JPH10306246A - Additive for recording solution and recording solution containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject additive capable of showing defoaming properties and providing excellent printed images, by including a compound which contains a specific repeating unit and is blocked with a fluoroalkyl group at one end. SOLUTION: This additive comprises a compound in which one end of a molecular chain containing a repeating unit of a substitutable alkylene oxide is blocked with a fluoroalkyl, preferably a compound of the formula R<1> -A-B-Dn - R<2> (R<1> is an alkyl in which a part or the whole of hydrogen atoms are fluorinated; A is a single bond or an alkylene; B is an ester bond, a sulfide bond, etc.; D is an ethylene oxide, unit, etc.; (n) is an integer of 1-200; R<2> is an R<1> -A-B or an alkyl). The additive is mixed with a water-soluble dye and an aqueous medium to give a recording solution. The content of the additive is preferably 0.01-10 wt.% based on the total weight of the recording solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an additive for a recording liquid and a recording liquid containing the same, and more particularly to an additive for an ink jet recording liquid and a writing liquid, and a recording liquid and a writing liquid containing the same.

[0002]

2. Description of the Related Art Ink jet recording is a method in which ink is ejected from fine nozzles as droplet particles, and a flight direction of the particles is electrically controlled to draw a pattern. Air flows in from the ink supply unit, the inside of the nozzle dries,
Also, if air flows in from the nozzle discharge part due to impact or the like, the air that has flowed in absorbs the discharge pressure, so that ink cannot be discharged, and as a result, printing can be performed. Will be gone.
In general, an inkjet ink contains a surfactant in order to adjust the surface tension, so that it is very easy to foam when it comes into contact with a gas such as air. Several methods have been proposed to solve such a problem. For example, in Japanese Patent Application Laid-Open No. Hei 6-340071, a hydrophilic layer is provided on the inner surface of a passage through which ink passes so that when air flows into a nozzle of a recording head of an ink jet printer, the air can be easily sucked out. It is devised to form. In addition, Tokuno Sho 6
JP-A-0-48552 and JP-A-60-229969 report that an antifoaming agent or a foam inhibitor such as a fatty acid ester, metal soap, or silicone is added to an ink to prevent the generation of foam. I have.

[0003]

However, a method for forming a hydrophilic layer on the inner surface of a passage through which ink passes inside a nozzle of a recording head of an ink jet printer is as follows.
It is extremely difficult to coat the hydrophobized layer on the fine ink ejection ports, which is not only unsuitable for industrial production, but also sorbitan fatty acid esters and polypropylene glycol in resins such as polysulfone and polyethersulfone as the main body material. It is difficult to form a coating film of a system surfactant from the viewpoints of releasability, adhesion, and stability over time.
In addition, in a method in which an antifoaming agent such as a fatty acid ester, a metal soap, or silicone is added to an ink and used, the antifoaming agent such as silicone is generally hydrolyzed and condensed because the inkjet ink exhibits alkalinity. It has the drawback of easily increasing the viscosity of the ink-jet ink.Defoaming agents such as fatty acid esters and metal soaps have weak defoaming properties and must be used in large amounts because they have low defoaming properties. Has the drawback of increasing.

An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide an excellent defoaming property comprising a compound having a replaceable alkylene oxide repeating unit and having at least one end blocked with a fluoroalkyl group. To provide an additive for ink jet recording and writing and a recording liquid containing the same.

[0005]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, have accomplished the present invention. That is, the present invention relates to the following inventions. 1) A recording liquid additive comprising a compound in which one end of a molecular chain having a replaceable alkylene oxide repeating unit is blocked with a fluoroalkyl group. 2) A compound in which one end of a molecular chain having a replaceable alkylene oxide repeating unit is blocked with a fluoroalkyl group is represented by the following general formula (1): R ¹ -ABD _n -R ² (1) ( In the formula, R ¹ may have a branched structure, may contain an ether bond, may contain a chlorine atom, a bromine atom or an iodine atom, and has an alkyl group in which some or all of the hydrogen atoms have been fluorinated. A represents a single bond, a cycloalkylene or an alkylene which may contain an ether bond, B represents an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond or an alkanolaminoalkyl,
D represents an ethylene oxide unit or a propylene oxide unit or a mixed unit thereof, n represents an integer of 1 to 200, and R ² represents R ¹ -A-
Represents B- or an alkyl group. The above-mentioned additive for recording liquid, which is a compound represented by the formula:

3) A compound in which one end of a molecular chain having a repeatable alkylene oxide unit is blocked with a fluoroalkyl group is a fluorinated alkyl compound having a carboxylic acid group, a carboxylic acid halide group or a carboxylic acid ester group (1) The recording liquid additive according to the above (1) or (2), which is a compound synthesized from a diol having a replaceable alkylene oxide repeating unit or a monol having an alkyl ether at one end. 4) a compound in which one end of a molecular chain having a replaceable alkylene oxide repeating unit is blocked with a fluoroalkyl group, a fluorinated alkyl compound having an epoxy group, and a diol having a replaceable alkylene oxide repeating unit or (1) The recording liquid additive according to the above (1) or (2), which is a compound synthesized from a monol having an alkyl ether at one end. 5) The recording liquid according to the above 2, wherein R ¹ is a compound represented by X (CF ₂ ) _m — (where X represents a hydrogen atom or a halogen atom, and m represents an integer of 1 to 20). Additives. 6) A recording liquid comprising a water-soluble dye, an aqueous medium, and the above-mentioned recording liquid additives 1 to 5. 7) The recording liquid according to 6 above, wherein the content of the recording liquid additive is in the range of 0.01 to 10% by weight based on the total weight of the recording liquid.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The additive of the present invention and a recording liquid containing the same will be described below. The compound of the present invention in which one end of a molecular chain having a substitutable alkylene oxide repeating unit is blocked with a fluoroalkyl group is represented by the following general formula (1): R ¹ -ABD _n -R ² (1) Are suitable. Wherein a chlorine atom, which may have a branched structure, may contain an ether bond,
A part or all of the hydrogen atoms, which may be substituted with a bromine atom or an iodine atom, represent a fluorinated alkyl group, A represents a single bond, a cycloalkylene or an alkylene which may contain an ether bond, and B represents Represents an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond or an alkanolaminoalkyl, D represents an ethylene oxide unit or a propylene oxide unit or a mixed unit thereof, and n represents 1 to 200. And R ² represents R ¹ -AB or an alkyl group.

