JP2002356315A - Aqueous solution containing hydroxylamine salt and its preserving method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous solution containing a hydroxylamine salt, of which the crystallizing property is improved when its dense aqueous solution is kept at low temperature, of which the component can be stably maintained when it is kept at high temperature and of which the handling and distribution properties are preferable because a preservation vessel is compact and light. SOLUTION: The aqueous solution containing the hydroxylamine salt of 18-35 mass% contains at least one of a phosphoric acid derivative and an aminopolycarboxylic acid of 1-30 mass% and exhibits pH of 2-6, and it is preserved in a plastic vessel of which the oxygen permeability coefficient is 40 ml/m<2> .atm.day or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous solution in which a hydroxylamine salt is concentrated and an aqueous solution in which a hydroxylamine salt is dissolved is provided.

[0002]

2. Description of the Related Art Processing of a silver halide color photographic light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching step and a fixing step or a bleach-fixing step. In addition, rinsing processing, stabilizing processing, and the like are added as additional processing steps.

The color developing solution used in the color developing step includes:
A p-phenylenediamine compound as a color developing agent,
Hydroxylamine salts and sulfites as antioxidants,
Carbonates and the like have been commonly used as buffer agents. These color developing solutions are divided into several parts in order to reduce the weight as much as possible from the viewpoint of transportation and storage, and are handled in the form of a concentrated solution kit. Kit parts containing hydroxylamine salts, when used as concentrated solutions, may precipitate crystals when stored or transported in cold conditions in winter or the far north, or when stored or transported in summer or tropical areas. There is a problem that storage stability deteriorates.

[0004] Various techniques have been studied for many years to improve the stability of hydroxylamine. For example, a method of adding sodium ethylenediaminetetraacetate to a hydroxylamine salt solution as described in U.S. Pat. No. 3,145,082 is described in U.S. Pat. No. 3,647,449. A method of adding hydroxyalkylidene diphosphonic acid to a hydroxylamine salt solution as described in JP-A-5-17072.
As described in the specification of Japanese Patent No. 3, a method of adding mercaptothiazole to a hydroxylamine salt solution has been proposed. However, these methods are aimed at improving the storage stability of a hydroxylamine salt solution in an alkaline state, at a high temperature, or in the presence of a trace amount of heavy metal ions such as iron, copper, and nickel. A technique has not been known that simultaneously solves the problems of storage stability (crystal precipitation) at low temperatures in the state of a concentrated solution of an amine salt and stability during storage at high temperatures.

[0005] It is preferable to handle the hydroxylamine solution as concentrated as possible, because the size and weight of the container are reduced, so that the handling property is improved, and further, the cost for distribution is small, and this is preferable.

A non-corrosive composition for removing plasma etching residues using an aqueous solution containing a hydroxylamine salt as described in JP-T-2001-501649 has a structure similar to that of the present invention. A cleaning composition is known, and the concentration and pH of a hydroxylamine salt-containing aqueous solution partially overlap the present application, but the additives are different, and the patent is disclosed in JP-A-2001-501649.
The quaternary ammonium hydroxide, which is an essential constituent of the present invention, has no effect on the stability at low and high temperatures when used in the present application, and differs from the present application in constitution and purpose.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to firstly provide a method for improving the crystal deposition property even when a hydroxylamine salt is made into a concentrated aqueous solution and stored at a low temperature. Second, it is an object of the present invention to provide a method capable of stably maintaining components even when high-temperature storage is performed when a concentrated aqueous solution of a hydroxylamine salt is used. Further, the third object is to supply a concentrated hydroxylamine solution, so that the storage container can be small in size and light in weight, so that the aqueous solution containing hydroxylamine salt is extremely suitable in terms of handling and distribution. And a method for storing a hydroxylamine salt-containing aqueous solution.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in order to achieve the above object, and as a result, have come to the following configuration of the present invention.

(1) 18% by mass of hydroxylamine salt
The aqueous solution containing hydroxylamine salt containing 1 to 30% by mass of the compound represented by the general formula [1] or the aminopolycarboxylic acid in the aqueous solution containing 1 to 30% by mass and having a pH of 2 to 6 is contained. A hydroxylamine salt-containing aqueous solution, characterized in that:

(2) 18% by mass of hydroxylamine salt
In a hydroxylamine salt-containing aqueous solution containing 0.1 to 35% by mass, at least one compound represented by the general formula [2] or the general formula [3] or the general formula [4] is 1% by mass to 30% by mass. An aqueous solution containing a hydroxylamine salt, wherein the aqueous solution has a pH of 2 to 6.

(3) 18% by mass of hydroxylamine salt
In a hydroxylamine salt-containing aqueous solution containing 1 to 35% by mass, at least one of the compounds represented by the general formula [5] or the general formula [6] is 1% to 30% by mass.
An aqueous solution containing a hydroxylamine salt, wherein the aqueous solution has a pH of 2 to 6.

