JPH10306243A - Recording solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording solution capable of providing print excellent in fastness to water even on a plain paper, by including a specific fluorine-based compound, a water-soluble dye and an aqueous medium. SOLUTION: This recording solution contains (A) a fluorine-based compound containing a fluoroalkyl group and an amino group in the molecule, (B) a water- soluble dye and (C) an aqueous medium. The content of the component B is 0.2-12 wt.% based on the total weight of the recording solution and that of the component C is 10-80 wt.% of water and <=70 wt.% of an organic solvent mixable with water based on the total weight of the recording solution. The content of the component A is preferably 0.01-30 wt.%. Consequently the objective recording solution suitable for ink-jet recording and writing is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a recording liquid. More specifically, the present invention relates to ink for ink jet recording and writing.

[0002]

2. Description of the Related Art Ink jet printers have low noise,
It has features such as low running cost and easy color recording, and has been rapidly spreading in recent years as a digital signal output device. Recording inks used for printers can be of various types, such as inks mainly based on aqueous dyes or oily dyes, inks in which pigments are dispersed in an aqueous or oily medium, or solid inks that can be melted by heat. Inks have been proposed. In particular, inks based on water-based dyes are considered to be most suitable for social demands for sustaining the global environment because of the high safety of the ink material to living bodies and the environment, and the relatively low energy consumption of printers. . However, aqueous dyes have a problem in that they are inferior in water fastness to inks using oil dyes or pigments. Oil-based inks are excellent in water-fastness, but when oil-based inks are used in ink jet printers, harmful organic solvents are generated due to the large amount of ink used, which may adversely affect human bodies and the environment. In addition, an ink in which an oil-based dye or pigment is dispersed in an aqueous medium has a problem that a nozzle of an inkjet printer is clogged, or storage stability is poor, and precipitation occurs in the ink. There is a need for inks for inkjet printers.

[0003] Ink jet recording inks mainly composed of water-based dyes use water-soluble dyes. Therefore, when plain paper is used as the recording material, even when the print is dried, it is exposed to moisture. There was a problem in terms of the water fastness of the printed portion, such as stains on the surface and the flow of the aqueous dye when exposed to water. Various solutions have been proposed as means for solving this. As a method of compounding a compound having a fluoroalkyl group into an ink for ink jet recording, as an example, Japanese Patent Application Laid-Open No. 8-267902 discloses that a specific cationic fluorine-based surfactant and a polymer substance are contained in a liquid medium. By providing both, a liquid composition capable of obtaining an image having excellent water resistance is obtained, and the step (A) of adhering the liquid composition to a recording medium, and the step of applying an ink containing an anionic compound to the recording medium by an ink jet method A method for forming an image by the applying step (B) is disclosed. This method can improve the water fastness even when recording is performed on plain paper, but the dye aggregates when the liquid composition is mixed with the ink containing the dye. Therefore, it is necessary to carry out the step (A) and the step (B) separately. In order to improve the water resistance on plain paper for printing, in addition to the ink jet printer head for ink, the liquid composition dedicated to the liquid composition is used. There is a disadvantage that an ink jet printer head is required.

JP-A-3-37275 discloses dyes,
A liquid medium and a surfactant selected from the group consisting of polyoxyethylated ethers, anionic bitail fluoroalkyl, alkylarylsulfonates, alkylamine quaternary salts and mixtures thereof. A hot ink jet printing composition is disclosed. This fluoroalkyl group-containing surfactant has an anionic functional group (for example, carboxylate),
The structure is different from the present invention. Further, the fluoroalkyl group-containing surfactant alone does not have sufficient water resistance, and in order to further improve the water resistance, it is used in combination with a surfactant having an alkylamine quaternary salt which has a high risk of dye aggregation. There must be. Therefore, the present invention has a drawback that water fastness is insufficient or the nozzle tip is easily clogged.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous recording liquid and an ink for an ink jet printer capable of obtaining a print excellent in water fastness even when recording on plain paper. It is.

[0006]

Means for Solving the Problems In order to solve the problems associated with the prior art, the present inventors have conducted intensive studies, and as a result,
The present invention has been found that a recording liquid characterized by containing a fluoroalkyl group-containing compound containing a fluoroalkyl group and an amino group in a molecule, a water-soluble dye, and an aqueous medium can obtain a print having excellent water fastness. Was reached.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the recording liquid according to the present invention will be specifically described. First, a fluorine compound used in the recording liquid of the present invention will be described. The fluorine compound only needs to contain a fluoroalkyl group and an amino group in the molecule. Preferably, the fluoroalkyl group is a group in which at least one hydrogen atom of an alkyl group which may have a branched structure having 1 to 25 carbon atoms is substituted with a fluorine atom, and an ether bond is contained in the fluoroalkyl group. And the number of carbon atoms of the fluoroalkyl group is preferably from 1 to 8, and if it exceeds 25, the solubility decreases, which is not desirable. Further, the fluorine-based compound used in the present invention may contain a plurality of fluoroalkyl groups having different structures in the same molecule.

The fluoroalkyl group includes, for example, CF
_{3, F (CF 2) 2} , F (CF 2) 3, F (CF 2) 4, F (CF 2) 5, F (CF 2)
_{6, F (CF 2) 7} , F (CF 2) 8, F (CF 2) 9, F (CF 2) 10, HCF
_{2, H (CF 2) 2} , H (CF 2) 3, H (CF 2) 4, H (CF 2) 5, H (CF 2) 6
, H (CF ₂ ) ₇ , H (CF ₂ ) ₈ , H (CF 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, Cl (CF 2) 8, Cl (C
F ₂ ) ₂₉ , Cl (CF ₂ ) ₁₀ , CF (CF ₃ ) OC ₃ F ₇ , CF (CF ₃ ) OCF ₂ CF (C
F 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 (CF ₃ )) ₄ -OC ₃ F
₇ , CF (CF ₃ ) (OCF (CF ₃ ) ₂ CF) ₅ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (C
F ₃ )) ₆ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₇ -OC ₃ F ₇ , CF (C
F ₃ ) (OCF ₂ CF (CF ₃ )) ₈ -OC ₃ F _{7 and the} like.

