JP2001115071A - Ink jet printing ink, ink set, and method for making decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet printing ink for image formation on decorative sheets where there is hard to develop bleedings and/or color unevennesses on images. SOLUTION: This ink jet printing ink is such as to be used for image formation on decorative sheets and comprise b wt.% of a water-soluble dye with a solubility of (a) g/100 g water at 20 deg.C, c wt.% of a water-miscible organic solvent and water; wherein the above (a), b and c meet the relationships described below: a<=20, 5<=c<=30, and 2<=[(a×c)/b]<=100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording ink, an ink set, and a method for producing a decorative sheet. More specifically, the present invention relates to a building, a building material, a vehicle, a ship, a machine, miscellaneous goods, household goods, or The present invention relates to an ink jet recording ink, an ink set, and a method for manufacturing a decorative sheet that can be used for image recording of a decorative sheet such as a toy.

[0002]

2. Description of the Related Art A decorative sheet is a sheet in which various characters and patterns are printed on a resin film.
It is used by sticking to vehicles, ships, machines, miscellaneous goods, household goods, toys and the like. Conventionally, characters and patterns on decorative sheets have been written by screen printing or gravure printing, so the production of decorative sheets requires a plate making process. Not suitable. On the other hand, in recent years, the field of use of decorative sheets has expanded, and decorative sheets having various patterns have been demanded according to applications, and it has been strongly desired that the patterns be multicolor and high-definition. However, in the conventional manufacturing method using printing, the plate-making process must be repeatedly performed every time a pattern is changed, and the cost is remarkably increased when a variety of small-quantity products are used.

[0003]

As a method for producing a small number of kinds of decorative sheets, for example, Japanese Patent Application Laid-Open No. 7-13743 is known.
No. 5 proposes a method of forming a pattern on a predetermined transparent sheet by an ink jet recording method to produce an interior decoration sheet such as wallpaper. However, unlike the case where an image is formed on paper, an OHP film, or the like, the decorative sheet is then used in a processing step such as pasting to an object.
It is often placed under high temperature (around 80 ° C). Further, even after the decorative sheet is attached to the object, it is often placed in various environments regardless of whether it is outdoors or indoors. The present inventors have conducted intensive studies and found that when a decorative sheet often placed in a severe environment is produced by inkjet recording using a known ink for paper or OHP, the following problems may occur. I found it. 1) Normally, the decorative sheet is heated to a high temperature (around 80 ° C.) when the decorative sheet is attached to the surface of the object. There is a problem that a phenomenon (so-called bleeding) in which an image on an application sheet flows out or a color material contained in the ink aggregates in a spot-like manner, causing color unevenness in the image. 2) Even when the high-temperature treatment is not performed, the decorative sheet on which an image is printed by an inkjet recording method is often exposed to high temperature and high humidity after being attached to an object. Phenomenon in which the upper image starts to flow (bleed)
May occur.

An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide an ink jet recording ink for forming an image on a decorative sheet in which a bleed phenomenon or color unevenness hardly occurs in an image portion. Also,
SUMMARY OF THE INVENTION It is an object of the present invention to provide an ink jet recording ink set for forming an image of a decorative sheet in which bleeding between colors in an image portion is reduced when a multicolor image is formed. Another object of the present invention is to provide a method for producing a decorative sheet using ink jet recording, in which bleeding and color unevenness are less likely to occur in an image area. Another object of the present invention is to provide a method for manufacturing a decorative sheet that can easily manufacture a decorative sheet at low cost.

[0005]

The inventors of the present invention have studied the cause of the occurrence of the bleed and the color unevenness. As a result, the bleed and the color unevenness are found in the water-soluble organic solvent slightly remaining in the image area of the decorative sheet. That the water-soluble dye forming the image area is re-dissolved. Furthermore, as a result of intensive studies based on this knowledge, the present invention has been completed. The means for solving the above problems are as follows. <1> An inkjet recording ink used for forming an image on a decorative sheet, wherein water at 20 ° C.
Water-soluble dye having a solubility of ag in g is b wt%
And c) a water-soluble organic solvent and water, and a, b, and c satisfy the following relational expression. a ≦ 205 ≦ c ≦ 302 2 ≦ {(axc) / b} ≦ 100 <2> The inkjet recording ink according to <1>, wherein at least one of the water-soluble dyes has a carboxylic acid group. <3> The inkjet recording ink according to <2>, wherein at least a part of the carboxylic acid group forms a salt with an ammonium ion. <4> An ink set for inkjet recording comprising three types of color inks each containing a water-soluble dye of magenta, yellow, and cyan, wherein the color ink is any one of <1> to <3>. An ink jet recording ink set which is the ink jet recording ink according to the above.

<5> By providing energy to the ink,
A method for producing a decorative sheet, comprising: discharging droplets of ink onto the surface of a sheet; and recording an image of the ink on the surface of the sheet to produce a decorative sheet.
> A method for producing a decorative sheet, wherein the ink according to any one of <4> to <4> is used in a combination in which the contact angle of the ink on the surface of the sheet at 20 ° C is 5 ° or more and 65 ° or less. <6> The method for producing a decorative sheet according to <5>, wherein the sheet and the ink are used in a combination in which the penetration rate of the ink into the surface of the sheet is 10 seconds or less at 20 ° C. <7> The method for producing a decorative sheet according to <6>, wherein the ink contains a water-soluble dye, and a material for coagulating and / or fixing the water-soluble dye and the ink coexists on the surface of the sheet.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Inkjet Recording Ink and Ink Set) The inkjet recording ink of the present invention is an ink which can be used in an inkjet recording type image recording apparatus. The ink jet recording method is a method of recording an image on a recording medium by applying energy to a liquid ink to discharge the ink from a nozzle, a slit, a porous slit film, or the like. There are a continuous type and an on-demand type as an ink jet recording system. The former is a charge control type (Hetz system), and the latter is an electromechanical conversion system (Kyse system).
r method) and an electrothermal conversion method (thermal ink jet method), and the ink for ink jet recording of the present invention can be used for various types of ink jet image recording apparatuses.