In a compound represented by the general formula (1) having at least one terminal of a molecular chain having a repeatable unit of a displaceable alkylene oxide and blocked with a fluoroalkyl group, an applicable fluorinated alkyl group (R
¹ ) is CF ₃ , F (CF ₂ ) ₂ , F (CF ₂ ) ₃ , F (C
_{F 2) 4, F (CF} 2) 5, F (CF 2) 6, F (CF 2) 7, F (CF 2) 8, F (C
F ₂ ) ₉ , F (CF ₂ ) ₁₀ , HCF ₂ , H (CF ₂ ) ₂ , H (CF ₂ ) ₃ , H (C
F ₂ ) ₄ , H (CF ₂ ) ₅ , H (CF ₂ ) ₆ , H (CF ₂ ) ₇ , H (CF ₂ ) ₈ , H (C
F ₂ ) ₉ , H (CF ₂ ) ₁₀ , ClCF ₂ , Cl (CF ₂ ) ₂ , Cl (CF ₂ ) ₃ ,
Cl (CF ₂ ) ₄ , Cl (CF ₂ ) ₅ , Cl (CF ₂ ) ₆ , Cl (CF ₂ ) ₇ , C
_{l (CF 2) 8, Cl} (CF 2) 29, Cl (CF 2) 10, CF (CF 3) OC 3 F 7, CF
(CF ₃ ) OCF ₂ CF (CF ₃ ) -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₂ -OC ₃ F
₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₃ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (C
F ₃ )) ₄ -OC ₃ F ₇ , CF (CF ₃ ) (OCF (CF ₃ ) ₂ CF) ₅ -OC ₃ F ₇ , CF (C
F ₃ ) (OCF ₂ CF (CF ₃ )) ₆ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₇ -O
C ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₈ -OC ₃ F _{7 and the} like.
Particularly preferred is an X (CF ₂ ) _m — group. On this occasion,
The number of carbon atoms of R ¹ is such that a compound having a substitutable alkylene oxide repeating unit represented by the above general formula (1) and having at least one terminal of its molecular chain blocked by a fluoroalkyl group is soluble in water It is sufficient if the cohesive force of the fluorine moiety is expressed in water, and therefore, usually 2 to 10 is preferable. When the carbon number of R ¹ is 1, the cohesive force of the fluorine moiety is hardly exhibited, and even when added to the ink, the defoaming property is not high. When the carbon number exceeds 10, the solubility in water or the ink decreases, which is not preferable.

In a compound having a repeating unit of a substitutable alkylene oxide represented by the general formula (1) and having at least one end of its molecular chain blocked by a fluoroalkyl group, A is a single bond, alkylene , Cycloalkylene, alkylene which may contain an ether bond is applicable, and B is an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond or an alkanolaminoalkyl. . R represented by the general formula (1)
¹ ethylene oxide unit or a propylene oxide unit or repeated mixing unit thereof, for illustrating a connection portion between the D _n, generally it is difficult to define, replaceable alkylene oxide represented by the general formula (1) Is determined by a raw material used for producing a compound having a repeating unit having at least one terminal blocked with a fluoroalkyl group. A or B, which is a bonding portion, has a repeating unit of a substitutable alkylene oxide represented by the general formula (1), and is stable when a compound having at least one end blocked with a fluoroalkyl group is added to the ink. Any type of bonding may be used, but considering that the ink exhibits alkalinity, for A, alkylene, cycloalkylene, alkylene which may contain an ether bond, B
As for, an amide bond, a urethane bond, a thiourethane bond, an ether bond and the like are preferable.

In a compound having a repeating unit of a substitutable alkylene oxide represented by the general formula (1) and having at least one end blocked with a fluoroalkyl group, an applicable ethylene oxide unit, that is, an ethylene oxide unit or The propylene oxide unit or a mixture thereof is repeated, and _n of D n is an integer of 1 to 200. When the value of n is smaller than the molecular weight of the fluorinated alkyl group (R ¹ ), it is difficult to dissolve in water or ink when the molecular weight is small. It becomes difficult to do. Therefore, the value of n is preferably 2-100, more preferably 2-50. In a compound having a substitutable alkylene oxide repeating unit represented by the general formula (1) and having at least one end blocked with a fluoroalkyl group, applicable R ² is R ¹ -AB or alkyl. R represents a group
^1- AB is, for example, R ¹ , A and B described above.
You can choose from a combination of Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Next, a process for producing a compound having a repeatable alkylene oxide repeating unit according to the present invention and having at least one terminal of its molecular chain blocked by a fluoroalkyl group will be described. In the present invention, a method for producing a compound having a substitutable alkylene oxide repeating unit, in which at least one terminal of the molecular chain is blocked with a fluoroalkyl group, varies depending on the bonding mode of the compound.

For example, a compound having a repeating unit of a substitutable alkylene oxide having an ester bond and having at least one terminal of its molecular chain blocked by a fluoroalkyl group may be a carboxylic acid, a carboxylic acid halide or a carboxylic acid ester. Fluorinated alkyl compounds having a branched structure, fluorinated alkyl compounds having a branched structure, fluorinated alkyl compounds which may contain an ether bond, fluorinated alkyl compounds which may contain methine or methylene, fluorinated alkyl compounds which may contain chlorine, bromine or iodine The compound can be synthesized by reacting a compound with a diol having a repeating unit of ethylene oxide or a monol having an alkyl ether at one end. Carboxylic acid, carboxylic acid halide, fluorinated alkyl compound having a carboxylic acid ester, fluorinated alkyl compound having a branched structure, fluorinated alkyl compound which may contain an ether bond, fluorinated alkyl compound which may contain methine or methylene, chlorine Examples of fluorinated alkyl compounds that may contain, bromine or iodine include trifluoroacetic acid, perfluoropropionic acid, perfluoropropanoic acid, perfluorovaleic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid , Perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluoro (2,
5,8-trimethyl-3,6,9-trioxadodecanoyl) fluoride, perfluoro (2,5,8,11
-Tetramethyl-3,6,9,12-tetraoxapentadecanoyl) fluoride, 3H-tetrafluoropropionic acid, 5H-octafluorovaleric acid, 5H-
Octafluorovaleryl chloride, 7H-dodecafluoroheptanoic acid, 7H-dodecafluoroheptanoyl chloride, 9H-hexadecafluorononanoic acid, 9H-
Hexadecafluorononanoyl chloride, 11H-icosafluoroundecanoyl chloride, 3-chlorotetrafluoropropionic acid, 3-chlorotetrafluoropropionyl chloride, 3,4-dichloropentafluorobutanoic acid, 3,4-dichloropentafluoro Butyryl chloride, 3,5,6-trichlorooctafluorohexanoic acid, 3,5,6-trichlorooctafluorohexanoyl chloride, 2,2-bis (trifluoromethyl) propionic acid, 2,2-bis (trifluoro Methyl) propionyl fluoride, methyl perfluoropropionate, ethyl perfluoropropionate, methyl perfluorobutyrate, ethyl perfluorobutyrate, methyl perfluorooctanoate, ethyl perfluoroocta Benzoate, methyl difluoroacetate, main dust difluoroacetate, ethyl difluoroacetate, ethyl 5H- octafluoro pentanoate, ethyl 7H- dodecafluoro heptanoate, ethyl 9H- hexadecafluoro nonanoate, ethyl 11
H-icosafluoroundecanoate and the like.
Examples of the diol having a repeating unit of ethylene oxide or the monool having an alkyl ether at one end include monoethylene glycol, diethylene glycol, tetraethylene glycol, various poly (ethylene glycol) s having different molecular weights, and poly (ethylene glycol) methyl. Ether, poly (ethylene glycol)
Ethyl ether, poly (ethylene glycol) propyl ether, poly (ethylene glycol) butyl ether and the like can be mentioned.