The amino group can be used for primary, secondary and tertiary. The substituted alkyl group of the secondary or tertiary amino group has 1 to 10 carbon atoms which may have a branched structure, and preferably has 1 or 2 carbon atoms. If the number of carbon atoms exceeds 10, the solubility decreases, which is not desirable. In addition, a hydroxyl group,
It may contain a carboxyl group. The same molecule may contain a plurality of amino groups having different structures.

Next, a method for producing the fluorine-based compound in the present invention will be described. The compound is obtained by a reaction of introducing a fluoroalkyl group into a compound having an amino group (hereinafter, referred to as a base compound). At this time, it is convenient to use a reaction with an active hydrogen-containing functional group and a functional group capable of reacting therewith. The active hydrogen-containing functional group is a functional group having a hydrogen atom directly bonded to oxygen or nitrogen, and includes, for example, a primary amino group, a secondary amino group, a hydroxyl group, and a carboxyl group. Examples of the functional group capable of reacting with active hydrogen include an epoxy group, a carboxylic anhydride, an isocyanate group, and a methylol group. Numerous reactions are possible depending on the combination of these functional groups,
Reactions that do not actually proceed (for example, the reaction between a carboxyl group and a carboxylic anhydride) are excluded. One of the methods for obtaining the fluorine-based compound is to use an amino group-containing compound having an active hydrogen-containing functional group as a base compound, and to combine the base compound with a fluoroalkyl group-containing compound having a functional group capable of reacting with active hydrogen. A method of obtaining a reacted compound may be mentioned.
Examples of the reaction include a reaction between a base compound having a hydroxyl group and a fluoroalkyl group-containing compound having an epoxy group, and a reaction between a base compound having a primary amino group and a fluoroalkyl group-containing compound having an epoxy group.

Second, an amino group-containing compound having a functional group capable of reacting with active hydrogen is used as a base compound,
There is a method of obtaining a compound obtained by reacting the base compound with a fluoroalkyl group-containing compound having an active hydrogen-containing functional group. Examples of the reaction include a reaction between a base compound having an isocyanate group and a fluoroalkyl group-containing compound having a hydroxyl group, and a reaction between a base compound having an epoxy group and a fluoroalkyl group-containing compound of a compound having a hydroxyl group. The use of a substrate compound or a fluoroalkyl group-containing compound having a plurality of highly reactive functional groups in the same molecule is difficult to obtain as a single compound, and the reaction in the molecule may occur due to the desired reaction. This is not possible because the yield of the fluorine-based compound is lowered and the molecular weight is likely to be increased to cause gelation. Examples of these combinations include a combination having a primary amino group and an epoxy group, and a combination of a hydroxyl group and an isocyanate group. It is not necessary to introduce a fluoroalkyl group into all of the reactive groups in the base compound, as long as the fluoroalkyl groups can be uniformly dissolved or dispersed in the recording liquid, and the reactive groups may be left.

The composition of the reaction may be a composition in which the produced fluorine-based compound can be uniformly dissolved or dispersed in the composition of the recording liquid described later. Since the solubility varies depending on the fluorine content and the number of carbon atoms of the hydrophobic fluoroalkyl group, and the structure of the hydrophilic amino group, the composition cannot be determined uniformly. It is preferably about 30% by weight. 0.01
If the amount is less than 30% by weight, the water resistance decreases, and if the amount exceeds 30% by weight, the solubility in the recording liquid decreases. These reactions can be performed under known reaction conditions.

Examples of the fluoroalkyl group-containing compound having a hydroxyl group include 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 6- (perfluoroethyl) hexanol, 1H,
1H-heptafluorobutanol, 2- (perfluorobutyl) ethanol, 6- (perfluorobutyl) hexanol, 2-perfluoropropoxy-2,3,
3,3-tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 3- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 2- (perfluorooctyl) ethanol,
3- (perfluorooctyl) propanol, 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, 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 the fluoroalkyl group-containing compound having a carboxylic acid group include trifluoroacetic acid, perfluoropropionic acid, perfluorobutanoic acid, perfluorovaleic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, Perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, 3H-tetrafluoropropionic acid, 5H-octafluorovaleric acid, 7H-dodecafluoroheptanoic acid, 9H-hexadecafluorononanoic acid, 3-chlorotetrafluoro Examples thereof include propionic acid, 3,4-dichloropentafluorobutanoic acid, 3,5,6-trichlorooctafluorohexanoic acid, and 2,2-bis (trifluoromethyl) propionic acid. As the fluoroalkyl group-containing compound having an epoxy group, for example, 3-perfluorobutyl-1,2-epoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 3-perfluorooctyl-1,2-epoxypropane , 3-perfluorodecyl-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-epoxypropane, 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- (1H, 1H, 9H-hexadedecafluorononyloxy) -1,2-epoxypropane and the like Is mentioned.

The obtained fluorine compound is purified by a known method such as distillation of a solvent, column chromatography, reprecipitation, and dialysis, and is added to the ink. When water or a water-soluble organic solvent is selected as the reaction solvent, if it is suitable for the composition of the aqueous medium of the recording liquid, it may be added to the ink as it is, or may be added after concentration by adjusting the concentration. The number average molecular weight of the fluorine compound is 400 to 100,000, preferably 80
Desirably, it is 0 to 20,000. If it is less than 400, the water resistance decreases, and if it exceeds 100,000, the viscosity of the recording liquid increases, and there is a disadvantage that the print density in an inkjet printer decreases. The base compound can be freely selected and used as long as it satisfies the above factors.
A radical (co) polymer obtained by the following method may be used. Methods for obtaining the base compound as a (co) polymer of an amino group-containing compound having an active hydrogen-containing functional group include the following (1-1), (1-2), and (1-3).