The ink jet recording ink of the present invention is
It contains a water-soluble dye, a water-soluble organic solvent, and water. The water-soluble dye has a solubility in 100 g of water of 2
Use at 20 ° C or less at 0 ° C. When the solubility of the water-soluble dye is within the above-mentioned range, it is possible to suppress the occurrence of bleeding and color unevenness even when the decorative sheet is applied to an object, even when subjected to high-temperature processing. In addition, even when the decorative sheet is placed under high temperature and high humidity after being attached to the object, occurrence of bleed can be suppressed. The solubility of the water-soluble dye in 100 g of water is 20 ° C.
Is preferably 1 g or more because the image density of the formed image becomes good. From a similar point of view, the water-soluble dye water 10
The solubility for 0 g is more preferably 2 g or more and 15 g or less at 20 ° C. When two or more water-soluble dyes are used, the average value of the solubility of the water-soluble dye contained in the ink is 20 g or less at 20 ° C. In addition, the average value of the solubility is a value represented by {sum of (solubility of each water-soluble dye × concentration of each water-soluble dye)} / sum of the concentration of the water-soluble dye.

[0009] The solubility of the water-soluble dye in water is measured as follows. Ultrapure water 1 adjusted to 20 ° C
00g, the water-soluble dye was dissolved, and the concentration was 1% by weight, 2% by weight, 3% by weight,. . . . . An aqueous solution of X% by weight is prepared in each case. The aqueous solutions of various concentrations prepared in 1 wt% increments are each stirred for 1 hour, and then passed through a 0.2 μm filter. From the aqueous solution in which no insoluble water-soluble dye is observed on the filter, the solubility of the water-soluble dye is calculated from the concentration of the aqueous solution having the maximum concentration (% by weight).

As the water-soluble dye, commercially available dyes or newly synthesized dyes can be used. Among them, a direct dye or an acidic dye which can obtain a vivid color is preferable. Specifically, C.I. I. Direct Blue-1, -2, -6, -8, -22, -34, -70,-
71, -76, -78, -86, -142, -199,
-200, -201, -202, -203, -207,
-218, -236, -287 and -307, C.I.
I. Direct Red-1, -2, -4, -8, -9,
-11, -13, -20, -28, -31, -33,-
37, -39, -51, -59, -62, -63, -7
3, -75, -80, -81, -83, -87, -9
0, -94, -95, -99, -101, -110 and -189, C.I. I. Direct Violet-10
7, C.I. I. Direct Yellow-1, -2, -4,-
8, -11, -12, -26, -27, -28, -3
3, -34, -41, -44, -48, -86, -8
7, -88, -132, -135, -142, -144
And -173, C.I. I. Acid Blue-1, -7,
-9, -15, -22, -23, -27, -29, -4
0, -43, -55, -59, -62, -78, -8
0, -81, -90, -102, -104, -111,
-185 and -254, C.I. I. Acid Red-
1, -4, -8, -13, -14, -15, -18,-
21, -26, -35, -37, -249 and -25
7, C.I. I. Acid Yellow-1, -3, -4,-
7, -11, -12, -13, -14, -19, -2
3, -25, -34, -38, -41, -42, -4
4, -53, -55, -61, -71, -76 and-
79 and the like. These dyes are obtained so that a desired hue is obtained and the solubility is in the above range.
They can be used alone or in combination.

The water-soluble dye usually has a hydrophilic group such as a hydroxyl group, a carboxylic acid group and a sulfonic acid group in the molecule. As the water-soluble dye, it is preferable to use at least one water-soluble dye having a carboxylic acid group, since the occurrence of bleeding and color unevenness can be further suppressed.

It is preferable that at least a part of the hydrophilic group of the water-soluble dye forms a salt together with a counter ion, since blurring of the image area can be further reduced. In particular, it is preferable that the water-soluble dye has a carboxylic acid group, and at least a part of the carboxylic acid group forms an ammonium salt having an ammonium ion as a counter ion.

The ink for ink jet recording of the present invention is:
Contains a water-soluble organic solvent. The water-soluble organic solvent refers to an organic solvent that is compatible with each other without phase separation when mixed with water. As the water-soluble organic solvent, polyhydric alcohols, polyhydric alcohol ethers, nitrogen-containing organic solvents, monohydric alcohols, sulfur-containing organic solvents, carbonates, and the like can be used. Specifically, as polyhydric alcohols, ethylene glycol, diethylene glycol,
Propylene glycol, polypropylene glycol, butylene glycol, triethylene glycol, 1,5-
Pentanediol, 1,2,6-hexanetriol,
Glycerin and the like. Examples of the polyhydric alcohol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether. . Examples of the nitrogen-containing organic solvents include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, and triethanolamine. Examples of monohydric alcohols include ethanol, isopropyl alcohol, butyl alcohol, benzyl alcohol and the like. Examples of the sulfur-containing organic solvents include thiodiethanol, thiodiglycerol, sulfolane, dimethylsulfoxide and the like. As the carbonates, propylene carbonate, ethylene carbonate and the like can be used.

The ink jet recording ink of the present invention contains water. As the water, tap water, ion exchange water,
Although distilled water, ultrapure water and the like can be used, it is particularly preferable to use ion-exchanged water, distilled water, ultrapure water so as not to mix impurities in the ink.

The content of the water-soluble organic solvent in the ink for ink jet recording of the present invention is 5% by weight or more and 30% by weight or less, preferably 6% by weight or more and 25% by weight or less. If the content of the water-soluble organic solvent is less than 5% by weight, the moisture retention of the ink tends to decrease, and as a result,
Clogging at the tip of the print head of the ink jet recording apparatus is likely to occur. On the other hand, if the content of the water-soluble organic solvent exceeds 30% by weight, the decorative sheet after printing is placed in a high-temperature, high-humidity environment (for example, the decorative sheet is heated by heat treatment, and When sticking on the surface)
In addition, bleeding is likely to occur in the image area, or the color material in the image area becomes spot-like, which tends to cause color unevenness.