The esterification reaction can be carried out by a generally known method, so that the reaction temperature, reaction time, reaction pressure, reaction catalyst and the like do not need to be particularly specified.
The reaction solvent has a desired displaceable alkylene oxide repeating unit, assists in forming a compound in which at least one end is blocked with a fluoroalkyl group, and dissolves the reaction starting material and the product well, and All solvents can be used as long as they do not react with. A repeating unit of the substitutable alkylene oxide having an ester bond, at least one terminal as an example of a compound blocked with a fluoroalkyl group, for example, _{F (CF 2) 2 COO (} CH 2 CH 2 O) n CO ( CF ₂ ) ₂ F (average molecular weight of polyethylene oxide is 600), F (CF ₂ ) ₃ COO
(CH ₂ CH ₂ O) _n CO (CF ₂ ) ₃ F (average molecular weight of polyethylene oxide is 600), F (CF ₂ ) ₄ COO (CH ₂ CH ₂ O) _n CO (CF ₂ ) ₄ F
(The average molecular weight of polyethylene oxide is 600), F
(CF ₂ ) ₅ COO (CH ₂ CH ₂ O) _n CO (CF ₂ ) ₅ F (average molecular weight of polyethylene oxide is 600), H (CF ₂ ) ₂ COO (CH ₂ CH ₂ O) _n CO
(CF ₂ ) ₂ H (Polyethylene oxide has an average molecular weight of 60
_{0), H (CF 2)} 3 COO (CH 2 CH 2 O) n CO (CF 2) 3 H ( average molecular weight of polyethylene oxide is _{600), H (CF 2)} 4 COO (CH 2 CH
₂ O) _n CO (CF ₂ ) ₄ H (average molecular weight of polyethylene oxide is 600), H (CF ₂ ) ₅ COO (CH ₂ CH ₂ O) _n CO (CF ₂ ) ₅ H (average molecular weight of polyethylene oxide is 600), F (CF ₂ ) ₃ O [C
F (CF ₃ ) CF ₂ O] ₂ CF (CF ₃ ) COO (CH ₂ CH ₂ O) _n COCF (CF ₃ ) [OCF ₂ CF (C
F ₃ )] ₂ O (CF ₂ ) ₃ F (average molecular weight of polyethylene oxide is 900), F (CF ₂ ) ₄ COO (CH ₂ CH ₂ O) _n CH ₃ (average molecular weight of polyethylene oxide is 550), H (CF ₂ ) ₄ COO (CH ₂ CH
₂ O) _n CH ₃ (Polyethylene oxide has an average molecular weight of 55
0) and the like.

Compounds having a substitutable alkylene oxide repeating unit having an amide bond and having at least one end blocked with a fluoroalkyl group include fluorinated alkyl compounds having a carboxylic acid, carboxylic acid halide, and fluorine having a branched structure. Having a repeating unit of a fluorinated alkyl compound, a fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, a fluorinated alkyl compound which may contain chlorine, bromine or iodine, and ethylene oxide. It can be synthesized from a reaction with a diamine compound having a primary amine at the end or a monoamine compound having an alkyl ether at one end. Carboxylic acid, fluorinated alkyl compound having a carboxylic acid halide, fluorinated alkyl compound having a branched structure, fluorinated alkyl compound optionally containing an ether bond, fluorinated alkyl compound optionally containing methine or methylene, chlorine, bromine or iodine Examples of the fluorinated alkyl compound that may include: trifluoroacetic acid, perfluoropropionic acid, perfluoropropanoic acid, perfluorovaleic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononane acid,
Perfluorodecanoic acid, perfluoroundecanoic acid, perfluoro (2,5,8-trimethyl-3,6,9-trioxadodecanoyl) fluoride, perfluoro (2,5,8,11-tetramethyl-3, 6,9,12
-Tetraoxapentadecanoyl) fluoride, 3H
-Tetrafluoropropionic acid, 5H-octafluorovaleryl acid, 5H-octafluorovaleryl chloride, 7H-dodecafluoroheptanoic acid, 7H-dodecafluoroheptanoyl chloride, 9H-hexadecafluorononanoic acid, 9H-hexadecafluoro Nonanoyl chloride, 11H-icosafluoroundecanoyl chloride, 3-chlorotetrafluoropropionic acid, 3-
Chlorotetrafluoropropionyl chloride, 3,4
-Dichloropentafluorobutanoic acid, 3,4-dichloropentafluorobutyryl chloride, 3,5,6-trichlorooctafluorohexanoic acid, 3,5,6-trichlorooctafluorohexanoyl chloride, 2,2-
Bis (trifluoromethyl) propionic acid, 2,2-bis (trifluoromethyl) propionyl fluoride and the like can be mentioned. Examples of the diamine having a repeating unit of ethylene oxide or the monoamine having an alkyl ether at one end include, for example, α, ω-bis (3-aminopropyl) -poly (ethylene glycol)
Ether, α, ω-bis (3-aminopropyl) -diethylene glycol ether and the like.