(4) 18% by mass of hydroxylamine salt
In a hydroxylamine salt-containing aqueous solution containing from 35 to 35% by mass, 0.2% by mass to 10% by mass of at least one compound selected from the above-mentioned general formula [7] or [8] or a polyethylene oxide sorbitan derivative is contained. A hydroxylamine salt-containing aqueous solution having a pH of 2 to 6.

(5) The aqueous solution containing a hydroxylamine salt according to any one of the above (1) to (4),
A method for storing a hydroxylamine salt-containing aqueous solution, wherein the aqueous solution is stored in a plastic container of not more than ml / m ² · atm · day.

(6) The method for storing an aqueous solution containing a hydroxylamine salt according to the item (5), wherein the plastic container is a flexible bag.

Hereinafter, the present invention will be described more specifically. In the present invention, the aqueous solution containing hydroxylamine salt is 18% by mass.
By keeping the specific compound in a specific concentration range and maintaining the pH at 2 to 6, surprisingly, the storage stability at low temperature in a concentrated hydroxylamine solution state (crystal precipitation) It has been found that the problem of stability during high-temperature storage can be solved at the same time, and the present invention can be constituted.

Details of the compound represented by the general formula [1]
Will be described. In the general formula [1], R ¹~ R⁷Are each independently
Hydrogen atom, -OH, -COOM, -PO_Three(M)_Two, -S
O_ThreeM, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms
Represent. M represents a hydrogen atom or an alkali metal atom, and n and m
Represents 0 or 1, but is not 0 at the same time.

In the general formula [1], the alkyl group preferably has 1 to 4 carbon atoms, may be linear or branched, and may have a substituent. Preferred examples of the substituent _{-OH, -COOM, -PO 3 (M} ) 2, -SO 3 M,
—NR ⁸ R ⁹ , wherein R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents a hydrogen atom or an alkali metal, and is preferably an alkali metal. n, m
Represents 0 or 1, but is not 0 at the same time. R ¹ ~
R ⁹ may be the same or different.

Preferred examples of the compound represented by the general formula [1] are shown below, but the present invention is not limited thereto.

[0019]

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Next, the aminopolycarboxylic acid will be described in detail. As the aminopolycarboxylic acid of the present invention, compounds represented by the following general formulas [AI] to [A-IV] are preferably used.

[0021]

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Wherein A _{1 to} A ₄ may be the same or different and each represents a hydrogen atom, a hydroxy group, —COOM, —PO
₃ (M ₁ ) ₂ , —CH ₂ COOM ₂ , —CH ₂ OH or an alkyl group having 10 or less carbon atoms. However, at least one of A _{1 to} A ₄ is -COOM, -PO ₃ (M ₁ ) ₂ , -CH ₂ C
OOM ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0023]

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[Wherein A₁₁~ A₁₄Are the same or different
-CH_TwoOH, -COOM_ThreeOr -PO
_Three(M_Four)_TwoRepresents M_Three, M_FourAnd are each a hydrogen atom, an
Monium group, alkali metal or organic ammonium group
You. X is an alkylene group having 2 to 6 carbon atoms or-(B₁O)_n
-B_TwoRepresents-. n represents an integer of 1 to 8;₁Passing
And B _TwoMay be the same or different, and each has 1 to 5 carbon atoms.
Represents an alkylene group. ] In the general formula [A-II]
As the alkylene group represented by X, ethylene, propylene
And groups such as len and butylene. X represents-(B₁
O)_n-B_TwoIn, B₁And B_TwoAlkylene represented by
Examples of the group include methylene, ethylene, trimethylene and the like.
Can be These alkylene groups are substituted with methyl
Group, a lower alkyl group such as an ethyl group, a hydroxy group, etc.
It may be.

[0025]

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[Wherein R _{1 to} R ₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. W represents a divalent linking group. L ₃ is

[0027]

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[0028] represents any, Y ₁ to Y ₃ each represent an alkylene group or an arylene group, X ₂ and X ₃ each represent an oxygen atom or a sulfur atom, each of R ₄ to R ₈ hydrogen atoms, Represents an alkyl group or an aryl group. Examples of the alkyl group represented by R _{1 to} R ₃ include linear, branched and cyclic ones having 1 to 10 carbon atoms, and a methyl group and an ethyl group are particularly preferable. The aryl group represented by R _{1 to} R ₃ is preferably a phenyl group. R _{1 to} R ₃
May have a substituent when is an alkyl group or an aryl group. Examples of the substituent of R _{1 to} R ₃ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group,
Alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group,
Aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group,
Sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group, etc. But preferably

[0029]

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Is a substituent represented by Where Ra, R
b, Rc, Rd and Re represent a hydrogen atom, an alkyl group or an aryl group.