Further, the solubility of the water-soluble dye in 100 g of water at 20 ° C. in the ink for ink-jet recording of the present invention is ag, the content of the water-soluble dye and the content of the water-soluble organic solvent in the ink for ink-jet recording of the present invention. Are defined as b weight% and c weight%, respectively, the following relational expression holds. When 2 ≦ (axc) / b ≦ 100 (axc) / b is less than 2, it is difficult to obtain a satisfactory color tone. On the other hand, when (a × c) / b exceeds 100,
Bleeding occurs in the image part, and the color material in the image part becomes spot-like, causing color unevenness. When two or more water-soluble dyes are contained, b (% by weight) indicates the total content of the water-soluble dyes, and when two or more water-soluble organic solvents are contained, c (weight%)
(% By weight) indicates the total content of the water-soluble organic solvent.

The content b (% by weight) of the water-soluble dye in the ink for ink-jet recording of the present invention is determined in a range where a, b and c satisfy the above relational expression. Preferably, it is 0.05% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 8% by weight or less, particularly preferably 0.1% by weight or less.
It is not less than 8% by weight and not more than 6% by weight. If the content of the water-soluble dye exceeds 10% by weight, clogging of the tip of the print head of the ink jet recording apparatus is likely to occur. On the other hand, when the content of the water-soluble dye is less than 0.05% by weight, the image density may decrease. a, b, and c
Satisfies the above relational expression, and b is preferably 0.05% by weight or more and 10% by weight or less, because there is no such adverse effect. When two or more water-soluble dyes are used in combination, it is preferable that the total content of each water-soluble dye falls within the above range.

The content of the water-soluble dye may be 0.1 to 2.0% by weight, and the ink for inkjet recording of the present invention may be used as a photo ink. Photo-ink is preferable because high gradation can be obtained by overprinting and a high-quality image equivalent to a photograph can be formed. Also, an ink set of photo ink and normal ink may be used.
In this case, at least one of the photo ink and the normal ink is the ink jet recording ink of the present invention, and preferably both are the ink jet recording ink of the present invention.

The ink jet recording ink of the present invention may contain a surfactant. When a surfactant is contained, the surface tension of the ink can be easily adjusted to a desired range. As the surfactant, a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant that hardly affect the dissolution state of the water-soluble dye are preferable.
Nonionic and anionic surfactants are more preferred. Examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Fatty acid ester, fatty acid alkylolamide, acetylene alcohol ethylene oxide adduct, polyethylene glycol polypropylene glycol block copolymer,
Examples thereof include polyoxyethylene ether of glycerin ester and polyoxyethylene ether of sorbitol ester.

Examples of the anionic surfactant include an alkylbenzene sulfonate, an alkylphenyl sulfonate, an alkylnaphthalene sulfonate, a higher fatty acid salt,
Sulfate and sulfonate of higher fatty acid ester, higher alkyl sulfosuccinate and the like. Examples of the amphoteric surfactant include betaine, sulfobetaine, sulfate betaine, and imidazoline. In addition, silicone surfactants such as polysiloxane polyoxyethylene adducts, fluorine surfactants such as oxyethylene perfluoroalkyl ether, biosurfactants such as spiculisporic acid, rhamnolipid, and lysolecithin alone or the surfactant It may be added in combination with the agent.

In the ink for ink jet recording of the present invention, cellulose derivatives such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethyleneglycol, ethylcellulose, carboxyethylcellulose, etc., polysaccharides and derivatives thereof, and other water-soluble polymers are used for controlling ink properties. And polymer emulsions, cyclodextrins, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, and the like.

The ink jet recording ink of the present invention may contain an antioxidant, a fungicide, a conductive agent, an antioxidant, an ultraviolet absorber, a chelating agent, and the like, if necessary. . As the chelating agent,
Ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), ethylenediamine-di (o-hydroxyphenylacetic acid) (EDDHA), nitrilotriacetic acid (NT
A), dihydroxyethylglycine (DHEG), trans-1,2-cyclohexanediaminetetraacetic acid (CyD
TA), diethylenetriamine-N, N, N ',
N ″, N ″ -pentaacetic acid (DTPA), glycol ether diamine-N, N, N ′, N′-tetraacetic acid (GEDT
A) and the like.

The ink jet recording ink of the present invention may contain a viscosity modifier. As the viscosity modifier, it is also useful to add polysaccharides and derivatives thereof in addition to methylcellulose, ethylcellulose and derivatives thereof, glycerin and polyglycerin and adducts of polyethylene oxide and polypropylene oxide. For example, glucose, fructose, mannitol, D
-Sorbitol, dextran, xanthan gum, curdlan, cycloamylose, maltitol and their derivatives.

The ink for ink jet recording of the present invention may contain an acidic or basic substance for the purpose of adjusting the pH of the ink. Examples of the substance for adjusting the pH include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl-1-propanol, ammonia, and ammonium phosphate. , Potassium phosphate, sodium phosphate, lithium phosphate, sodium sulfate, acetate, lactate, benzoate, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, propionic acid, P-toluenesulfonic acid and the like. In addition, generally used pH buffers, for example, good buffers may be used.

The ink-jet recording ink of the present invention comprises:
It can be prepared by mixing and stirring a water-soluble dye, a water-soluble organic solvent, water, and other additives as desired.

The surface tension of the ink for ink jet recording of the present invention at 20 ° C. is preferably from 20 to 45 mN / m, and more preferably from 25 to 40 mN / m. When the surface tension is in the above range, wettability with a decorative sheet (a sheet before image formation), which is a recording agent, is improved, which is preferable. The surface tension of the inkjet recording ink can be increased or decreased by adjusting the content of each component.

When a multicolor image is formed, ink sets for cyan, magenta, and yellow ink jet recording are used, and it is preferable that all the color inks of the ink set are the inks for ink jet recording of the present invention. When the three color inks are the inks for ink jet recording of the present invention, color bleeding occurring between primary colors of cyan, magenta, and yellow and between secondary colors can be reduced, and a colorful multicolor image can be formed. It is preferable because it can be formed.

The surface tension of these inks at 20 ° C. is preferably from 20 to 45 mN / m, and more preferably from 25 to 40 mN / m, since the wettability with a decorative sheet as a recording agent is good.