(1-1) a radical-polymerizable unsaturated group-containing monomer having at least one amino group in the molecule;
A copolymer with a radical-polymerizable unsaturated group-containing monomer having at least one active hydrogen-containing functional group in a molecule. (1-2) A radical-polymerizable unsaturated group-containing monomer having at least one amino group in a molecule is polymerized in the presence of a chain transfer agent or a polymerization initiator having an active hydrogen-containing functional group. (Co) polymers. (1-3) A radical polymerizable unsaturated group-containing monomer having at least one amino group in a molecule is prepared by reacting a radical transferable monomer having an active hydrogen-containing functional group and a polymerization initiator, or a polymerization initiator. (Co) polymers obtained by polymerization into

Since the base compounds obtained by the methods (1-2) and (1-3) have an active hydrogen-containing functional group at the terminal of the molecular chain, a fluorine compound having a fluoroalkyl group introduced at the terminal of the molecular chain. System compound can be obtained. A method for obtaining the base compound as a (co) polymer of an amino group-containing compound having a functional group capable of reacting with active hydrogen includes the following (2). (2) A radical polymerizable unsaturated group-containing monomer having at least one tertiary amino group in the molecule and a radical polymerizable unsaturated group having at least one functional group capable of reacting with active hydrogen in the molecule. Copolymer with a saturated group-containing monomer. The (co) polymer may be random, block or graft copolymer. Examples of these copolymers schematically include the following structures.

(1-1) Structural formula

Embedded image However, R ¹ each independently represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and R ³ represents a hydroxyl group or a carboxyl group.

X represents a group selected from the groups represented by the following structures;

Embedded image

Y represents a group represented by the following structure (where a is an integer of 0 or more).

Embedded image

N and m each represent an integer of 1 or more (provided that m may be 0 when R ² is a hydrogen atom). (1-2) Structural formula

Embedded image

However, R ¹ , R ² , R ³ , X and Y have the same definitions as described above. R ⁴ represents a hydroxyl group or a carboxyl group as a structure derived from a chain transfer agent, and a group represented by the following structure as a structure derived from an initiator;

Embedded image

Z represents a group represented by the following structure as a structure derived from a chain transfer agent;

Embedded image

The structure derived from the initiator is a group represented by the following structure:

Embedded image

N represents an integer of 1 or more, and m represents an integer of 0 or more.
M is 1 or more when a copolymer is used in combination with at least one monomer having a radical polymerizable unsaturated group. (1-3) Structural formula

Embedded image

Where R ¹ , R ² , R ³ , R ⁴ , X, Y, Z,
m and n have the same definitions as described above. (2) Structural formula

Embedded image However, R ¹ , X, Y, and n have the same definitions as described above.

R ⁵ represents an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and R ⁶ represents a structure shown below.

Embedded image b + c represents an integer of 1 or more, but b and c do not simultaneously become 1 or more (when b is 1 or more, c is 0, and when c is 1 or more, b is 0).

The radical polymerizable unsaturated group-containing monomer having at least one amino group in the molecule can be used without any particular limitation as long as the constituent group is present in the molecule. For example, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminomethyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N-methylaminopropyl (meth) ) Acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-ethylaminomethyl (meth) acrylamide, N -Ethylaminoethyl (meth) acrylamide, N-ethylaminopropyl (meth) acrylamide, N, N-diethylaminomethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N Diethylaminopropyl (meth) acrylamide, (meth) acrylamides, dimethylaminoethyl (meth) acrylate, (meth) acrylates such as diethylaminoethyl (meth) acrylate.

Further, it is preferable that the amino group of the monomer is a tertiary amino group. Examples thereof include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-
Dimethylaminopropyl (meth) acrylamide, N,
N-diethylaminomethyl (meth) acrylamide,
N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide and the like can be mentioned. Of these, N, N-dimethylaminopropylacrylamide is particularly preferred.

The amino group of the monomer constituting the polymer may be a tertiary amino group. That is, after the polymerization reaction, the polymer may be subjected to any chemical reaction to construct a tertiary amine. For example, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide,
Aminopropyl (meth) acrylamide, N-methylaminomethyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N-methylaminopropyl (meth) acrylamide, N-ethylaminomethyl (meth) acrylamide, N-ethyl A part of a polymer composed of aminoethyl (meth) acrylamide, N-ethylaminopropyl (meth) acrylamide, or the like,
A method of constructing a tertiary alkylamine derivative by reacting with an alkyl halide such as methyl iodide, methyl bromide, or methyl chloride is exemplified. These polymers may be used alone or in combination. A part of the polymer may have these structures.

Further, these monomer species can be freely selected and used within a range that does not cause problems such as gelation during polymerization in consideration of the desired physical properties and the like of the recording liquid. The monomers can be used alone or in combination of two or more. The amount used is not particularly limited as long as it satisfies the required performance such as solubility.
It may be selected in the range of 0 to 99% by weight, preferably 40 to 95% by weight. If less or more than this, the waterfastness is not sufficient.

The radically polymerizable unsaturated group-containing monomer having at least one active hydrogen-containing functional group in the molecule can be used without any particular limitation as long as the monomer has a constituent group in the molecule. For example, as a compound having a hydroxyl group as an active hydrogen-containing functional group, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
C2-C10 hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, 2
-(Meth) acryloyloxyethyl 2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 3-chloro-2
(Meth) acrylates such as hydroxypropyl (meth) acrylate and (meth) acrylates having a plurality of hydroxyl groups in one molecule such as glycerol mono (meth) acrylate are also included. Further, ε-caprolactone, δ-
Lactone-modified (meth) acrylate to which 1 to 5 mol of a lactone such as caprolactone is added. Examples of the lactone-modified (meth) acrylate include the following Praxel FA series and Praxel FM series (both manufactured by Daicel Chemical Industries, Ltd.). Praxel FA-1 (1 mol of 2-hydroxyethyl acrylate and 1 mol of ε-caprolactone) ), Praxel FA-4 (a monomer obtained by adding 4 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate), Praxel FM-1 (a monomer obtained by adding ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate) 1 mol of a monomer added), Praxel FM-3 (a monomer obtained by adding 3 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl methacrylate), and Praxel FM-4 (a monomer obtained by adding 1 mol of 2-hydroxyethyl methacrylate to 1 mol of 2-hydroxyethyl methacrylate) -A monomer to which 4 mol of caprolactone has been added), Triethylene glycol monomethacrylate (eg NOF Corp. BLENMER PE series, PE-30, PE-90, PE-200, PE-3
50). Examples of the compound having a carboxyl group as an active hydrogen-containing functional group include (meth) acrylic acid, maleic acid, 2-methacryloyloxyethylsuccinic acid, and 2-methacryloyloxyethylphthalic acid. Examples of the compound having an amino group as an active hydrogen-containing functional group include, among the above-mentioned monomers having at least one radically polymerizable unsaturated group and at least one amino group in the molecule, a primary amino group and a secondary amino group. Examples include monomers having an amino group.