Next, examples of the alkylene group represented by Y _{1 to} Y ₃ include a methylene group, an ethylene group, and a propylene group, and examples of the arylene group include a phenylene group. These alkylene groups and arylene groups represented by Y _{1 to} Y ₃ may have a substituent. As the substituent may be those raised as an example the substituents of the R ₁ to R _3, preferably, at _{-OH -COOH -CH 2 COOM -CH 2 OH} -CONH 2 -CH 2 CONH 2 -CONHCH 3 (M represents a hydrogen atom, an alkali metal, or an ammonium group).

In the general formula [A-III], the divalent linking group represented by W is preferably an alkylene group having 2 to 8 carbon atoms (including a cyclohexylene group or the like), a carbon atom having 6 to 8 carbon atoms. 10 arylene groups,

[0033]

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(B ₁ and B ₂ represent an alkylene group or an arylene group, and n represents 1 to 3),

[0035]

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(Z is a hydrogen atom, unsubstituted or —COO
M, -SO ₃ M, an alkyl group substituted with -OH, an aryl group, M represents a hydrogen atom, an alkali metal, an ammonium group) and the like, or a combination.

[0037]

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[Wherein R _{1 to} R ₃ and R _{6 to} R ₉ each represent a hydrogen atom, an alkyl group or an aryl group which may be substituted, and R ₄ and R ₅ each represent a hydrogen atom, a halogen atom,
A cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, a sulfonyl group, a sulfinyl group, an alkyl group or an aryl group which may be substituted, and R ₄ and R ₅
May together form a 5- or 6-membered ring.
A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or an ammonium salt thereof. Y represents an alkylene group or an arylene group, and may have a substituent. t and u each independently represent 0 or 1. Among the compounds represented by the general formula [A-IV], preferred are compounds represented by the following general formulas [BI] or [B-II].

[0039]

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Wherein R ₁ and R ₂ are each a hydrogen atom,
L _{1 to} L ₄ each represent an alkylene group or an arylene group, and M ₁ and M ₂ each represent a hydrogen atom, an alkali metal, an ammonium group, or an organic ammonium group. W represents a divalent linking group. ]

[0041]

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Wherein R _{1 to} R ₄ are each of the general formula [B-
I] has the same meaning as R ₁ and R ₂ , and L _{1 to} L _4, M ₁ , M ₂ and W also have the same meanings as those in formula [BI]. Hereinafter, specific examples of the aminopolycarboxylic acid according to the present invention will be described.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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As the aminopolycarboxylic acid according to the present invention, the following aminopolycarboxylic acids can be used in addition to the compounds represented by the above general formulas [AI] to [A-IV]. [A'-1] Ethylenediaminetetraacetic acid [A'-2] Trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] Dihydroxyethylglycine [A'-4] Ethylenediaminetetrakismethylenephosphonic acid [A'-5] ] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxyethylethylenediamine triacetic acid [A'-10] Ethylenediaminepropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A ' -15] triethylenetetrami Hexacetic acid [A'-16] Ethylenediaminetetrapropionic acid [A'-17] 1,3-Propylenediaminetetraacetic acid [A'-18] Glycoletherdiaminetetraacetic acid Further described in JP-A-4-174432, pp. 7-11. Exemplified Compounds 1 to 71 and 4-204533 No. 25
Aminopolycarboxylic acids of Exemplified Compounds 1 to 36 described on pages 30 to 30 can also be used.

Next, the compound represented by the general formula [2] and the compound represented by the general formula [3] will be described in detail.

The compound represented by the general formula [2] or [3] used in the present invention has a sulfonate or a sulfonate directly bonded to an unsaturated conjugated ring showing aromaticity. 1 shows a compound. One or more sulfonic acid groups or sulfonic acid ester groups may be present. One compound may have a plurality of aromatic rings, or may be a polymer. Examples of the salt include an alkali metal salt such as lithium, sodium and potassium, and an ammonium salt.

In the general formula [2] or [3], A to
The saturated or unsaturated alkyl group representing F or G to N preferably has 1 to 10 carbon atoms. The carbon number may be linear or have a side chain.

Specific examples of the compound represented by the general formula [2] or [3] are shown below, but the invention is not limited thereto. In addition, all the exemplified compounds are shown as sodium salts,
Part or all of the sulfonic acid or sulfonic acid ester may be an acid or another salt such as potassium or lithium.

[0060]

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[0061]

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Next, the compound represented by formula (4) will be described in detail. In the general formula [4], R ₄₁ represents a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and M ₄₁ represents a hydrogen atom or an alkali metal such as potassium, sodium and lithium.

Examples of the substituent for R ₄₁ include a sulfonic acid group, a hydroxyl group, an amino group, a carboxylic acid group, an alkoxy group, an alkyl group, and an alkylene group.