In order to further enhance the sharpness of an image, it is preferable to use a black ink for the ink set for ink jet recording. The black ink used may be a dye ink or a pigment ink. When a dye ink is used as the black ink, the black ink is preferably the ink for inkjet recording of the present invention. When a dye is used as the coloring material of the black ink, the dye may be Basacid Black X34.
liquid, BasacidBlack X38 l
liquid (above BASF), Special Black SP Liquid, Special Black HF (Bayer
C.), C.I. I. Direct Black-4, -9, -1
1, -17, -19, -22, -32, -80, -15
1, -154, -168, -171, -194 and-
195, C.I. I. Food black-1 and -2, C.I.
I. Acid Black-1, -2, -7, -16, -2
4, -26, -28, -31, -48, -52, -6
3, -107, -112, -118, -119, -12
1, -172, -194 and -208.
These may be used alone or as a mixture of two or more. These contents are determined arbitrarily,
A content of 0.5% by weight to 10% by weight in the black ink is preferably used.

When a dye is used as the coloring material of the black ink, the solubility in water is preferably not more than 20 g / 100 g water at 20 ° C. as in the case of the cyan, magenta and yellow inks. More preferably, at least one of the dyes has a carboxylic acid group as a hydrophilic group. In order to obtain even better environmental stability, it is preferable that a part of the counter ion of the water-soluble dye is an ammonium salt.

Since there is no problem with the transparency of the coloring material in the black ink, a pigment may be used as the coloring material. As the pigment, carbon black, inorganic pigments, organic pigments, oily dyes, disperse dyes and the like can be used, but carbon black is preferably used from the viewpoint of ease of handling. Furnace black, lamp black, acetylene black, channel black and the like, for example, Raven7
000, Raven5750, Raven5250, R
aven 5000 ULTRA II, Raven 3
500, Raven2000, Raven1500, R
aven1250, Raven1200, Raven1
190 ULTRA II, Raven 1170, Rav
en1255, Raven1080, Raven106
0 (all manufactured by Columbian Carbon Co., Ltd.), Regal4
00R, Regal330R, Regal660R, M
ogul L, Black Pearls L, Mon
arch 700, Monarch 800, Mona
rch 880, Monarch 900, Monar
ch 1000, Monarch 1100, Mona
rch 1300, Monarch 1400 (all manufactured by Cabot Corporation),

Color Black FW1, Col
or Black FW2, Color Black
FW2V, Color Black 18, Color
Black FW200, Color Black
S150, Color Black S160, Col
or Black S170, Pritex35, P
ritexU, Pritex Vritex140
U, Printex140V, Special Bla
ck 6, Special Black 5, Spec
ial Black 4A, Special Black
k4 (all manufactured by Degussa), No. 25, no. 33,
No. 40, no. 47, no. 52, no. 900,
No. 2300, MCF-88, MA600, MA
7, MA8, and MA100 (all manufactured by Mitsubishi Chemical Corporation), but are not limited thereto. In addition, magnetic fine particles such as magnetite and ferrite, titanium black and the like may be used as a black pigment.

When a pigment is used as a coloring material of the black ink, a surface-treated pigment may be used as the pigment.
Examples of the surface treatment of the pigment include a surface treatment with an alcohol such as ethanol and methanol, a surfactant treatment, a pigment derivative treatment for replacing an acidic group or a basic group, and a pigment coating reaction treatment for coating the pigment surface with another substance. , Surface chemical reaction treatment for introducing a substituent by a condensation reaction or a graft reaction, coupling reaction treatment for surface treatment with a silane coupling agent, aluminate coupling agent, etc., plasma reaction treatment, CVD treatment, and the like. . The surface-treated pigment can be obtained as a commercial product,
For example, Cabojet 300 (Cabot), Mic
rojet CW-1 (Orient Chemical Co., Ltd.).

When a pigment is used as a coloring material of the black ink, it is preferable to add a dispersant since the pigment is easily dispersed in a solvent. In particular, when using a pigment that has not been subjected to the surface treatment as a coloring material, when a dispersing aid is added,
It is effective. As the dispersant, a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like can be used. More preferred. Therefore, it is more preferable to use a dispersant prepared in a clean environment. As the polymer dispersant, a polymer having a hydrophilic structure part and a hydrophobic structure part is preferable. As the polymer having a hydrophilic structure portion and a hydrophobic structure portion, a condensation polymer and an addition polymer can be used. Examples of the condensation polymer include known polyester dispersants. Examples of the addition polymer include an addition polymer of a monomer having an α, β-ethylenically unsaturated group. The addition polymer includes a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group and an α, β-
Copolymers obtained by appropriately combining and copolymerizing with a monomer having an ethylenically unsaturated group are exemplified. Further, a polymer obtained by polymerizing a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group alone may be used.

Examples of the monomer having an α, β-ethylenically unsaturated group having a hydrophilic group include monomers having a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphate group, and the like, for example, acrylic acid, methacrylic acid, crotonic acid. , Itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, vinylsulfonic acid, styrenesulfonic acid, sulfonated vinylnaphthalene, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, bismethacrylic Roxyethyl phosphate, methacryloxyethylphenyl acid phosphate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and the like. Examples of the monomer having an α, β-ethylenically unsaturated group having a hydrophobic group include styrene derivatives such as styrene, α-methylstyrene, vinyltoluene, vinylcyclohexane, vinylnaphthalene, vinylnaphthalene derivatives, alkyl acrylate, methacrylic acid. Acid alkyl esters, methacrylic acid phenyl esters, methacrylic acid cycloalkyl esters, crotonic acid alkyl esters, itaconic acid dialkyl esters, and maleic acid dialkyl esters.