The radically polymerizable unsaturated group-containing monomer having at least one functional group capable of reacting with active hydrogen in the molecule is not particularly limited as long as it has the constituent group in the molecule. it can. For example, as a compound having an isocyanate group, 2-isocyanatoethyl (meth)
Glycidyl (meth) acrylate and (meth) acrylate having an alicyclic epoxy group (eg, Daicel Chemical Industries, Ltd.)
And M100, A100, and M101) having a methylol group include N-methylolacrylamide, and the carboxylic anhydride includes maleic anhydride. Active hydrogen-containing functional groups or monomers having a functional group capable of reacting with active hydrogen can be freely selected and used within a range that does not cause problems such as gelation during polymerization in consideration of the desired physical properties of the recording liquid. At this time, these monomers can be used alone or in combination of two or more. The amount used is not particularly limited as long as it satisfies the required performance such as solubility, but it is 0.01 to 40% by weight, preferably 0.1 to 20% by weight in the raw material monomer.
You can choose from the range. When the amount is less than 0.01% by weight, water fastness is not sufficient, and when the amount is more than 40% by weight, solubility in a recording liquid is undesirably reduced. Examples of the chain transfer agent having an active hydrogen-containing functional group include, for example, compounds having a hydroxyl group such as thioglycerol and 2 mercapto-ethanol. Examples of the compound having a carboxyl group include thioglycolic acid and 3-mercaptopropionic acid.

As the polymerization initiator having an active hydrogen-containing functional group, for example, those having a hydroxyl group include 2,2'-
Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [1,1
-Bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis [2- (hydroxymethyl) pro Pionitrile]
And the like. Examples of those having a carboxyl group include 4,4′-azobis (4-cyanovaleric acid). In order to adjust the compatibility with other components in the recording liquid, other radically polymerizable unsaturated monomers may be used as long as problems such as gelation do not occur during polymerization in consideration of the desired physical properties. The copolymers may be used together to form a copolymer. These can be freely selected and can be used alone or in combination of two or more. When used, the amount of use can be selected within the range of 0.1 to 70% by weight, preferably 1 to 20% by weight based on the raw material monomer. In general, any of these monomers having radical polymerization ability can be used.

For example, alkyl (carbon number 1) such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate
-22) (meth) acrylates. Benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-phenoxyethyl (meth)
Acrylate, nonylphenoxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-
Hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate,
Phenoxy polyethylene glycol acrylate (eg:
Kyoeisha Chemical Co., Ltd. P-200A), Nonylphenoxypolyethylene glycol (meth) acrylate (eg, Kyoeisha Chemical Co., Ltd. NP-4EA, NP-8EA, NP-10)
(Meth) acrylates having a substituted or unsubstituted phenyl group such as EA). Styrene methyl styrene, para-
Styrenes such as styrenesulfonic acid and maleimide derivatives such as N-phenylmaleimide and N- (2-methylphenyl) maleimide. Contains a ring structure or a ring structure containing a hetero atom such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate (eg, Nippon Kayaku Co., Ltd.) Organic (meth) acrylates. Alkyl ether (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and N-butoxyethyl (meth) acrylate; Methoxy polyethylene glycol monomethacrylate (eg, Blemmer PME series, manufactured by NOF Corporation, P
ME-100, PME-200, PME-400), polypropylene glycol monomethacrylate (eg, Blemmer PP series, manufactured by NOF Corporation, PP-500,
PP-800, PP-1000), polyethylene glycol polypropylene glycol monomethacrylate (Example: Blemmer PEP series manufactured by NOF Corporation, 7
0 PEP-370B), polyethylene glycol polytetramethylene glycol monomethacrylate (eg, Blemmer 55PET-800 manufactured by NOF Corporation), polypropylene glycol polytetramethylene glycol monomethacrylate (eg, Blemmer NK manufactured by NOF Corporation)
H-5050), polypropylene glycol monoacrylate (eg, Blemmer AP-40 manufactured by NOF Corporation)
0), polyethylene glycol monoacrylate (eg:
(Blenmer AP-350 manufactured by NOF Corporation), (meth) acrylates of alkoxy polyethylene glycol or alkoxy polypropylene glycol such as ethoxydiethylene glycol (meth) acrylate. (Meta)
Acrylonitrile, N-isopropylacrylamide,
N- (1,1-dimethyl-3-oxobutyl) (meth)
Examples include amide compounds of (meth) acrylate such as acrylate and N- (meth) acryl morpholine, and derivatives thereof. Vinyl compounds having a ring structure or a ring group containing a hetero atom, such as vinylcyclohexane, N-vinylpyrrolidone, and vinyloxazoline. Maleimide derivatives such as N-cyclohexylmaleimide. Maleic esters such as diethyl maleate and di-2-ethylhexyl maleate. Fumaric acid esters such as diethyl fumarate and di-2-ethylhexyl fumarate; Vinyl chloride, N
-Aliphatic vinyl esters such as vinylacetamide, N-vinyl-N-methylacetamide, vinyl acetate and vinyl propionate. Aliphatic vinyl compounds such as N-vinylformamide and derivatives thereof; Vinyl chloride and the like can be mentioned. Aliphatic vinyl ethers such as vinyl methyl ether;

Further, monomers having a plurality of radically polymerizable groups such as allyl (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate are also included. These include urethane (meth) acrylate (eg, manufactured by Kyoeisha Chemical Co., Ltd.
Urethane acrylate series, AH-600, AI-
600, AT-600) and the like. When a monomer having a plurality of radically polymerizable groups is used, the amount used to prevent gelation during polymerization because it becomes a crosslinking point is the content and initiator of the radically polymerizable group in the monomer, Although it varies depending on the amount of the chain transfer agent used, it is preferably 0.01 to 10% by weight based on all monomers. The radical (co) polymer can be synthesized according to the following procedure. That is, polymerization is carried out by blending a monomer selected under the above-described conditions, a radical polymerization initiator, and, if necessary, a chain transfer agent. At this time, other radical polymerizable monomers may be used in combination as needed.