Compounds having a substituted alkylene oxide repeating unit having an amide bond and having at least one end blocked with a fluoroalkyl group include fluorinated alkyl compounds having an amino group and fluorinated alkyl compounds having a branched structure. A fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, a fluorinated alkyl compound which may contain chlorine, bromine or iodine and a dicarboxylic acid having a repeating unit of ethylene oxide or one terminal Can be synthesized from a reaction with a monocarboxylic acid in which is an alkyl ether. A fluorinated alkyl compound having an amino group, a fluorinated alkyl compound having a branched structure, a fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, may contain chlorine, bromine or iodine Examples of fluorinated alkyl compounds include 1
H, 1H-heptafluorobutylamine, 1H, 1H-
Pentadecafluorooctylamine and the like can be mentioned. Examples of a dicarboxylic acid having a repeating unit of ethylene oxide or a monocarboxylic acid having an alkyl ether at one end include poly (ethylene glycol) bis (carbonylmethyl) ether.

Since the amidation reaction can be carried out by a generally known method, there is no need to particularly define the reaction temperature, reaction time, reaction pressure, reaction catalyst and the like.
The reaction solvent has a desired displaceable alkylene oxide repeating unit, assists in forming a compound in which at least one end is blocked with a fluoroalkyl group, and dissolves the reaction starting material and the product well, and All solvents can be used as long as they do not react with. Examples of compounds having a substitutable alkylene oxide repeating unit having an amide bond and at least one end of which is blocked with a fluoroalkyl group include, for example, F (CF ₂ ) ₂ CONHC ₃ H ₆ O (CH ₂ CH ₂ O ₂ ) C ₃ H ₆ NHCO (C
F ₂ ) ₂ F, H (CF ₂ ) ₂ CONHC ₃ H ₆ O (CH ₂ CH ₂ O ₂ ) C ₃ H ₆ NHCO (CF ₂ ) ₂ H
, F (CF ₂ ) ₃ CONHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCO (CF ₂ ) ₃ F (the average molecular weight of polyethylene oxide is 600), F (CF ₂ )
₄ CONHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCO (CF ₂ ) ₄ F (average molecular weight of polyethylene oxide is 600), H (CF ₂ ) ₄ CONHC ₃ H ₆ O
(CH ₂ CH ₂ O) _n C ₃ H ₆ NHCO (CF ₂ ) ₄ H (average molecular weight of polyethylene oxide is 600), F (CF ₂ ) ₃ O [CF (CF ₃ ) CF ₂ O] ₂ CF (C
F ₃ ) CONHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCOCF (CF ₃ ) [OCF ₂ CF (CF ₃ )]
₂ O (CF ₂ ) ₃ F (The average molecular weight of polyethylene oxide is 9
00).

The compound having a repeating unit of a displaceable alkylene oxide having a urethane bond and having at least one end blocked with a fluoroalkyl group is a fluorinated alkyl compound having an isocyanate group, a fluorinated alkyl compound having a branched structure, A fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, a fluorinated alkyl compound which may contain chlorine, bromine or iodine, and a diol having a repeating unit of ethylene oxide or one end of which is alkyl It can be synthesized from a reaction with a monol that is an ether. A fluorinated alkyl compound having an isocyanate group, a fluorinated alkyl compound having a branched structure, a fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, may contain chlorine, bromine or iodine Examples of the fluorinated alkyl compound include 1H, 1H-heptafluorobutyl isocyanate, 1H, 1H-pentadecafluorooctyl isocyanate, and the like.

The compound having a repeating unit of a displaceable alkylene oxide having a urethane bond and having at least one end blocked with a fluoroalkyl group is a fluorinated alkyl compound having a hydroxyl group, a fluorinated alkyl compound having a branched structure, A fluorinated alkyl compound that may contain an ether bond, a fluorinated alkyl compound that may contain methine or methylene, a fluorinated alkyl compound that may contain chlorine, bromine or iodine, and a diisocyanate having a repeating unit of ethylene oxide or one terminal alkyl. It can be synthesized from a reaction with a monoisocyanate which is an ether. Fluorinated alkyl compound having a hydroxyl group, fluorinated alkyl compound having a branched structure, fluorinated alkyl compound which may contain an ether bond, fluorinated alkyl compound which may contain methine or methylene, fluorine which may contain chlorine, bromine or iodine Examples of the alkylated compound include 2,2,2-trifluoroethanol, 2,2,2
3,3,3-pentafluoropropanol, 6- (perfluoroethyl) hexanol, 1H, 1H-heptafluorobutanol, 2- (perfluorobutyl) ethanol, 3-perfluorobutyl-2-iodopropanol, 6- ( Perfluorobutyl) hexanol, 2-perfluoropropoxy-2,3,3,3-tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 3- (perfluorohexyl) propanol,
3-perfluorohexyl-2-iodopropanol,
6- (perfluorohexyl) hexanol, 2- (perfluorooctyl) ethanol, 3- (perfluorooctyl) propanol, 3-perfluorooctyl-
2-iodopropanol, 6- (perfluorooctyl) hexanol, 2- (perfluorodecyl) ethanol, 6- (perfluoro-1-methylethyl) hexanol, 2- (perfluoro-3-methylbutyl) ethanol, 6- (Perfluoro-3-methylbutyl) hexanol, 2- (perfluoro-5-methylhexyl)
Ethanol, 3- (perfluoro-5-methylhexyl) -2-iodopropanol, 6- (perfluoro-
5- (methylhexyl) hexanol, 2- (perfluoro-7-methyloctyl) ethanol, 3- (perfluoro-7-methyloctyl) -2-iodopropanol, 6- (perfluoro-7-methyloctyl) hexanol, 2- (perfluoro-9-methyldecyl) ethanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol,
1H, 1H, 7H-dodecafluoroheptanol, 1
H, 1H, 9H-hexadecafluorononanol, 2-
Fluoroethanol, 2H-hexafluoro-2-propanol, 1H, 1H, 3H-hexafluorobutanol, 2,2-bis (trifluoromethyl) propanol and the like can be mentioned. Examples of diisocyanates having a repeating unit of ethylene oxide or monoisocyanates having an alkyl ether at one end include α,
ω-bis (3-isocyanatopropyl) -poly (ethylene glycol) ether, α, ω-bis (3-isocyanatopropyl) -diethylene glycol ether, and the like.