Preferred copolymers for use as the polymer dispersant include, for example, styrene-styrene sulfonic acid copolymer, styrene-maleic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid Copolymer, vinyl naphthalene-maleic acid copolymer, vinyl naphthalene-methacrylic acid copolymer, vinyl naphthalene-acrylic acid copolymer, acrylic acid alkyl ester-acrylic acid copolymer, methacrylic acid alkyl ester-methacrylic acid, Styrene-methacrylic acid alkyl ester-methacrylic acid copolymer, styrene-acrylic acid alkyl ester-acrylic acid copolymer, styrene-methacrylic acid phenyl ester-methacrylic acid copolymer, styrene-methacrylic acid cyclohexyl ester-methacrylic acid copolymer Coalescence And the like. Further, copolymers obtained by appropriately copolymerizing a monomer having a polyoxyethylene group and a hydroxyl group with these polymers can also be preferably used. When a pigment having an acidic functional group on the surface is used as the coloring material of the black ink, it is preferable to use a copolymer of a monomer having a cationic functional group as the polymer dispersant. The polymer is preferably used because it has a high affinity for the pigment and is used as a polymer dispersant because the dispersion stability of the pigment is improved. Examples of the monomer having a cationic functional group include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate,
N, N-dimethylaminomethacrylamide, N, N-
Dimethylaminoacrylamide, N-vinylpyrrole,
N-vinylpyridine, N-vinylpyrrolidone, N-vinylimidazole and the like can be mentioned.

The copolymer may have any structure such as a random, block, and graft copolymer.
The polymer dispersant may have a low molecular weight, but preferably has a weight average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ , and 2.0 × 10 ^{3 to} 9.0 × 10 ³ . Is more preferable, and more preferably 2.5 × 10 ^{3 to} 8.0 × 10 ³ .

As the polymer dispersant, polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid,
Polyvinyl sulfonic acid, polyalginic acid, polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer, formalin condensate of naphthalenesulfonic acid, polyvinylpyrrolidone, polyethyleneimine,
Polyamines, polyamides, polyvinyl imidazoline, aminoalkyl acrylate / acrylamide copolymer, chitosan, polyoxyethylene fatty acid amide, polyvinyl alcohol, polyacrylamide, cellulose derivatives such as carboxymethyl cellulose, carboxyethyl cellulose, polysaccharides and derivatives thereof, etc. Can be used.

In the dispersant having an acidic group as a free radical, the acidic group is preferably a carboxylic acid group or a sulfonic acid group, and preferably has both acidic groups. Carboxylic acid and sulfonic acid are preferred because they dissociate and d quickly, and by adjusting the pH of the black ink to an appropriate range, a high surface charge density can be obtained and the dispersibility of the pigment is further improved. Among them, it is preferable to use a dispersant whose free radical has a carboxylic acid group. When a dispersant having a carboxylic acid group is used, after the ink droplets have landed on the recording material, the pigment in the ink droplets has an appropriate agglomeration property, reduces image bleeding, and improves image fixability. It is preferable because the quality is improved. The dispersant having an acidic group is preferable when at least a part of the acidic group forms a salt with a basic compound, since the water solubility of the dispersant increases.
For example, among the polymers, compounds that can form a salt with a polymer having an acidic group include sodium, potassium,
Examples thereof include alkali metals such as lithium, aliphatic amines such as monomethylamine, dimethylamine and triethylamine, alcohol amines such as monomethanolamine, monoethanolamine, diethanolamine, triethanolamine and diisopropanolamine, and ammonia. Among them, basic compounds of alkali metals such as sodium, potassium and lithium are preferable. A basic compound of an alkali metal is preferable because it is a strong electrolyte and has a large effect of accelerating the dissociation of an acid.

The dispersants may be used alone or in combination of two or more. Since the preferable range of the dispersant varies depending on the type of the coloring material used, it cannot be unconditionally determined. However, in general, the total amount is 0.1 to 100% by weight based on the content of the coloring material. Is preferably 1 to 50% by weight, more preferably 3 to 20% by weight.

The black ink containing a pigment as a coloring material is
For example, in an aqueous solution containing a predetermined amount of a dispersant, a predetermined amount of a pigment is added, and after sufficient stirring, dispersion is performed using a disperser, and coarse particles are removed by centrifugation or the like. It can be prepared by adding an agent or the like, stirring and mixing, and performing filtration. Alternatively, it can be prepared by mixing a predetermined solvent, adding a predetermined amount of a dispersant, and then adding a pigment and dispersing the mixture using a disperser. Examples of the disperser include a colloid mill, a flow jet mill, a slasher mill, a high-speed disperser, a ball mill, an attritor, a sand mill, a sand grinder,
Ultra Fine Mill, Eiger Motor Mill, Dyno Mill, Pearl Mill, Agitator Mill, Kobol Mill, 3
Roll, roll, extruder, kneader,
Examples include a microfluidizer, an optimizer, a laboratory homogenizer, an ultrasonic homogenizer, and an accumulator, and these may be used alone or in combination.

The black ink has a surface tension of 20 ° C.
Is preferably 20 to 70 mN / m, and 30 to 55 mN / m.
More preferably, it is mN / m. Further, the viscosity of the black ink at 20 ° C. is preferably 1 to 10 mPa · s, and more preferably 1 to 5 mPa · s. It is preferable that the viscosity is in the above range, because the ejection stability of the ink is improved.

(Preparation Method of Decorative Sheet) In the preparation method of the decorative sheet of the present invention, energy is supplied to the ink to discharge droplets of the ink onto the surface of the sheet, and the image formed of the ink is formed on the surface of the sheet Recording a decorative sheet to produce a decorative sheet, that is, a method for producing a decorative sheet using an inkjet recording method,
The sheet and the ink are used in a combination in which the contact angle of the ink on the surface of the sheet at 20 ° C. is 5 degrees or more and 65 degrees or less. The contact angle is preferably 8 degrees or more and 50 degrees or less at 20 ° C.
More preferably, it is 10 degrees or more and 45 degrees or less. still,
The term “contact angle” as used herein refers to the contact angle of an ink droplet one second after one drop of ink is dropped on a sheet, and can be measured with a commercially available contact angle meter.

If the contact angle of the ink on the sheet surface is within the above range, bleeding and color unevenness may occur even when the decorative sheet is subjected to high temperature and / or high humidity after image formation. It is preferable because it is difficult. When the inkjet recording ink of the present invention is used as the ink,
It is preferable that the contact angle can be adjusted to the above range for any of the sheets, and the versatility is improved. As the inkjet recording method that can be used in the method for producing a decorative sheet of the present invention, both a continuous type and an on-demand type can be used, and a charge control type (Het).
z method), the latter is electromechanical conversion method (Kyser method), electrothermal conversion method (thermal ink jet method)
Any of the ink jet recording methods can be used.