Next, among the compounds represented by the general formula [4], specific exemplified compounds which are preferably used in the present invention will be shown.

(4-1) methanesulfonic acid (4-2) ethanesulfonic acid (4-3) sodium allylsulfonic acid (4-4) n-propanesulfonic acid (4-5) isopropylsulfonic acid (4-6) ) Vinylsulfonic acid (4-7) Sodium n-hexanesulfonate (4-8) Sodium n-octanesulfonate (4-9) Sodium n-octane-1,8-disulfonate (4-10) Dodecylsulfonic acid Potassium (4-11) Sodium 1-carboxy-n-octane-8-sulfonate (4-12) Sodium 2-methyl-2-propene-1-sulfonate Next, a compound represented by the above formula (5) Will be described in detail. In the general formula [5], examples of the substituent include a hydroxy group, a carboxy group, a sulfonyl group, an alkoxy group, a carbamoyl group, and a sulfamoyl group. Those preferably used are those in which A ₁ , A ₂ and A ₃ are each unsubstituted. Most preferably, A
₁ , A ₂ , A ₃ are —CH ₂ CH ₂ —, —CH (CH ₃ ) —CH
₂ -.

L ₁ , l ₂ and l ₃ are each 0 or 1 to 1
Represents an integer of 500. Here, l ₁ + l ₂ + l ₃ ≧ 1.

When the compound represented by the general formula [5] in the present invention is, for example, a copolymer obtained by mixing and copolymerizing two kinds of monomers A and B, those having the following sequence are also included. Is done. -ABABABABABA- -AABABABABAAABA-
BBAA- -AAAAAABABBBBBB-
A-A-A-A-A- Among these copolymers, particularly preferred compounds are block copolymers of ethylene glycol and propylene glycol (pluronic nonionic) represented by the following general formula [5 ']. It is.

[0068] Formula [5 '] _{HO- (CH 2 CH 2 -O)} l 4 - [CH (CH ₃₎ CH ₂
—O] l ₅ — (CH ₂ CH ₂ —O) l ₆ —H In the formula, l ₄ , l ₅ , and l ₆ are l ₁ , l ₂ , and l in the general formula [5].
l ₃ as synonymous.

In the compound represented by the general formula [5 '] in the present invention, the content (% by mass) of ethylene oxide in the total molecular weight is preferably 70% by mass or more.
Particularly preferably, the content is 80% by mass or more.

Preferred specific examples of the compound represented by the general formula [5] are as follows.

[0071]

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[0072]

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[0073]

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In the following, the general formula [5] and the general formula
The specific compound represented by [5 '] is shown. HO- (CH_Two-CH_Two-O) n "-H average molecular weight 5-34 300 5-35 600 5-36 1000 5-37 1500 5-38 2000 5-39 3000 5-40 4000 5-41 6000 5-42 10000 5-43 15000 5 -44 20000 5-45 30000 HO- (CH_TwoCH_Two-O) a '-[CH (CH_Three) -CH_Two-O] b '-(CH _Two CH_Two-O) c'-H Ethylene oxide content (% by mass) in total molecules Average molecular weight 5'-1 80 8350 5'-2 80 10800 5'-3 50 4600 5'-4 70 6500 5'-580 5000 5'-650 3500 5'-770 70850 5'-8 50 4150 Represented by the general formulas [5] and [5 '] in the present invention.
The most preferred of the compounds
Tylene glycol (sometimes called PEG)
You.

In the case of polyethylene glycol,
Those having an average molecular weight in the range of 2,000 to 20,000 are preferred, and those in the range of 3,000 to 15,000 are particularly preferred.

Here, the average molecular weight in the present invention is a molecular weight calculated from a hydroxyl value. The compound represented by the general formula [5] may be used alone or in combination of two or more.

Next, the compound represented by formula (6) will be described in detail. In the general formula [6], R ₁ represents an optionally substituted hydroxyalkyl group or an optionally substituted aminoalkyl group, and the hydroxyalkyl group and the aminoalkyl group preferably have 1 to 10 carbon atoms, more preferably 2 to 6. Examples of the substituent include a hydroxy group, a carboxy group, a carbonyl group, a sulfo group, a phosphono group, an ammonium group, a nitro group, an amino group, and a halogen atom. R ₂ and R ₃ each include a hydrogen atom, an alkyl group which may have a substituent, and a benzyl group which may have a substituent.
The alkyl group which may have a straight-chain or branched-chain substituent is preferable.