The urethanization reaction can be carried out by a generally known method, and therefore, the reaction temperature, reaction time, reaction pressure, reaction catalyst and the like need not be particularly specified.
The reaction solvent has a desired displaceable alkylene oxide repeating unit, assists in forming a compound in which at least one end is blocked with a fluoroalkyl group, and dissolves the reaction starting material and the product well, and All solvents can be used as long as they do not react with. Examples of compounds having a repeating unit of a displaceable alkylene oxide having a urethane bond and at least one end of which is blocked with a fluoroalkyl group include, for example, F (CF ₂ ) ₂ OCONHC ₃ H ₆ O (CH ₂ CH ₂ O ) ₂ C ₃ H ₆ NHCOO (C
F ₂ ) ₂ F, H (CF ₂ ) ₂ OCONHC ₃ H ₆ O (CH ₂ CH ₂ O) ₂ C ₃ H ₆ NHCOO (CF ₂ ) ₂
H, F (CF ₂ ) ₃ OCONHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCOO (CF ₂ ) ₃ F
(The average molecular weight of polyethylene oxide is 600), F
(CF ₂ ) ₄ OCONHC ₃ H ₆ O (CH ₂ CH ₂ O) nC ₃ H ₆ NHCOO (CF ₂ ) ₄ F (average molecular weight of polyethylene oxide is 600), H (CF ₂ ) ₄ O
CONHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCOO (CF ₂ ) ₄ H (average molecular weight of polyethylene oxide is 600), F (CF ₂ ) ₃ O [CF (CF ₃ )
CF ₂ O] ₂ CF (CF ₃ ) OCONHC ₃ H ₆ O (CH ₂ CH ₂ O) nC ₃ H ₆ NHCOOCF (CF ₃ )
[OCF ₂ CF (CF ₃ )] ₂ O (CF ₂ ) ₃ F (the average molecular weight of polyethylene oxide is 900).

Compounds having a urea bond-substitutable alkylene oxide repeating unit and having at least one end blocked with a fluoroalkyl group include a fluorinated alkyl compound having an isocyanate group, a fluorinated alkyl compound having a branched structure, A fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, a fluorinated alkyl compound which may contain chlorine, bromine or iodine and a repeating unit of ethylene oxide, and both terminals are primary It can be synthesized from a reaction with a diamine compound which is an amine or a monoamine compound having an alkyl ether at one end. A fluorinated alkyl compound having an isocyanate group, a fluorinated alkyl compound having a branched structure, a fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, may contain chlorine, bromine or iodine Examples of the fluorinated alkyl compound include 1H, 1H-heptafluorobutyl isocyanate, 1H, 1H-pentadecafluorooctyl isocyanate, and the like.
Examples of the diamine having a repeating unit of ethylene oxide or the monoamine having an alkyl ether at one terminal include α, ω-bis (3-aminopropyl) -poly (ethylene glycol) ether and α, ω-
Bis (3-aminopropyl) -diethylene glycol ether and the like can be mentioned. For the ureation reaction, a generally known method can be used.
The reaction time, reaction pressure, reaction catalyst and the like need not be particularly specified. The reaction solvent has a desired displaceable alkylene oxide repeating unit, assists in forming a compound in which at least one end is blocked with a fluoroalkyl group, and dissolves the reaction starting material and the product well, and All solvents can be used as long as they do not react with.

Compounds having a repeating unit of a displaceable alkylene oxide having an ether bond and having at least one terminal blocked with a fluoroalkyl group include a fluorinated alkyl compound having an epoxy group, a fluorinated alkyl compound having a branched structure, A fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, a fluorinated alkyl compound which may contain chlorine, bromine or iodine, and a diol having a repeating unit of ethylene oxide or one end of which is alkyl It can be synthesized from a reaction with a monol that is an ether. Having a repeating unit of a displaceable alkylene oxide having a urea bond,
Examples of compounds in which at least one end is blocked with a fluoroalkyl group include, for example, F (CF ₂ ) ₃ CH ₂ NHCONHC ₃ H ₆ O (CH ₂ C
H ₂ O) ₂ C ₃ H ₆ NHCONHCH ₂ (CF ₂ ) ₃ F, H (CF ₂ ) ₃ CH ₂ NHCONHC ₃ H ₆ O
_{(CH 2 CH 2 O) 2} C 3 H 6 NHCONHCH 2 (CF 2) 3 H, F (CF 2) 3 CH 2 NHCONHC
_{3 H 6 O (CH 2 CH} 2 O) n C 3 H 6 NHCONHCH 2 (CF 2) 3 F (600 average molecular weight of polyethylene _{oxide), H (CF 2) 3} CH 2 NHCONH
_{C 3 H 6 O (CH 2} CH 2 O) n C 3 H 6 NHCONHCH 2 (CF 2) 3 H ( average molecular weight of polyethylene oxide is 600), and the like.

A fluorinated alkyl compound having an epoxy group, a fluorinated alkyl compound having a branched structure, a fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, chlorine, bromine or iodine is used. Examples of the fluorinated alkyl compound that may be contained include 3-perfluorobutyl-1,
2-epoxypropane, 3-perfluorohexyl-
1,2-epoxypropane, 3-perfluorooctyl-1,2-epoxypropane, 3-perfluorododecyl-1,2-epoxypropane, 3- (perfluoro-
3-methylbutyl) -1,2-epoxypropane, 3-
(Perfluoro-5-methylhexyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) -1,2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2 -Epoxy propane, 3
-(2,2,3,3-tetrafluoropropoxy)-
1,2-epoxypropane, 3- (1H, 1H, 5H-
Octafluoropentyloxy) -1,2-epoxypropane, 3- (1H, 1H, 7H-dodecafluoropeptyloxy) -1,2-epoxypropane, 3- (1
H, 1H, 9H-hexadodecafluorononyloxy)
-1,2-epoxypropane and the like.

The compound having a repeating unit of a displaceable alkylene oxide having an ether bond and having at least one end blocked with a fluoroalkyl group is a fluorinated alkyl compound having an alkyl halide or a fluorinated alkyl compound having a branched structure. Compound, fluorinated alkyl compound which may contain ether bond, fluorinated alkyl compound which may contain methine or methylene, fluorinated alkyl compound which may contain chlorine, bromine or iodine and diol having repeating unit of ethylene oxide or one terminal Can be synthesized from a reaction with a monol in which is an alkyl ether.

Fluorinated alkyl compounds having an alkyl halide, fluorinated alkyl compounds having a branched structure, fluorinated alkyl compounds which may contain an ether bond, fluorinated alkyl compounds which may contain methine or methylene, chlorine, bromine or iodine Examples of the fluorinated alkyl compound that may contain perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, 2- (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, (Fluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perful Rodeshiru) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro -5
-Methylhexyl iodide, 2- (perfluoro-
5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro- 9-methyldecyl) ethyl iodide,
2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide and the like.