Further, it is preferable to use the sheet and the ink in a combination in which the penetration rate of the ink into the surface of the sheet is 20 seconds or less at 20 ° C., because the effect is further increased. The permeation rate at 20 ° C. is preferably 8 seconds or less, and more preferably 5 seconds or less. The permeation speed refers to the time after printing 100% coverage on a sheet until no ink remaining on the image surface is visually recognized.

Examples of the sheet on which an image is recorded with ink include a support and a sheet having at least one layer for fixing the ink on the support. This sheet is different from paper and an OHP sheet which can be used as a recording material for ordinary ink jet recording in that transparency is regarded as important and almost no sizing agent is contained therein. Further, the sheet preferably has flexibility.

As a more specific form of the sheet,
Examples include a sheet in which a transparent, translucent, white or light-colored film is used as a support, and at least one surface is an ink receiving layer. The ink receiving layer has a function of fixing an ink droplet ejected from the tip of the inkjet recording head in place. The ink receiving layer contains at least a binder. Examples of the binder include polyvinyl alcohol, modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, polyester, polyacrylic acid, silanol, vinyl acetate, oxidized starch, etherified starch, and cellulose derivatives (for example, carboxymethyl cellulose). , Hydroxyethyl cellulose), casein, gelatin, soy protein, maleic anhydride resin, conjugated diene copolymer latex (eg, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer), acrylate ester and methacrylate ester Polymers or copolymers, acrylic acid-based copolymer latexes such as acrylic acid and methacrylic acid polymers or copolymers, ethylene vinyl acetate copolymers, Functional group-modified polymer latex of the above-mentioned various polymers with a monomer containing a functional group such as a xyl group, an aqueous adhesive such as a thermosetting synthetic resin system (eg, melamine resin, urea resin), polymethyl methacrylate, polyurethane Resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, alkyd resin and the like. These resins can be used alone or as a mixture.

The ink receiving layer preferably contains a material for coagulating and / or fixing the water-soluble dye. Examples of the substance that aggregates and / or fixes the water-soluble dye include inorganic pigments. As the inorganic pigment, an inorganic pigment having a specific surface area by BET of 100 g / m ² or more is preferable, and an inorganic pigment having a specific surface area of 200 g / m ² or more is more preferable. If the specific surface area is less than 100 g / m ² , the image density may decrease. Examples of the material of the inorganic pigment include kaolin, talc, soft calcium carbonate, hard calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, and silicate. Calcium, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples include hydrolyzed halloysite, magnesium carbonate, and magnesium hydroxide.

Other materials for coagulating and / or fixing the water-soluble dye include cationic fixing agents, pigment dispersants, thickeners, flow improvers, mold release agents, foaming agents, penetrants,
Examples include coloring dyes, coloring pigments, fluorescent whitening agents, ultraviolet absorbers, preservatives, fungicides, waterproofing agents, wet paper strength agents, dry paper strength agents, and antioxidants.

The material for aggregating and / or fixing the water-soluble dye only needs to coexist with the ink on the surface of the sheet, and may be contained in a layer other than the receiving layer of the sheet. It may be contained in the sheet, or may be sprayed on the sheet during the process of producing the decorative sheet (before or after inkjet recording). Especially, it is preferable to contain it in the ink receiving layer.

When the ink receiving layer is composed of a binder resin and an inorganic pigment, the content of the binder resin is preferably 3 to 70% by weight, and more preferably 5 to 50% by weight based on the inorganic pigment. Is more preferred. When the content of the binder resin is less than 3% by weight, the strength of the ink receiving layer may decrease.
The image quality of the formed image may be reduced.

Examples of the support for the sheet include transparent, translucent, white and light-colored plastic films. As the plastic film, polyethylene terephthalate, polyethylene, polypropylene,
Synthetic resin films such as polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyamide and the like, and, if desired, uniaxial stretching or biaxial stretching Used as

An adhesive layer is formed on the back surface of the support (the surface to be adhered to the object and generally opposite to the side on which the ink receiving layer is formed) and the surface. Is also good.
It is preferable to form an adhesive layer because the produced decorative sheet can be easily attached to an object. For convenience of transportation and storage, release paper may be further attached to the adhesive layer. Further, a heat-sealing layer or a pressure-bonding layer exhibiting adhesiveness may be formed by heating or pressing. The adhesive layer, the heat-sealing layer, or the pressure-bonding layer may be formed on the object.

The ink receiving layer is prepared by applying a coating solution prepared by dissolving or dispersing a binder resin and, if desired, additives such as the inorganic pigment or the like in a solvent onto the support and drying the coating solution. It can be formed on a support. Examples of the solvent include water, a water-soluble organic solvent such as alcohol, and a mixed solvent thereof. Application is, for example, an air knife coater, a curtain coater,
Die coater, blade coater, gate roll coater, bar coater, rod coater, roll coater,
It can be performed by various devices such as a bill blade coater, a short dwell blade coater, and a size press. After the ink receiving layer is formed on the support, the surface may be smoothed using a calender such as a machine calender, a TG calender, a super calender, and a soft calender.

In order to make the ink receiving layer and the support more firmly adhere to each other, it is preferable that the surface of the support is subjected to a modification treatment such as a corona discharge treatment, a plasma treatment or a flame treatment.

The sheet is 10 to 120 for easy handling.
μm, more preferably 20 to 100 μm.

[0057] The sheet may have a protective layer. The protective layer may be provided before forming an image on a sheet, or may be provided after forming an image on a sheet.
Usually, it is provided on the surface of the decorative sheet opposite to the surface to be attached to the object. Further, an optical protection layer, for example, an ultraviolet absorbing layer may be provided on the sheet surface or in the sheet.

The decorative sheet produced by the method of the present invention can be attached to an object to be decorated after printing on the ink receiving layer by ink jet recording. The printing surface may be a surface to be attached to the object or a surface opposite to the surface to be attached. When the printing surface is the surface to be attached to the object, mirror printing is performed as necessary. After the sheet is attached to the object, an image may be formed on the sheet by an inkjet recording method to produce a decorative sheet.