Examples of the substituent include a hydroxy group, a carboxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an ureido group, an acyl group, a cyano group, a nitro group, an amino group, a sulfo group, an alkylsulfonyl group and an alkylsulfonylamino group. , An arylsulfonyl group, an arylsulfonylamino group, a phosphono group, a phosphonate residue, and a halogen atom. Preferably a hydroxy group, a carboxyl group, an alkoxycarbonyl group,
They are a carbamoyl group and an amino group, and may be further substituted with a hydroxy group, a carboxy group, a sulfo group, or an amino group.

R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _1, or R ₁ and R ₂ and R ₃ may be linked to form a ring.

Preferred specific examples of the compound represented by the general formula [6] are shown below, but the present invention is not limited thereto. (6-1) Ethanolamine (6-2) Diethanolamine (6-3) Triethanolamine (6-4) Di-isopropanolamine (6-5) 2-Methylaminoethanol (6-6) 2-Ethylaminoethanol (6-7) 2-dimethylaminoethanol (6-8) 2-diethylaminoethanol (6-9) 1-diethylamino-2-propanol (6-10) 3-diethylamino-1-propanol (6-11) 3- Dimethylamino-1-propanol (6-12) isopropylaminoethanol (6-13) 3-amino-1-propanol (6-14) 2-amino-2-methyl-1,3-propanediol (6-15) Ethylenediaminetetraisopropanol (6-16) benzylethanolamine (6-17) 2-amido No-2- (hydroxymethyl)-
1,3-propanediol (6-18) 1,3-diaminopropanol (6-19) 1,3-bis (2-hydroxyethylmethylamino) -propanol (6-20) triisopropanolamine The above-mentioned general formula [7 ] And the compound represented by the general formula [8] will be described in detail.

In the general formula [7], A ₇ is a monovalent organic group, for example, an alkyl group having 6 to 50, preferably 6 to 35 carbon atoms (for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). Or an alkyl group having 1 to 35 carbon atoms or 2 to 3 carbon atoms.
5 is an aryl group substituted with 5 alkenyl groups. A preferred group substituted on the aryl group has 1 to 1 carbon atoms.
An alkyl group (e.g., an unsubstituted alkyl group such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), a substituted alkyl group such as benzyl, phenethyl or the like; An anenyl group (for example, an unsubstituted alkenyl group such as oleyl, cetyl, allyl group, etc.) is exemplified.

Examples of the aryl group include phenyl, biphenyl, naphthyl and the like, and a phenyl group is preferred. The position to be substituted with the aryl group may be any of the ortho, meta and para positions, and a plurality of groups can be substituted. X ₇ is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and examples thereof include the groups described for A ₇ .

In the general formula [8], M ₈ represents a hydrogen atom of an alkali metal (for example, Na, K, Li, etc.), an ammonium salt or an alkanolamine salt;
And A ₈ is a monovalent organic group, for example, an alkyl group having 6 to 20, preferably 6 to 12 carbon atoms (eg, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). ) Or having 3 to 2 carbon atoms
An aryl group substituted with an alkyl group of 0, preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl, dodecyl, etc.).

Examples of the aryl group include phenyl, tolyl, xylyl, biphenyl, naphthyl and the like, preferably phenyl or tolyl. The position at which the alkyl group is bonded to the aryl group is ortho,
The meta or para position may be used.

Examples of the compounds represented by formulas [7] and [8] are shown below, but are not limited thereto.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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Among the above exemplified compounds, preferred is 7-
23, 7-28, 7-31, 7-32, 7-33, 7-
34, 7-36, 7-37, 7-47, 8-8.

Next, the polyethylene oxide sorbitan and its derivatives will be described in detail. The polyethylene oxide sorbitan and its derivative in the present application are a compound obtained by adding polyoxyethylene to sorbitan and a compound derived from the compound. Examples of the polyethylene oxide sorbitan derivative include sorbitan fatty acid esters. These can be obtained as commercial products, for example, polyoxyethylene sorbitan monooleate (trade name: Nonion O, manufactured by NOF Corporation)
T-221) and ICI Tween 80 (TWEEN)
80) and the like.

The compounds represented by the general formulas [1] to [6] and the aminopolycarboxylic acid are used in the range of 1% by mass to 30% by mass, and used in the range of 3% by mass to 20% by mass. In this case, the effects of the present invention are more remarkably exhibited. Further, the compound represented by the above general formula [7] or [8] and polyethylene oxide sorbitan and a derivative thereof
It is used in the range of 0.2% by mass to 10% by mass, and when used in the range of 0.4% by mass to 5% by mass, the effects of the present invention are more remarkably exhibited.

The pH of the hydroxylamine salt-containing aqueous solution according to the present invention is 2 to 6, and from the viewpoint of more remarkably exhibiting the effects of the present invention, the pH is more preferably 2.
It is in the range of 5-4.5.