Since the etherification reaction can be carried out by a generally known method, the reaction temperature, reaction time, reaction pressure, reaction catalyst and the like need not be particularly specified.
The reaction solvent has a desired displaceable alkylene oxide repeating unit, assists in forming a compound in which at least one end is blocked with a fluoroalkyl group, and dissolves the reaction starting material and the product well, and All solvents can be used as long as they do not react with. Examples of the compound having a repeating unit of a displaceable alkylene oxide having an ether bond and at least one end of which is blocked with a fluoroalkyl group include, for example, F (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ O (CH ₂ CH ₂ O) _n CH ₂ CH (O
H) CH ₂ (CF ₂ ) ₄ F (average molecular weight of polyethylene oxide is 600), H (CF ₂ ) ₄ CH ₂ OCH ₂ CH (OH) CH ₂ O (CH ₂ CH ₂ O) _n CH ₂ C
_{H (OH) CH 2 OCH 2} (CF 2) 4 H ( average molecular weight of polyethylene oxide is _{600), (CF 3 2)} CF (CF 2) 2 CH 2 CH (OH) CH 2 O (CH 2 C
H ₂ O) _n OCH ₂ CH (OH) CH ₂ (CF ₂ ) ₂ CF (CF ₃ ) (average molecular weight of polyethylene oxide is 600), F (CF ₂ ) ₄ CH ₂ CH ₂ O (CH ₂ CH
₂ O) _n CH ₂ CH ₂ (CF ₂ ) ₄ F (average molecular weight of polyethylene oxide is 600), (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n CH ₃
(Average molecular weight of polyethylene oxide is 600), H
(CF ₂ ) ₄ CH ₂ O (CH ₂ CH ₂ O) _n CH ₂ (CF ₂ ) ₄ H (average molecular weight of polyethylene oxide is 600), CF ₂ ClCFClO (CH ₂ CH ₂ O) _n
CFClCF ₂ Cl (Polyethylene oxide has an average molecular weight of 4
00).

Compounds having a repeating unit of a displaceable alkylene oxide having an alkanolaminoalkyl and having at least one end blocked with a fluoroalkyl group are fluorinated alkyl compounds having an epoxy group and fluorinated alkyl compounds having a branched structure. A fluorinated alkyl compound which may contain an ether bond, a fluorinated alkyl compound which may contain methine or methylene, a fluorinated alkyl compound which may contain chlorine, bromine or iodine, and a repeating unit of ethylene oxide, and both ends are 1 It can be synthesized from a reaction with a diamine compound which is a secondary amine or a monoamine compound having an alkyl ether at one end. The reaction for forming the alkanolaminoalkyl can be carried out by a generally known method, and therefore, the reaction temperature, reaction time, reaction pressure, reaction catalyst and the like need not be particularly specified. The reaction solvent has a desired displaceable alkylene oxide repeating unit, helps to form a compound in which at least one end is blocked with a fluoroalkyl group, and dissolves the reaction starting material and the product well, and All solvents can be used as long as they do not react with. Examples of compounds having a substitutable alkylene oxide repeating unit having an alkanolaminoalkyl and having at least one terminal blocked with a fluoroalkyl group include, for example, F (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ NHC ₃ H ₆ O (CH ₂ CH
₂ O) _n C ₃ H ₆ NHCH ₂ CH (OH) CH ₂ (CF ₂ ) ₄ F (average molecular weight of polyethylene oxide is 600), H (CF ₂ ) ₄ CH ₂ OCH ₂ CH (OH) CH
₂ NHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCH ₂ CH (OH) CH ₂ OCH ₂ (CF ₂ ) ₄ H
(Average molecular weight of polyethylene oxide is 600), (C
F ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ NHC ₃ H ₆ O (CH ₂ CH ₂ O) _n C ₃ H ₆ NHCH ₂
CH (OH) CH ₂ (CF ₂ ) ₂ CF (CF ₃ ) (the average molecular weight of polyethylene oxide is 600).

In the present invention, the compound having a replaceable alkylene oxide repeating unit, wherein at least one terminal of the molecular chain is blocked with a fluoroalkyl group, may be used alone or in combination of two or more. It can be used in the range of 0.01 to 10% by weight based on the total weight of the recording liquid. If the amount added is less than 0.01% by weight, the generation of bubbles cannot be prevented as an antifoaming agent. If the amount is more than 10% by weight, the dye will sediment or the viscosity will increase. In order to effectively exhibit its function as an antifoaming agent, the range is preferably 0.05 to 5% by weight. In the present invention, the compound having a substitutable alkylene oxide repeating unit, the molecular weight of which at least one terminal of the molecular chain is blocked by a fluoroalkyl group, has a substitutable alkylene oxide repeating unit, and has at least one terminal Ink containing a compound in which is blocked with a fluoroalkyl group,
There is no particular limitation as long as it can be ejected from the ink jet printer head, but since a high molecular weight usually results in an increase in the viscosity of the ink, which makes it impossible to eject the ink, it has a replaceable alkylene oxide repeating unit. The molecular weight of a compound in which at least one terminal is blocked with a fluoroalkyl group is 200 to 5
It is preferably in the range of 000, preferably 300 to 10,000.
A range of 00 is preferred.

The water-soluble dye used in the present invention is not particularly limited as long as it can be dissolved in water. Examples of the direct dye described in the color index (COLOUR INDEX) include:
Acid dyes, basic dyes, reactive dyes, food dyes and the like can be mentioned. Specific examples of direct dyes include, for example, CIDirect Black 2, 4
, 9, 11, 14, 17, 17, 19, 22, 27, 32, etc., CIDirect B
lue (direct blue) 1,2,6,8,15,22,2
5, 34, 69, 70, etc., CIDirect Brown (Direct
Brown) 1A, 2, 6, 25, 27, 44, 58, 95, etc., CIDi
rect Green 1,6,8,2
8, 33, 37, 63, etc., CIDirect Orange (Direct
Orange) 6, 8, 10, 26, 29, 39, 41, 49, 51, etc., C.
I.DirectRed (Direct Red) 1, 2, 4, 8,
9, 11, 13, 17, 20, 23, etc., CIDirect Violet (direct violet) 1, 7, 9, 12, 35, 48, 51
Etc., CIDirect Yellow1,
2, 4, 8, 11, 12, 24, 26, 27, 28 and the like.
Examples of the acid dye include CIAcid Black 1, 2, 7, 16, 17, 24, 26, 28, 3
1, 41, 48, 52, etc., CIAcid Blue (acid blue) 1
, 7, 9, 22, 23, 25, 27, 29, 40, etc., CIAcid Bro
wn (Acid Brown) 4, 14 etc., CIAcid Green
(Acid Green) 3, 9, 12, 16, 19, 20, 25,
27 mag, CIAcid Orange 7, 8
, 10, 33, 56, etc., CIAcid Red 1, 4, 6, 8, 13, 14, 15, 18, 19, 21, 26, 2
7, 30, 32, 34, etc., CIAcid Violet (acid violet) 7, 11, 15, 34, 35, 41, 43, etc., CIAcid
Yellow 1,3,4,7,11,1
2, 13, 14, 17, 18, 19, 23, 25, 29, 34, 36, 38 and the like.