The produced decorative sheet is affixed to wood, plastic, glass, metal, building material, or the like, and used for decoration of an object or information display. As a method of attaching the decorative sheet to the object, the pressure-bonding layer, the heat-sealing layer, or the adhesive layer of the decorative sheet (or the object) is brought into contact with the object (or the decorative sheet), If desired, a method of bonding by pressing and / or heating may be used.

[0060]

The present invention will be described below in more detail with reference to examples. (Example 1) The following constituent materials were mixed and stirred, sufficiently dissolved, and then subjected to pressure filtration using a 0.45 μm filter to obtain cyan ink 1. C. I. Direct Blue 307 2.0% by weight (solubility in 100g of water at 20 ° C: 13g; having a carboxylic acid group as a hydrophilic group) Diethylene glycol 6.0% by weight Ethylene glycol 2.0% by weight Thiodiglycol 2.0% by weight Diethylene glycol monobutyl ether 1.0% by weight Ultrapure water 87.0% by weight

The following constituent materials were mixed and stirred, sufficiently dissolved, and then subjected to pressure filtration using a 0.45 μm filter to obtain magenta ink 1. C. I. Direct Red 227 3.0% by weight (solubility 10 g in water 100 g at 20 ° C .; having a carboxylic acid group as a hydrophilic group) I. Acid Red 52 0.1 wt% (solubility 40 g in 100 g of water at 20 ° C .; having a sulfonate group as a hydrophilic group) Glycerin 10.0 wt% Ethylene glycol 9.0 wt% Sulfolane 5.0 wt% Surface activity Agent (“Olefin E1010”: Nissin Chemical Co., Ltd.) 0.1% by weight Ultra pure water 72.8% by weight

The following constituent materials were mixed and stirred, sufficiently dissolved, and then subjected to pressure filtration using a 0.45 μm filter to obtain Yellow Ink 1. C. I. Direct Yellow 132 3.5% by weight (Solubility 8 g in 100 g of water at 20 ° C .; Carboxylic acid group as hydrophilic group, counter ion replaced by ammonium salt) Diethylene glycol 15.0% by weight Sulfolane 10.0% by weight Thio Diethanol 10.0% by weight Surfactant 0.3% by weight ("Pluronic PE4300": manufactured by BASF) 61.2% by weight of ultrapure water

The following constituent materials were mixed and stirred to obtain a black ink 1. Cabojet 300 15.0% by weight (Carbon black amount 20% by weight) Diethylene glycol 10.0% by weight Sulfolane 5.0% by weight Isopropyl alcohol 2.0% by weight Surfactant 0.1% by weight (polyoxyethylene oleyl ether: E .O. Number 20 mol / 1 molecule) Ultrapure water 67.9% by weight

The produced cyan ink 1, magenta ink 1, yellow ink 1, and black ink 1 were each filled in an ink cartridge integrated with a printer head. Next, each of the ink cartridges is set in a cartridge holder of a printer modified from an inkjet printer JetWind300C (manufactured by Fuji Xerox Co., Ltd.), and cyan, magenta, and yellow single-color images are formed on a sheet prepared as follows. Then, a decorative sheet was produced.・ Preparation of sheet Polyethylene terephthalate (thickness 100
μm, manufactured by Toray Industries Co., Ltd.), and a coating solution having the following composition was applied to one surface thereof with a bar coater so that the film pressure after completion was 10 μm, and dried in a dryer at 150 ° C. for 10 minutes to obtain a sheet. Was prepared. 8.0 parts by weight of fine alumina powder (AKP-015, manufactured by Sumitomo Chemical Co., Ltd.) 10.0 parts by weight of polyvinyl alcohol (product name: PVA117, manufactured by Kuraray Co., Ltd.) 82.0 parts by weight of ultrapure water

The obtained decorative sheet was coated with an adhesive on the surface opposite to the printing surface, and heated and pressed at 80 ° C. in a white plastic box to be bonded. The occurrence of bleed during thermocompression bonding and the occurrence of bleed after long-term storage were visually observed and evaluated according to the following criteria. 1) Bleeding test at the time of thermocompression bonding 〇: After affixed on the object, the formed image on the decorative sheet was observed, but no bleeding occurred. Δ: The formed image on the decorative sheet was observed after being stuck on the object, and although there was very small bleed, it was in a range where there was no practical problem. ×: After the image was formed on the decorative sheet after being stuck on the object, the occurrence of bleed was clearly recognized visually. 2) Bleeding test after long-term storage The sample obtained in the above test was left in a sunshine place outdoors for one month. The sample was evaluated based on the same criteria as in 1). Further, a full image was formed, and the above 1) and 2) were evaluated. The presence or absence of bleeding between colors was evaluated according to the following criteria. 3) Evaluation of bleeding between colors: No bleeding between colors occurred. Δ: Some bleeding between colors occurred, but could not be visually confirmed. ×: Bleeding between colors occurred, which could be visually confirmed.

Table 1 below shows the results of the evaluation. Also,
For cyan toner 1, magenta toner 1, yellow toner 1 and black toner 1, water-soluble dye 2
The solubility ag in 100 g of water at 0 ° C., the content c weight% of the water-soluble organic solvent in the ink, and {(ax × c) / b} (b is the content (% by weight) of the water-soluble dye in the ink Are shown in Table 1 together. still,
When two or more water-soluble dyes are used, a indicates the average solubility, and the average solubility is [｛the solubility of each dye ×
Sum of each dye concentration) / total concentration of dye]. Table 1 below also shows the contact angle and penetration rate of each ink with the decorative sheet.