The mode of polymerization can be carried out by a conventionally known radical polymerization method. The radical polymerization initiator,
Except for the case where the polymerization initiator having an active hydrogen-containing functional group described above is used, all those usually used as general radical polymerization reaction initiators can be used. For example, 2,2′- Azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2-cyano-2-propylazo-formamide, dimethyl 2,2'-azobis (2-
Azo-based polymerization of 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis {2-methyl-N- (2-hydroxyethyl) -propionamide}, etc. Initiators, such as isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxide, t-butylcumyl peroxide, t
Peroxide polymerization initiators such as -butyl hydroperoxide; and the like, and these can be used alone or in combination of two or more. At this time,
For the purpose of lowering the concentration of the reaction residue and the like, the same or different polymerization initiators may be additionally added during the reaction. The addition amount is preferably 0.1 to 30% by weight. However, the use of a peroxide-based polymerization initiator, when using N-vinylpyrrolidone or the like as a radical polymerizable unsaturated monomer, because there is an inappropriate combination such as because the oxidation-reduction reaction has priority over the polymerization, It is preferable to use an azo polymerization initiator. The reaction can be performed at normal pressure. Since the reaction is a radical reaction, the reaction is performed in an inert atmosphere (for example, nitrogen, argon, or the like).

The reaction temperature is not particularly limited, but may be any temperature at which the radical polymerization initiator is decomposed, and is usually 40 to 40.
The temperature is preferably in the range of 180 ° C., and a method of gradually increasing the temperature from a low temperature to a high temperature may be employed. When the reaction temperature is lower than 40 ° C., the reaction requires a long time,
When the temperature exceeds ℃, the pressure at the time of the reaction increases, and the reaction operation becomes difficult. Although the reaction time is not particularly limited, it can be generally carried out in the range of 1 to 24 hours, and is preferably in the range of 3 to 10 hours industrially.

It is preferable to carry out the reaction in a solution in order to simplify the polymerization reaction operation and to smoothly carry out the reaction. The polymerization solvent is substantially inert to the raw materials during the polymerization reaction,
A material capable of dissolving or dispersing these materials can be appropriately selected from conventionally known materials and used. For example,
Esters such as water, ethyl acetate, butyl acetate and amyl acetate; alcohols such as methanol, ethanol, isopropanol, butanol, 1,2,6-hexanetriol and glycerin; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone , Diethyl ether, tetrahydrofuran, 1,4-
Ethers such as dioxane, amides such as N, N-dimethylformamide, N-methylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, 1-methyl -2-pyrrolidone, 2-pyrrolidone, ε
-Pyrrolidones such as caprolactam, aromatic hydrocarbons such as benzene, toluene and xylene, N-pentane n-
Hexane, aliphatic hydrocarbons such as cyclohexane, ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, triethylene glycol, hexylene glycol, diethylene glycol,
Glycols such as dipropylene glycol and polyethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol,
-Propoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether And glycol ethers such as dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol. These solvents are 2
A mixture of more than one species may be used.

The mixing ratio of the organic solvent is not particularly limited, and an appropriate ratio may be selected depending on the viscosity and solubility of the obtained polymer and raw materials. Usually 1 to
Although it is about 80% by weight, it is 5 to 4 due to the operability of the reaction and the ease of handling of the purification of the product (if necessary).
0% by weight is desirable. There is no particular limitation on the method of controlling the molecular weight, but the amount of the polymerization initiator is adjusted (add a large amount to reduce the molecular weight, conversely, add a small amount to increase the molecular weight), or add a chain transfer agent And other methods can be generally used. Except for the case where the above-described chain transfer agent having an active hydrogen-containing functional group is used as the chain transfer agent, generally used compounds can be selectively used, for example, 2,4-diphenyl-4-methyl-1-pentene. And cyclohexyl mercaptan, benzyl mercaptan, t-butyl mercaptan, dimethylaminoethyl mercaptan and the like. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent varies depending on the polymerizability and copolymerizability of the raw material monomers and the content of the polymerization initiator.
A range of weight% is preferred.

The radical (co) polymer thus obtained has a number average molecular weight of 400 to 100,000, preferably 800 to 20,000. 400
If it is less than 10, it is necessary to add a large amount of a chain transfer agent or an initiator, and there is a drawback that a large amount of by-products are generated accordingly. If it exceeds 100,000, the viscosity of the recording liquid becomes large even if a fluoroalkyl group is introduced. This has the disadvantage that the print density in an ink jet printer is reduced. The obtained radical (co) polymer is purified by a known method such as solvent evaporation, column chromatography, reprecipitation, or dialysis, if necessary, before the fluoroalkyl group introduction reaction. The amount of the fluorine compound used in the present invention is 0.01 to 2 in the recording liquid.
0% by weight is preferred. If it is less than 0.01% by weight, water resistance is reduced, and if it exceeds 20% by weight, there is a disadvantage that printing with an ink jet printer becomes difficult. Further, the fluorine compounds can be used alone or in combination of two or more.

The water-soluble dye used in the recording liquid includes
There is no particular limitation as long as it can be dissolved in water, and examples thereof include direct dyes, acid dyes, basic dyes, reactive dyes and food dyes described in Color Index. More specifically, as a direct dye, for example, CIDirect Blac
k (direct black) 2, 4, 9, 11, 14, 17, 1
9, 22, 27, 32, etc., CIDirect Blue 1, 2, 6, 8, 15, 22, 25, 34, 69, 70, etc.
I.Direct Brown (Direct Brown) 1A, 2, 6
, 25, 27, 44, 58, 95, etc., CIDirect Green 1, 6, 8, 28, 33, 37, 63, etc., C.I.
I.Direct Orange 6, 8, 1
0, 26, 29, 39, 41, 49, 51, etc., CIDirectRed (Direct Red) 1, 2, 4, 8, 9, 11, 13, 17, 17, 2
0, 23 etc., CIDirect Violet (Direct Buy I
Let) 1, 7, 9, 12, 35, 48, 51 etc., CIDirect
Yellow (direct yellow) 1, 2, 4, 8, 11,
12, 24, 26, 27, 28 and the like.