As the basic dye, for example, CIBasi
c Black (Basic Black) 2, 8, CIBasic
Blue (Basic blue) 1, 3, 5, 7, 9, 9, 2
4, 25, 26 etc., CIBasicBrown (basic brown) 1,12. CIBasic Green 1,4. CIBasic Orange (Basic Orange) 2, 15, 21 etc.CIBasic Red (Basic Red) 1, 2, 9, 12 etc., CIBasic Violet (Basic Violet) 1, 3, 5, 7, 9, 9, 24, 25 etc.
I.Basic Yellow 1, 2, 1
1, 12, 14, 21, 32, 36 and the like.

As the reactive dye, for example, CIReac
tive Black 1,3,5,
6, 8 etc. CIReactive Blue (reactive blue) 2, 5, 7, 12, 13, 14, 15, 17, 18, 19 etc. CIRea
ctive Brown (reactive brown) 1, 7 etc., C.
I. Reactive Green (reactive green) 5 etc.
CIReactive Orange 2,
5, 7, 16, etc., CIReactive Red (reactive red) 6, 7, 11, 12, 15, 17, 21, 23, etc., CIReacti
ve Violet (reactive violet) 2, 4, 5
, 8 and the like, CIReactive Yellow (reactive yellow) 1, 2, 3, 13, 14, 15 and the like. As food dyes, for example, CIFood Black (food black) 2, CIFood Blue (food blue) 3, 4
,Five . CIFood Green 2, 3
, CIFood Red (food red) 2, 3, 7, 9
, 14, 52, 87, 92, 94, 102 etc., CIFood Violet
(Food violet) 2, CIFoodYellow (food yellow) 3, 4, 5 and the like.

The content of the water-soluble dye ranges from 0.2 to 12% by weight, preferably from 2 to 8% by weight, based on the total weight of the recording liquid. Examples of the water-soluble medium used for the recording liquid include water and an organic solvent miscible with water, such as alcohols (methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, 1,2-propanediol). ,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 400), polyethylene glycol (# 600), Glycerin, etc.), ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 1,4-dioxane, etc.), ketones (acetone, diacetone alcohol, etc.), nitrogen-containing aqueous solution Organic solvents (triethylamine, triethanolamine, diethanolamine, tripropanolamine, N-methylpyrrolidone, N-ethyl Pyrrolidone, N, N- dimethylformamide, pyridine, 1,3-dimethyl - imidazolidinone), dimethyl sulfoxide and the like. Among them, those having a boiling point higher than that of water have a function as a wetting agent for preventing drying of the nozzle tip, and therefore polyalkylene glycols (eg, polyethylene glycol, polypropylene glycol, etc.) and lower alkyl ethers (eg, Ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, etc.).

The preferable content of the water-soluble medium in the recording liquid is in the range of 10 to 80% by weight of water and 70% by weight or less of an organic solvent miscible with water, based on the total weight of the recording liquid. If necessary for the ink composition, an antiseptic / fungicide (eg, sodium dehydroacetate), a chelating reagent (eg, sodium ethylenediaminetetraacetate), a rust inhibitor (eg, ammonium thioglycolate), an oxygen absorber (eg, sulfurous acid) Sodium), a pH adjuster, a viscosity adjuster, a penetrant, a nozzle drying inhibitor, and the like. The recording liquid of the present invention is prepared by adding the above dye to an aqueous medium and mixing with a magnetic stirrer, a stirrer, a paint conditioner or the like, and if necessary, the above-mentioned antiseptic / antifungal agent, chelating reagent, rust inhibitor, oxygen After adding an absorbent, a pH adjuster, a viscosity adjuster, a penetrant, a nozzle drying inhibitor, etc., a compound having a repeatable unit of the displaceable alkylene oxide of the present invention and at least one end of which is blocked with a fluoroalkyl group. May be added and further mixed.

The ink of the present invention has a diameter of 10 to 100.
In order to pass through a fine nozzle of μm, it is preferable to filter with a filter or the like in order to remove insoluble matter after production.
In the present invention, a commercially available recording liquid for an ink jet printer may be added with a compound having a replaceable alkylene oxide repeating unit of the present invention and at least one end of which is blocked with a fluoroalkyl group.
Examples of commercially available recording liquids for ink jet printers that can be used include, for example, a print cartridge black (product number 516) manufactured by Hewlett-Packard Co., Ltd.
26A or 51645A) or print cartridge color (product number 51625A or 51641)
Recording liquid contained in A), Black B manufactured by Canon Inc.
J cartridge BC-20, BJ cartridge BC-2
1. Recording liquid included in ink cartridge BCI-21Black or ink cartridge BCI-21Color, ink cartridge manufactured by Seiko Epson Corporation (model numbers MJIC4, MJIC2), recording liquid included in color ink cartridges (model numbers MJIC4, MJIC2), etc. Is mentioned.

[0034]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Synthesis Example 1 In a 20 ml flask equipped with a thermometer, a reflux condenser, a nitrogen inlet tube and a stirrer, 0.92 g of 3-perfluorobutyl-1,2-epoxypropane, 1.00 g of poly (ethylene Glycol) and 0.3 g
Of triethylamine, and the mixture was reacted for 8 hours while maintaining the solution temperature at 80 ° C. while stirring under a nitrogen gas atmosphere. After the completion of the reaction, low-boiling components were distilled off under reduced pressure (5 mmHg / 80 ° C.). After cooling, 1.83 g of a pale yellow transparent liquid was obtained. When the molecular weight of this liquid was measured by GPC, the number average molecular weight was 1200 in terms of polystyrene. From the IR spectrum, the absorption at around 1424 cm ^{-1 due} to the methylene group adjacent to the epoxy ring had disappeared.

