above group, hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms,
A hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, Y is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. is there. ) [Chemical 3] (In the formula, at least one of R ⁸ , R ⁹ and R ¹⁰ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when R ⁸ is not the above group, hydrogen, ammonium, alkali metal, alkaline earth metal, alkyl group having 1 to 9 carbon atoms, 2 carbon atoms
To 9 alkenyl group, a hydroxy alkenyl group of a hydroxyalkyl group, or 3-9 carbon atoms, R ⁹ or R ¹⁰
Is a hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and Z is hydrogen or ammonium. , Primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. ) 2. A paper-making process in which a sulfosuccinic acid derivative represented by the general formula [1], the general formula [2], the general formula [3] or the general formula [4] is dispersed or dissolved in water or an alkaline aqueous solution. A method for producing low-density paper, characterized in that it is added to. [Chemical 4] (However, in the formula, one or both of R ¹ and R ² are an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group, or-.
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when only ^one of R ¹ and R ² is the above group, the other is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkali It is an earth metal, aluminum, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and X is hydrogen, ammonium, primary , Secondary, tertiary or quaternary ammonium, alkali metals, alkaline earth metals or aluminum. ) [Chemical 5] (In the formula, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-(AO) nR ³ And A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20. , R ⁴ ,
When R ⁵ , R ⁶ or R ⁷ is not the above group, hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms,
A hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, Y is hydrogen, ammonium, primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. is there. ) [Chemical 6] (In the formula, at least one of R ⁸ , R ⁹ and R ¹⁰ is an alkyl group having 10 to 36 carbon atoms, an alkenyl group, a hydroxylalkyl group, a hydroxyalkenyl group or-
(AO) nR ³ , A is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group, an alkenyl group, a hydroxyalkyl group or a hydroxylalkenyl group having 10 to 36 carbon atoms, and n is 1 to 20 and when R ⁸ is not the above group, hydrogen, ammonium, alkali metal, alkaline earth metal, alkyl group having 1 to 9 carbon atoms, 2 carbon atoms
To 9 alkenyl group, a hydroxy alkenyl group of a hydroxyalkyl group, or 3-9 carbon atoms, R ⁹ or R ¹⁰
Is a hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a hydroxyalkyl group or a hydroxyalkenyl group having 3 to 9 carbon atoms, and Z is hydrogen or ammonium. , Primary, secondary, tertiary or quaternary ammonium, alkali metal, alkaline earth metal or aluminum. )