Examples of the acid dye include CIAcid Bl
ack (acid black) 1, 2, 7, 16, 17, 24, 2
6, 28, 31, 41, 48, 52, etc., CIAcid Blue (acid
Blue) 1, 7, 9, 22, 22, 23, 25, 27, 29, 40, etc., C.
I.Acid Brown 4, 14, etc., CIAc
id Green 3, 9, 12, 16, 1
9, 20, 25, 27, etc., CIAcid Orange (acid orange) 7, 8, 10, 33, 56, etc., CIAcid Red (acid red) 1, 4, 6, 8, 8, 13, 14, 15, 18, 19, Two
1, 26, 27, 30, 32, 34, etc., CIAcid Violet (acid violet) 7, 11, 15, 34, 35, 41, 43, C.I.
I.Acid Yellow 1,3,4,7
, 11,12,13,14,17,18,19,23,25,29,34,3
6, 38 and the like. As the basic dye, for example,
CIBasic Black 2, 8, C.
I.Basic Blue 1, 3, 5, 7
, 9, 24, 25, 26, etc., CIBasicBrown (basic
Brown) 1,12. CIBasic Green 1,4. CIBasic Orange 2,15,21 etc.CIBasic Red 1,2,9,12 etc., CIBasic Violet (basic violet) 1,3,5,7,9,24,25 etc.
CIBasic Yellow 1, 2,
11, 12, 14, 21, 32, 36 and the like.

As the reactive dye, for example, CIReacti
ve Black (reactive black) 1, 3, 5, 6
, 8 etc. CIReactive Blue (reactive blue) 2, 5, 7, 12, 13, 14, 15, 17, 18, 19 etc. CIRe
active 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, C.
I.Food Red (food red) 2, 3, 7, 9, 14,
52, 87, 92, 94, 102, etc., CIFood Violet (food
Violet) 2, CIFood 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 in the recording liquid include water and an organic solvent miscible with water. For example, 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 include those having a function as a wetting agent for preventing drying of the nozzle tip, and therefore polyalkylene glycols (eg, polyethylene glycol, polypropylene glycol, etc.), 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. The method for preparing the recording liquid is not particularly limited,
After dissolving the compound of the present invention in water and a water-soluble medium, it is preferable to add a water-soluble dye or an aqueous solution thereof while stirring with a screw, a magnetic stirrer or the like. The solution may be heated to 30-50 ° C. to increase the dissolution rate. The pH of the recording liquid is determined by the stability of the dye and compound.
A range of pH 6-14 is preferred. The method for adjusting the pH is not particularly limited. Preservatives and fungicides (for example, sodium dehydroacetate), chelating reagents (for example, sodium ethylenediaminetetraacetate), and rust preventives (for example, ammonium thioglycolate) as long as the desired performance of the recording liquid composition is not impaired. Various additives such as an oxygen absorbent (eg, sodium sulfite), a pH adjuster, an antifoaming agent, a viscosity adjuster, a penetrant, and a nozzle drying inhibitor may be added.

The preparation of the recording liquid has been described above. Even when the compound of the present invention is added and dissolved in a commercially available recording liquid for an ink jet printer or the like, a recording liquid having excellent water fastness can be obtained. . Examples of commercially available recording liquids for inkjet printers include recording liquids contained in print cartridge black (product number HP51626A) or print cartridge color (product number HP51625A) manufactured by Hewlett-Packard Co., Ltd. Black BJ cartridge BC-20,
BJ cartridge BC-21, ink cartridge BC
I-21Black or ink cartridge BCI
Recording liquid contained in -21Color, an ink cartridge manufactured by Seiko Epson Corporation (model number MJIC4, MJ
IC2), color ink cartridge (model number MJIC)
4, recording liquids contained in MJIC2). The method of addition to commercially available inks for ink jet printers is not particularly limited, but it is preferable to add the fluoroalkyl group-containing compound of the present invention or a solution thereof. To increase the dissolution rate, add water and an aqueous solvent
It may be heated to 0 ° C. The recording liquid thus prepared and the recording liquid for an ink jet printer do not cause precipitation and are excellent in water fastness and stability.

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 After charging 10.00 g of N, N-dimethylaminopropylacrylamide and 1.16 g of 3-mercaptopropionic acid in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube. Dimethyl 2,2-azobis (2-methylpropionate) 1.4
38.0 g of n-butyl acetate in which 75 g was dissolved was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours. Then, the temperature was increased to 95 ° C., and the reaction was further continued for 2 hours. After cooling to room temperature, 50 g of a pale yellow suspension was obtained. The solvent is distilled off from this solution using a rotary vacuum evaporator, the remaining highly viscous liquid is dissolved in 100 g of acetone, and the solvent is again distilled off using a rotary vacuum evaporator. Subsequently, after vacuum drying at 60 ° C. for 24 hours, it was dissolved in acetone and reprecipitated with hexane.
Vacuum dry at ℃ overnight to obtain the product. The molecular weight of the obtained product was measured by gel permeation chromatography (hereinafter abbreviated as GPC), and the result was Mn = 7000.
Met. The obtained product is referred to as Compound A.

Synthesis Example 2 10.00 g of N, N-dimethylaminopropylacrylamide and 0.90 g of 2-mercaptoethanol were charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. Later dimethyl 2,2
-1.475 g of azobis (2-methylpropionate)
Was dissolved therein, 38.0 g of n-butyl acetate was added, and the mixture was heated with stirring under a nitrogen atmosphere and kept at 80 ° C. for 4 hours.
The temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, 50 g of a pale yellow transparent solution was obtained. The solvent was distilled off from this solution using a rotary vacuum evaporator, and the remaining highly viscous liquid was dissolved in 100 g of n-butyl acetate.
The solvent is again distilled off using a rotary vacuum evaporator. Subsequently, after vacuum drying at 60 ° C. for 24 hours, dissolved in n-butyl acetate and reprecipitated with hexane.
Vacuum dry at ℃ overnight to obtain the product. As a result of measuring the molecular weight of the obtained product by GPC, Mn was 3,200. The obtained product is referred to as Compound B.