The hydroxylamine salt according to the present invention is a salt of an inorganic acid or an organic acid with hydroxylamine such as hydroxylamine sulfate, hydroxylamine nitrate, hydroxylamine phosphate, hydroxylamine oxalate, hydroxylamine citrate and hydroxylamine hydrochloride. Means

In the present invention, the hydroxylamine salt solution of the present invention has an oxygen permeability coefficient of 40 ml / m ² · atm.
The effect of the present invention can be more remarkably exhibited by storing in a plastic container having a temperature of 20 days or less and a relative humidity of 65% or less, more preferably 20 ml / m ² · atm · day or less.

Incidentally, the oxygen permeability coefficient is calculated as “O ₂ permeation of plastic container, modern packing” (O ₂ permeation of plastic container).
plasticcontainer, Modern P
acking; J. Callay, 1968)
It can be measured by the method described in February, pages 143 to 145.

The plastic packaging material forming the container used in the present invention is made of a plastic having a small oxygen permeability coefficient, such as polyvinylidene chloride, nylon, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl chloride and the like. Sheets; or sheets obtained by laminating a metal foil such as aluminum on these sheets or sheets formed by evaporating a metal such as aluminum; and applying these sheets to sheets made of polyethylene or ethylene-vinyl acetate copolymer, etc. Laminated sheets; and the like can be used. These sheets may be used alone to form a container, or a plurality of sheets may be used in combination to form a container.

Among these plastic packaging materials,
In particular, polyvinylidene chloride, nylon, and a saponified ethylene-vinyl acetate copolymer can be preferably used because the oxygen permeability coefficient is small, the strength when formed into a container is large, and the container can be easily processed. .

The specific form of the container is not particularly limited. For example, when obtaining a cubic type container which may be in any form such as a bottle type, a cubic type, a pillow type, etc. It can also be molded as a laminate by coextrusion using a plastic packaging material. In particular, a flexible pillow-type container is preferable because it is compact and easy to handle.

When the number of sheets forming the outer wall of the container is one, the sheet has an oxygen permeability coefficient of 4 as described above.
0 ml / m ² · atm · day or less, but when the number of sheets forming the outer wall of the container is two, the oxygen permeability coefficient of these two sheets as a whole is 40 ml / m ^2. -Atm-day or less may be used.
As a sheet forming such an outer wall, a plastic sheet having a single layer structure, a plastic sheet having a multilayer structure formed by laminating a plurality of plastic sheets, or the like can be used. The plastic sheet may be a sheet made of only plastic, a sheet obtained by laminating a metal foil or paper or the like on the plastic sheet, or a metal sheet deposited on the plastic sheet. It may be a sheet.

As a one-layer plastic sheet,
For example, a plastic sheet made of polyvinylidene chloride, nylon, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinylidene chloride, or the like;
Sheets obtained by laminating a metal foil or paper made of aluminum or the like on these plastic sheets; sheets obtained by depositing a metal such as aluminum on the above-mentioned plastic sheet; and the like. Examples of a multi-layer plastic sheet obtained by laminating a plurality of plastic sheets include polyethylene terephthalate /
Polyvinyl alcohol / ethylene copolymer / polyethylene three-layer structure, stretched polypropylene / polyvinyl alcohol / ethylene copolymer / polyethylene three-layer structure, unstretched polypropylene / polyvinyl alcohol-ethylene copolymer / polyethylene three-layer structure, nylon / Aluminum foil / polyethylene three-layer structure, polyethylene terephthalate / aluminum foil / polyethylene three-layer structure, cellophane / polyethylene / aluminum foil / polyethylene four-layer structure, aluminum foil / paper / polyethylene three-layer structure, polyethylene terephthalate / polyethylene / Aluminum foil / polyethylene four-layer configuration, nylon / polyethylene / aluminum foil / polyethylene four-layer configuration, paper / polyethylene / aluminum foil / polyethylene four-layer configuration, 4-layer structure of polyethylene terephthalate / aluminum foil / polyethylene terephthalate / polypropylene, 4-layer structure of polyethylene terephthalate / aluminum foil / polyethylene terephthalate / high-density polyethylene, 4-layer structure of polyethylene terephthalate / aluminum foil / polyethylene / low-density polyethylene, polyvinyl alcohol・ Two-layer structure of ethylene copolymer / polypropylene, polyethylene terephthalate /
Aluminum foil / polypropylene three tank configuration, paper / aluminum foil / polyethylene three layer configuration, particularly preferably polyethylene / polyvinylidene chloride-coated nylon /
Polyethylene / ethyl vinyl acetate / polyethylene condensate 4-layer structure, polyethylene / polyvinylidene chloride-coated nylon / polyethylene 3-layer structure, ethyl vinyl acetate / polyethylene condensate / polyethylene / aluminum-coated nylon / polyethylene / ethyl vinyl acetate / polyethylene condensate Five layers, aluminum-deposited nylon / nylon / polyethylene / ethylvinyl acetate / polyethylene condensate four layers, stretched polypropylene / polyvinylidene chloride-coated nylon / polyethylene three layers, polyethylene / polyvinylidene chloride-coated nylon / polyethylene / Polyvinylidene chloride-coated nylon / polyethylene 5-layer structure, stretched polypropylene / polyvinyl alcohol / ethylene copolymer / low density polyethylene Layer structure, three-layer structure of stretched polypropylene / polyvinyl alcohol / ethylene copolymer / undrawn polypropylene, three-layer structure of polyethylene terephthalate / polyvinyl alcohol / ethylene copolymer / low density polyethylene, stretched nylon / polyvinyl alcohol / ethylene copolymer 3-layer structure of united / low density polyethylene,
Examples include a three-layer structure of undrawn nylon / polyvinyl alcohol / ethylene copolymer / low density polyethylene.