Synthesis Example 2 3.74 g of 2- (perfluorobutyl) ethyl iodide, 5.50 g of molecular weight 5 in a 20 ml flask equipped with a thermometer, a reflux condenser, a nitrogen introduction tube and a stirrer
50 poly (ethylene glycol) methyl ether and 0.5 g of sodium hydroxide were charged, and the mixture was reacted for 8 hours while maintaining the solution temperature at 80 ° C. while stirring under a nitrogen gas atmosphere. After completion of the reaction, the reaction solution was filtered to remove insolubles, and 6.
32 g of a pale yellow clear liquid were obtained. When the molecular weight of this liquid was measured by GPC, the number average molecular weight in terms of polystyrene was 750.

Synthesis Example 3 10 ml of tetrahydrofuran, 1.00 g of 5H-octafluorovaleryl chloride, 2.23 g of molecular weight 550 were placed in a 20 ml flask equipped with a thermometer, a reflux condenser, a nitrogen introducing tube and a stirrer. Of poly (ethylene glycol) methyl ether and 0.41 g of triethylamine, and reacted for 6 hours while maintaining the solution temperature at 50 ° C. while stirring under a nitrogen gas atmosphere. After completion of the reaction, the generated salt was separated by filtration and further reduced under reduced pressure (5 mmHg / 50
℃), low boiling components were distilled off, and after cooling, 3.00 g of a pale yellow transparent liquid was obtained. When the molecular weight of this liquid was measured by GPC, the number average molecular weight was 7 in terms of polystyrene.
It was 50. From the IR spectrum, an ester-based absorption appeared around 1760 cm ^-1 .

Synthesis Example 4 2.51 g of 3-perfluorobutyl-1,2-epoxypropane, 1.00 g of α, were placed in a 20 ml flask equipped with a thermometer, a reflux condenser, a nitrogen inlet tube and a stirrer.
ω-Bis (3-aminopropyl) -diethylene glycol ether was charged and reacted for 6 hours while maintaining the solution temperature at 50 ° C. while stirring under a nitrogen gas atmosphere. After the completion of the reaction, the components having a low boiling point were distilled off under reduced pressure (5 mmHg / 50 ° C.), and after cooling, 3.18 g of a colorless transparent liquid was obtained. When the molecular weight of this liquid was measured by GPC, the number average molecular weight in terms of polystyrene was 730. From the IR spectrum, the absorption at around 1424 cm ^{-1 due} to the methylene group adjacent to the epoxy ring had disappeared.

Examples 1-4 and Comparative Examples 1-2 A mixture having the following composition was stirred with a magnetic stirrer at room temperature to prepare an ink. The dyes and defoamers used are shown in Table 1 below. Composition CI Food Black 2 (dye) 4 g Diethylene ethylene glycol monoallyl ether 25 g Ethylene glycol 22 g Sodium dodecylbenzenesulfonate (surfactant) 2 g Additives (Amount used in Table 1) Water balance ── １００ Total 100g

Using the inks obtained above, various properties of the inks, changes over time in viscosity and defoaming properties were examined. As shown in Table 1, all were good. The polyether-modified silicone used in the comparative example had a high molecular weight when stored at a high temperature for a long time because the ink solution was weakly alkaline. In addition, diethylene glycol laurate was not effective in exhibiting the defoaming property with a small amount of addition as compared with the compounds of Synthesis Examples 1 to 4. The method for evaluating the time-dependent change of the viscosity and the defoaming property was performed as follows. Time-dependent change in viscosity: E-type viscometer (manufactured by Tokimec Co.) Measurement temperature 20 ° C Rotor used Standard cone (cone angle 1 ° 34 ') Rotor rotation speed 100rpm Antifoaming property: Ink with antifoaming agent The evaluation was based on the time until the generated bubbles disappeared after shaking the container containing half the amount 20 times. A foam which disappeared within 5 seconds was regarded as good.

[0040]

[Table 1]

[0041]

As described above, since the recording liquid of the present invention does not foam due to an impact or the like, it is possible to prevent air from flowing into the nozzle discharge portion of the printer and preventing ink from being discharged. An extremely good printed image can be provided without color loss of the formed image, and therefore, it is suitable as an ink jet recording and writing additive and a recording liquid containing the same.

Claims (7)

[Claims] 1. A recording liquid additive comprising a compound in which one end of a molecular chain having a repeatable alkylene oxide unit is blocked with a fluoroalkyl group. 2. A compound in which one end of a molecular chain having a repeatable alkylene oxide repeating unit is blocked with a fluoroalkyl group, is represented by the following general formula (1): R ¹ -ABD _n -R ² ( 1) (wherein, R ¹ may have a branched structure, may contain an ether bond, may contain a chlorine atom, a bromine atom or an iodine atom, and some or all of the hydrogen atoms are fluorinated) A represents an alkyl group, A represents a single bond, a cycloalkylene or an alkylene which may contain an ether bond, and B represents an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond or an alkanolaminoalkyl. Represents
D represents an ethylene oxide unit or a propylene oxide unit or a mixed unit thereof, n represents an integer of 1 to 200, and R ² represents R ¹ -A-
Represents B- or an alkyl group. The recording liquid additive according to claim 1, which is a compound represented by the formula: 3. A fluorinated alkyl compound having a carboxylic acid group, a carboxylic acid halide group or a carboxylic acid ester group, wherein the compound in which one end of a molecular chain having a replaceable alkylene oxide repeating unit is blocked with a fluoroalkyl group. 3. The additive for recording liquid according to claim 1, wherein the compound is a compound synthesized from a diol having a repeatable alkylene oxide repeating unit or a monol having an alkyl ether at one end. 4. A compound in which one end of a molecular chain having a substitutable alkylene oxide repeating unit is blocked with a fluoroalkyl group, the compound comprising a fluorinated alkyl compound having an epoxy group and a substitutable alkylene oxide repeating unit. The recording liquid additive according to claim 1, wherein the additive is a compound synthesized from a diol or a monol having an alkyl ether at one end. 5. R ¹ is X (CF ₂ ) _m —, wherein X represents a hydrogen atom or a halogen atom, and m represents 1
Represents an integer of ２０20. The recording liquid additive according to claim 2, which is a compound represented by the formula: 6. A recording liquid comprising a water-soluble dye, an aqueous medium, and the recording liquid additive according to claim 1. 7. The content of the recording liquid additive in the range of 0.01 to 10% by weight based on the total weight of the recording liquid.
The recording solution described in the above.