Synthesis Example 3 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser was charged with 10.00 g of N, N-dimethylaminopropylacrylamide and then charged with 2,2'-azobis. [2-Methyl-N- (2-hydroxyethyl) -propionamide] 65.5 g of N, N-dimethylformamide in which 1.855 g was dissolved was added, and the mixture was heated to 80 ° C. while stirring under a nitrogen atmosphere. After keeping for a time, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, 77 g of a pale yellow transparent solution was obtained.
The solvent is distilled off from this solution with a rotary vacuum evaporator, followed by vacuum drying at 60 ° C. for 24 hours, and then dissolved in acetone to remove insolubles by suction filtration.
The filtrate is reprecipitated with hexane and further dried under vacuum at 60 ° C. overnight to obtain a product. The molecular weight of the product obtained is determined by GP
As a result of measurement at C, Mn was 3,200. The obtained product is referred to as Compound C.

Synthesis Example 4 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 10.00 g of N, N-dimethylaminopropylacrylamide, 1.19 g of 2-hydroxyethyl methacrylate, and cyclohexyl. After charging 1.06 g of mercaptan, dimethyl 2,2 was added.
-Azobis (2-methylpropionate) 1.050 g
35.0 g of n-butyl acetate in which was dissolved was added, and the mixture was heated with stirring under a nitrogen atmosphere and kept at 80 ° C. for 4 hours.
The temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, 48 g of a pale yellow transparent solution was obtained. The solvent was distilled off from this solution using a rotary vacuum evaporator, and the remaining highly viscous liquid was dissolved in 100 g of n-butyl acetate.
The solvent is again distilled off using a rotary vacuum evaporator. Subsequently, after vacuum drying at 60 ° C. for 24 hours, dissolved in n-butyl acetate and reprecipitated with hexane.
Vacuum dry at ℃ overnight to obtain the product. As a result of measuring the molecular weight of the obtained product by GPC, Mn was 3,300. The obtained product is referred to as Compound D.

Synthesis Example 5 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 10.00 g of N, N-dimethylaminopropylacrylamide, 1.42 g of 2-isocyanatoethyl methacrylate, After charging 2.16 g of 2,4-diphenyl-4-methyl-1-pentene, n-butyl acetate 3 in which 1.050 g of dimethyl 2,2-azobis (2-methylpropionate) was dissolved.
5.0 g was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours. Then, the temperature was increased to 95 ° C., and the reaction was further continued for 2 hours. After cooling to room temperature, 50 g of a pale yellow transparent solution was obtained. The solvent was distilled off from this solution with a rotary vacuum evaporator, and the remaining highly viscous liquid was purified with n-acetic acid.
It is dissolved in 100 g of butyl, and the solvent is distilled off again using a rotary vacuum evaporator. Subsequently, after vacuum drying at 60 ° C. for 24 hours, it is dissolved in n-butyl acetate, reprecipitated with hexane, and further vacuum dried at 60 ° C. for 24 hours to obtain a product. As a result of measuring the molecular weight of the obtained product by GPC, Mn was 3,500. The obtained product is referred to as Compound E.

Synthesis Example 6 In a 50 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 3.00 g of Compound A was dissolved in 10 g of acetone, and then 3-fluorobutyl- 0.60 g of 1,2-epoxypropane was added, the temperature was raised under a nitrogen atmosphere, and the reaction was continued at 50 ° C. for 8 hours. After cooling to room temperature, 13 g of a clear reddish-brown solution was obtained.
The solution is reprecipitated with hexane and dried under vacuum at 60 ° C. overnight to obtain a product. The molecular weight of the obtained product was determined by GPC.
Was Mn = 7500. The obtained product is referred to as Compound AF.

Synthesis Example 7 Synthesis and purification were carried out in the same manner as in Synthesis Example 6, except that Compound A in Synthesis Example 6 was changed to Compound B and the amount of 3-fluorobutyl-1,2-epoxypropane was changed to 0.90 g. Was. As a result of measuring the molecular weight of the obtained product by GPC, Mn = 40
00. The obtained product is designated as compound BF1.

Synthesis Example 8 Compound A of Synthesis Example 6 was added to Compound B, and 0.60 g of 3-fluorobutyl-1,2-epoxypropane was added to 3- (1H,
1H, 7H-dodecafluoropeptyloxy) -1,2
-Synthesis example 6 except that 1.27 g of epoxypropane was used
Synthesis and purification were carried out in the same manner as described above. The molecular weight of the obtained product was measured by GPC and found to be Mn = 4100.
The obtained product is designated as compound BF2.

Synthesis Example 9 Synthesis and purification were carried out in the same manner as in Synthesis Example 6 except that Compound A of Synthesis Example 6 was changed to Compound C, and the amount of 3-fluorobutyl-1,2-epoxypropane was changed to 0.84 g. Was. As a result of measuring the molecular weight of the obtained product by GPC, Mn = 40
00. The obtained product is referred to as compound CF.

Synthesis Example 10 Synthesis and purification were carried out in the same manner as in Synthesis Example 6 except that Compound A in Synthesis Example 6 was changed to Compound D, and the amount of 3-fluorobutyl-1,2-epoxypropane was changed to 0.93 g. Was. As a result of measuring the molecular weight of the obtained product by GPC, Mn = 40
00. The resulting product is designated as compound DF.

Synthesis Example 11 Compound A of Synthesis Example 6 was added to Compound E, and 0.60 g of 3-fluorobutyl-1,2-epoxypropane was added to 2,2,3,3.
Synthesis and purification were performed in the same manner as in Synthesis Example 6, except that 0.47 g of 3,3-pentafluoropropanol was used. As a result of measuring the molecular weight of the obtained product by GPC, Mn = 4
000. The obtained product is designated as compound EF.

Example 1 The composition and amount (parts by weight) of the recording liquid are as follows. C.I. Food Black 2 3 Ethylene glycol monoallyl ether 24 Ethylene glycol 24 Compound AF 5 Water 44 ──────────────────────── Total 100

A raw material having the above composition was charged into a flask, and
The mixture was stirred at 2 ° C. for 2 hours, cooled to room temperature, and filtered with a 0.8 μm membrane filter to obtain a recording liquid.