The oxygen permeability coefficient is 40 ml / (m ² · a
tm.day) or less, a plastic sheet having a multi-layer structure formed by laminating a plastic sheet having high oxygen permeability but high flexibility made of, for example, polyethylene, ethylene-vinyl acetate copolymer, etc. In the case of forming a container, sufficient oxygen impermeability can be obtained, and a container having excellent durability with less occurrence of pinholes can be obtained.

The thickness of the sheet forming the outer wall of the container varies depending on the material of the container, and cannot be specified unconditionally. However, it is preferably about 5 to 1500 μm, particularly preferably 10 to 500 μm. .

[0108]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Hydroxylamine sulfate and additives were dissolved in water as shown in Tables 1 to 4 below, and the pH was adjusted to 30% sulfuric acid and 3%.
Prepared as in Tables 1 to 4 using 0% potassium hydroxide,
An experimental sample solution was prepared.

Each sample solution was divided into two equal parts, one was placed in a plastic bottle, sealed and stored at 2 to 4 ° C. for one week, and the state of crystal precipitation in the sample solution after storage was observed. Further, another one was similarly sealed in another plastic bottle, stored tightly at 50 ° C. for one week, and the remaining amount of hydroxylamine sulfate after storage was quantified.

The above results are summarized in Tables 1 to 4 below.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

[0115]

[Table 4]

In the table, HAS represents hydroxylamine sulfate. Experiment No. Additive OPD2 used in 1-2
Reference numeral 62 denotes Example 5 of JP-T-2001-501649.
And 2.39% by mass of TMAH (tetramethylammonium hydroxide). Furthermore, in the low-temperature storage evaluation, ○ indicates that no crystal precipitation was observed,
"△" is not harmful but slight crystals are observed.
"X" means that precipitation of crystals was recognized and there was a problem in practice.

From the above Tables 1 to 4, the hydroxylamine salt is 18% by mass to 35% by mass, and the compound represented by the general formulas [1] to [6] or the aminopolycarboxylic acid according to the present invention is used. When the content is 1% by mass to 30% by mass and the pH is in the range of 2 to 6, the problem of storage stability at low temperature (crystal precipitation) and stability during storage at high temperature in the state of concentrated hydroxylamine solution is solved. You can see that it can be solved.

The hydroxylamine salt is 18% by mass to 35% by mass, and the compound represented by the general formula [7] or [8] or the polyethylene oxide sorbitan derivative according to the present invention is 0.2% by mass. When the content is 10 to 10% by mass and the pH is in the range of 2 to 6, it is possible to solve the problems of storage stability at low temperature (crystal precipitation) and stability during storage at high temperature in the state of concentrated hydroxylamine solution. I understand.

Furthermore, it can be seen that, if even one of the above constituent elements is missing, all the effects of the present application cannot be satisfied and cannot be put to practical use.

Example 2 Experiment No. 1 of Example 1 Adjust the thickness and material of the plastic container containing the sample solution used in 1-3 appropriately,
A plastic container having an oxygen permeability coefficient shown in the following Table 5 was prepared, and stored in the same manner as in Example 1 except for the above. Incidentally, as the plastic container used in Example 1, a hard bottle having an oxygen permeability coefficient of 16 ml / m ² · atm · day was used. The results after storage are summarized in Table 5 below.

[0121]

[Table 5]

According to Table 5, the oxygen permeability coefficient of the container was 40.
ml / m ² · atm · day or less present at the time of the effect exerts more satisfactorily, further 20ml / m ² · atm · day
It turns out that it becomes especially favorable in the following cases.

Example 3 Experiment No. 2 of Example 2 The plastic container (hard bottle) used in 5-1 to 5-4 was subjected to the same experiment as in Example 2 using a flexible bag having a thickness of 50 to 330 μm and an oxygen permeability coefficient substantially the same. The crystal precipitation properties were each improved by one rank.