Example 2 The following constituent materials were mixed and stirred, sufficiently dissolved, and then subjected to pressure filtration using a 0.45 μm filter to obtain cyan ink 2. C. I. Direct Blue 307 2.5% by weight (4 g solubility in 100 g of water at 20 ° C .; having a carboxylic acid group as a hydrophilic group) Propylene glycol 20.0% by weight Diethylene glycol 5.0% by weight Diethylene glycol monobutyl ether 12.5% by weight Interface Activator (“Olefin E1010”: manufactured by Nissin Chemical Co.) 0.3% by weight Ultrapure water 59.7% by weight

The following constituent materials were mixed and stirred, sufficiently dissolved, and then filtered under pressure using a 0.45 μm filter to obtain magenta ink 2. Project Fast Magenta 2 2.5% by weight (5 g solubility in 100 g of water at 20 ° C .; Carboxysan group as a hydrophilic group; weight% in terms of solid content, manufactured by Zeneca Corporation) Glycerin 10.0% by weight Ethylene glycol 10.0 % By weight Sulfolane 10.0% by weight Surfactant 1.0% by weight ("Bluronic PE6400": manufactured by BASF) 66.5% by weight of ultrapure water

The following constituent materials were mixed and stirred, sufficiently dissolved, and then subjected to pressure filtration using a 0.45 μm filter to obtain a yellow ink 2. C. I. Direct Yellow 144 3.0% by weight (Solubility in water 100g at 20 ° C: 9g; having carboxylic acid group as hydrophilic group) Diethylene glycol 8.0% by weight Sulfolane 5.0% by weight Thiodiethanol 3.6% by weight Surfactant 1.0% by weight ("Pluronic PE4300": BASF) Ultrapure water 79.4% by weight

The following constituent materials were mixed and stirred to obtain a black ink 2. C. I. Direct black 154 4.0% by weight (Solubility 8 g in water 100g at 20 ° C .; having a carboxylic acid group as a hydrophilic group) Diethylene glycol 10.0% by weight Sulfolane 5.0% by weight Propylene glycol monobutyl ether 5.0% by weight Interface Activator 0.1% by weight (polyoxyethylene oleyl ether: EO number 20 mol / molecule) Ultrapure water 75.9% by weight

The obtained cyan ink 2, magenta ink 2, yellow ink 2, and black ink 2 were evaluated in the same manner as in Example 1. (In Example 2, a black monochrome image was formed using black ink 2. Formed and evaluated similarly). Table 1 shows the evaluation results.

Comparative Example 1 The following constituent materials were mixed and stirred, sufficiently dissolved, and filtered under pressure using a 0.45 μm filter to obtain a cyan ink 3. C. I. Acid Blue 9 2.0% by weight (Solubility in 100g of water at 20 ° C: 23g; having a sulfonate group as a hydrophilic group) Glycerin 3.0% by weight Diethylene glycol 3.0% by weight Diethylene glycol monobutyl ether> 1.0% by weight 91.0% by weight of pure water

The following constituent materials were mixed and stirred, sufficiently dissolved, and then filtered under pressure using a 0.45 μm filter to obtain a magenta ink 3. C. I. Acid Red 52 3.0% by weight (Solubility in 100 g of water at 20 ° C .: 25 g; having a sulfonate group as a hydrophilic group) Glycerin 5.0% by weight Ethylene glycol 3.0% by weight 2.0% by weight sulfolane Surface activity Agent (“Olefin E1010”: Nissin Chemical Co., Ltd.) 1.0% by weight Ultrapure water 86.0% by weight

The following constituent materials were mixed and stirred, sufficiently dissolved, and then filtered under pressure using a 0.45 μm filter to obtain a yellow ink 3. C. I. Direct Yellow 132 3.0% by weight (8 g solubility in 100 g of water at 20 ° C .; having a carboxylic acid group as a hydrophilic group) Diethylene glycol 15.0% by weight Sulfolane 10.0% by weight Thiodiethanol 20.0% by weight Surfactant 1.0% by weight ("Pluronic PE4300": BASF) Ultrapure water 51.0% by weight

The following constituent materials were mixed and stirred to obtain a black ink 3. Cabojet 300 20.0% by weight (Carbon black amount 20% by weight) Diethylene glycol 10.0% by weight Sulfolane 10.0% by weight Isopropyl alcohol 2.0% by weight Polyoxyethylene oleyl ether 1.0% by weight (EO number) : 20 mol / 1 molecule) Ultrapure water 57.0% by weight

The obtained cyan ink 2, magenta ink 2, yellow ink 2, and black ink 2 were evaluated in the same manner as in Example 1. (In Example 2, a black monochrome image was formed using black ink 2. Formed and evaluated similarly). Table 1 shows the evaluation results.

[0077]

[Table 1]

[0078]

According to the present invention, it is possible to provide an ink jet recording ink for forming an image on a decorative sheet in which bleeding and color unevenness are less likely to occur in the image area. Also,
ADVANTAGE OF THE INVENTION According to this invention, the ink set for inkjet recording for image formation of the decoration sheet which reduced the bleeding which arises between the colors of an image part can be provided. Further, according to the present invention, it is possible to provide a method for producing a decorative sheet using ink jet recording, in which bleeding and color unevenness hardly occur in an image portion.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 FC02 2H086 BA02 BA53 BA56 BA62 4J039 BC06 BC07 BC09 BC13 BC35 BC36 BC50 BC54 BC55 BE03 BE04 BE06 BE12 CA03 EA15 EA16 EA17 EA42 EA47 FA02 GA24

Claims (3)

[Claims] 1. An ink jet recording ink used for forming an image on a decorative sheet, wherein a water-soluble dye having a solubility of ag in 100 g of water at 20 ° C. is b% by weight, and a water-soluble organic solvent is c% by weight. % And water,
And a, b, and c satisfy the following relational expression. a ≦ 205 ≦ c ≦ 302 2 ≦ {(a × c) / b} ≦ 100 2. An ink jet recording ink set comprising three types of color inks each containing magenta, yellow and cyan water-soluble dyes, wherein the color ink is the ink according to claim 1. Is an ink set for inkjet recording. 3. A decoration sheet manufacturing method in which energy is supplied to ink to discharge ink droplets to the surface of the sheet, and an image made of ink is recorded on the surface of the sheet to manufacture a decoration sheet. Wherein the contact angle of the ink on the surface of the sheet at 20 ° C. with the ink of claim 1 is 5;
A method for producing a decorative sheet used in a combination of at least 65 degrees and at most 65 degrees.