Example 2 A recording solution was prepared in the same manner as in Example 1 except that the compound AF of Example 1 was changed to Compound BF1.

Example 3 A recording solution was prepared in the same manner as in Example 1 except that the compound AF in Example 1 was changed to Compound BF2.

Example 4 A recording liquid was prepared in the same manner as in Example 1 except that the compound AF in Example 1 was changed to Compound CF.

Example 5 A recording solution was prepared in the same manner as in Example 1 except that the compound AF in Example 1 was changed to Compound DF.

Example 6 A recording solution was prepared in the same manner as in Example 1 except that the compound AF in Example 1 was changed to Compound EF.

Comparative Example 1 A recording liquid was prepared in the same manner as in Example 1 except that Compound A of Example 1 was not added.

Comparative Example 2 Compound A of Example 1 was replaced with anionic fluorinated surfactant E
A recording liquid was prepared in the same manner as in Example 1 except that F-204 (manufactured by Tochem Products Inc.) was used.

Example 7 A flask was charged with 5 g of Compound AF, and a print cartridge black (product number 516) manufactured by Hewlett-Packard Co., Ltd.
26A) was charged, stirred at 60 ° C. for 2 hours, cooled to room temperature, and then filtered using a 0.8 μm membrane filter to obtain a recording liquid.

Example 8 A recording solution was prepared in the same manner as in Example 7 except that the compound AF of Example 7 was changed to Compound BF1.

Example 9 A recording solution was prepared in the same manner as in Example 7 except that the compound AF in Example 7 was changed to Compound BF2.

Example 10 A recording solution was prepared in the same manner as in Example 7 except that the compound AF in Example 7 was changed to Compound CF.

Example 11 A recording solution was prepared in the same manner as in Example 7 except that the compound AF in Example 7 was changed to Compound DF.

Example 12 A recording solution was prepared in the same manner as in Example 7 except that the compound AF in Example 7 was changed to Compound EF.

Comparative Example 3 A recording liquid was prepared in the same manner as in Example 7 except that the compound AF in Example 7 was replaced with an anionic fluorine-based surfactant EF-204 (manufactured by Tochem Products Co., Ltd.).

Example of Effect Using the obtained recording liquid, ink jet recording was performed by an ink jet printer (Desk Writer 550C, manufactured by Hewlett-Packard Co., Ltd.), and the water fastness was evaluated. The method is plain paper (recycled paper / neutral paper, NB Co., Ltd.)
(Ricoh NBSPAPER) and visually evaluated (1) the case of being immersed in water for 10 minutes after drying, and (2) the case of dropping water on the printed paper and rubbing it with a finger.

(Results) When the recording liquids of Examples 1 to 12 were used, bleeding hardly occurred in both (1) and (2). When the recording liquid of Comparative Example 1 and the print cartridge black (product number 51626A) manufactured by Hewlett-Packard Co., Ltd., were used, (1) and (2) all bleed badly. Comparative Example 2,
Sample No. 3 was more water-resistant, but had larger bleeding. The recording liquids of Examples 1 to 12 were sealed in a glass container.
Even after storage at 60 ° C. and 60 ° C. for 6 months, no precipitation of insoluble components was observed, and there was no change in physical properties or color tone of the liquid. The ejection stability in the inkjet printer was evaluated as follows. Using the recording liquids of Examples 1 to 12, intermittent ejection every 2 seconds and ejection after leaving for 2 months were examined.
In each case, recording was stable and uniform without clogging at the orifice tip. The images recorded with the recording liquids of Examples 1 to 12 were high in density and clear. After 3 months of exposure to room light, the rate of decrease in density was 1% or less.

[0077]

The recording liquid of the present invention can provide a print excellent in water fastness even when recording on plain paper, and is suitable as an ink for ink jet recording and writing or a recording liquid.

Claims (10)

[Claims] 1. A recording liquid comprising a fluorine compound containing a fluoroalkyl group and an amino group in a molecule, a water-soluble dye, and an aqueous medium. 2. The recording liquid according to claim 1, wherein the fluorine-containing compound has a fluoroalkyl group at a terminal of a molecular chain. 3. A compound obtained by reacting an amino group-containing compound having an active hydrogen-containing functional group with a fluoroalkyl group-containing compound having a functional group capable of reacting with the active hydrogen. Item 3. The recording liquid according to Item 1 or 2. 4. The compound obtained by reacting a fluoroalkyl group-containing compound having an active hydrogen-containing functional group with an amino group-containing compound having a functional group capable of reacting with the active hydrogen. Item 4. The recording liquid according to Item 1. 5. An amino group-containing compound having an active hydrogen-containing functional group, comprising a radical polymerizable unsaturated group-containing monomer having an amino group and a radical polymerizable unsaturated group-containing monomer having an active hydrogen-containing functional group. The recording liquid according to claim 3, which is a copolymer with a polymer. 6. An amino group-containing compound having an active hydrogen-containing functional group is prepared by converting a radical polymerizable unsaturated group-containing monomer having an amino group into a chain transfer agent or a polymerization initiator having an active hydrogen-containing functional group. The recording liquid according to claim 3, which is a (co) polymer obtained by polymerization below. 7. An amino group-containing compound having an active hydrogen-containing functional group is obtained by converting a radical polymerizable unsaturated group-containing monomer having an amino group into a chain transfer agent having an active hydrogen-containing functional group and a polymerization initiator. The recording liquid according to claim 3, which is a (co) polymer obtained by polymerization below. 8. The amino group-containing compound having a functional group capable of reacting with active hydrogen has a radical polymerizable unsaturated group-containing monomer having a tertiary amino group and a functional group capable of reacting with active hydrogen. The recording liquid according to claim 4, which is a copolymer with a radical polymerizable unsaturated group-containing monomer. 9. The recording liquid according to claim 1, wherein the amino group is a tertiary amino group. 10. The recording liquid according to claim 1, comprising 0.01 to 30% by weight of a fluorine compound.