[0124]

According to the method for storing a hydroxylamine salt-containing aqueous solution of the present invention, the precipitation of crystals can be suppressed even when the hydroxylamine salt is made into a concentrated aqueous solution at a low temperature, and the high temperature storage can be achieved. It was found that the components could be stably maintained even after the above. Furthermore, since the hydroxylamine salt-containing aqueous solution of the present invention can supply a concentrated hydroxylamine solution, the storage container can be small in size and light in weight, which is extremely suitable in terms of handleability and distribution. .

Claims (6)

[Claims] 1. The method of claim 1, wherein the content of the hydroxylamine salt is 18% by mass to 3%.
In a hydroxylamine salt-containing aqueous solution containing 5% by mass, 1% to 30% by mass of at least one kind of a compound represented by the following general formula [1] or an aminopolycarboxylic acid:
An aqueous solution containing a hydroxylamine salt, wherein the aqueous solution has a pH of 2 to 6. Embedded image [Wherein, R ^{1 to} R ⁷ are each independently a hydrogen atom, -OH, -C
_{OOM, -PO 3 (M) 2} , represents a -SO ₃ M, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. M represents a hydrogen atom or an alkali metal atom, and n and m represent 0 or 1, but are not 0 at the same time. ] 2. The method of claim 1, wherein the content of the hydroxylamine salt is 18% by mass to 3%.
In a hydroxylamine salt-containing aqueous solution containing 5% by mass, at least one compound represented by the following general formula [2] or the following general formula [3] or the following general formula [4] is contained in an amount of 1% by mass to 30% by mass. A hydroxylamine salt-containing aqueous solution having a pH of 2 to 6. Embedded image [In the formula, at least one of A to F is a sulfonic acid group or a sulfonic acid ester group, and the rest represent any of a hydrogen atom, a halogen atom, a hydroxyl group, and a saturated or unsaturated alkyl group. [Chemical formula 3] [In the formula, at least one of G to N is a sulfonic acid group or a sulfonic acid ester group, and the rest represent any of a hydrogen atom, a halogen atom, a hydroxyl group, and a saturated or unsaturated alkyl group. General formula [4] R ₄₁ —SO ₃ M ₄₁ [wherein, R ₄₁ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and M ₄₁ represents a hydrogen atom or Represents an alkali metal such as potassium, sodium, and lithium. ] 3. The method of claim 1, wherein the content of the hydroxylamine salt is 18% by mass to 3%.
In a hydroxylamine salt-containing aqueous solution containing 5% by mass, 1% to 30% by mass of at least one compound represented by the following general formula [5] or [6] is contained, and pH 2 to 6 A hydroxylamine salt-containing aqueous solution, which is characterized in that: General formula [5] HO- (A ₁ -O) l _1- (A ₂ -O) l _2- (A ₃ -O)
l ₃ -H wherein A ₁ , A ₂ , and A ₃ each represent a substituted or unsubstituted linear or branched alkylene group, which may be the same or different. l ₁ , l ₂ and l ₃ each represent 0 or an integer of 1 to 500] [In the formula, R ₁ represents a hydroxyalkyl group or an aminoalkyl group, and R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a benzyl group. R ₁ and R ₂ , R
₂ and R _3, R ₃ and R ₁ or R ₁ and R ₂ and R ₃ may respectively form a ring. ] 4. The method according to claim 1, wherein the amount of the hydroxylamine salt is 18% by mass to 3%.
The hydroxylamine salt-containing aqueous solution containing 5% by mass contains 0.2% by mass to 10% by mass of at least one compound selected from the following general formula [7] or the following general formula [8] or a polyethylene oxide sorbitan derivative. ,
A hydroxylamine salt-containing aqueous solution having a pH of 2 to 6. General formula [7] A ₇ -O- (B ₇ ) _m7- (C ₇ ) _n7 -X _{7 wherein} A ₇ is a monovalent organic group or a group having 3 to 35 carbon atoms.
And an aryl group substituted with an alkenyl group having 2 to 35 carbon atoms. B ₇ and C ₇ are each And may be the same or different (provided that
a, b and c are each 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group). m7
And n7 represent an integer of 1 to 100. X ₇ is a hydrogen atom,
Represents an alkyl group, an aralkyl group or an aryl group. ] Formula [8] _{A 8 -O- (CH 2 CH 2} O) n8 -SO 3 M 8 wherein, M ₈ represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt, n8 is 1 10
And A ₈ represents a monovalent organic group or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms. ] 5. The hydroxylamine salt-containing aqueous solution according to claim 1, which has an oxygen permeability coefficient of 40 m
A method for storing a hydroxylamine salt-containing aqueous solution, wherein the aqueous solution is stored in a plastic container of 1 / m ² · atm · day or less. 6. The method for storing a hydroxylamine salt-containing aqueous solution according to claim 5, wherein the plastic container is a flexible bag.