JP2019038117A - Image forming method, image forming apparatus, and method for manufacturing printed matter - Google Patents

Abstract

To provide an image forming method which is excellent in adhesion to a non-permeable base material and obtains high laminate strength.SOLUTION: An image forming method for forming an image on a non-permeable base material includes a step of imparting a composition for surface treatment containing water, a water-soluble organic solvent and urethane resin particles onto the non-permeable base material, a step of imparting non-site ink containing water, a water-soluble organic solvent and urethane resin particles thereto, and a step of imparting white ink containing water, a water-soluble organic solvent, urethane resin particles and a white coloring agent thereto.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an image forming method, an image forming apparatus, and a printed material manufacturing method.

  Inkjet printers have advantages such as low noise, low running cost, and easy color printing, and are widely used in general households as digital signal output devices. In recent years, not only for home use, but also, for example, a technique for forming an image on a packaging material such as food, beverages and daily necessities by ink jet has been developed.

  In Japan, non-absorbent printed materials such as plastic films (also referred to as non-permeable substrates and non-absorbent recording media) are used as printed materials to which ink jet is applied, and inks for that purpose have been developed. ing. An example of the need to directly print on such a plastic film by inkjet is, for example, the packaging printing application of food and daily necessities, and these applications are very high because there are many opportunities to see the printed matter at a close distance. Image quality is required.

Patent Document 1 discloses a technique in which a non-absorbable recording medium is applied in the order of a reaction liquid containing a flocculant and an ink containing a color material.
In addition, as is known from Patent Document 2, most of such packaging applications are printed with color ink on the back surface of a plastic film, and after printing white ink in order to improve concealability and color ink coloring, A packaging material in which an adhesive is applied on a printed layer and a heat-sealable film is laminated and laminated is generally used. In particular, in soft packaging applications, polypropylene (OPP), polyethylene terephthalate (PET), and nylon (ONY) are used in large amounts. In particular, polypropylene is the most used because it is inexpensive and has many excellent properties such as moldability, chemical resistance, and heat resistance.

  However, since polypropylene is a nonpolar and crystalline resin, water-based ink is easily repelled, it is difficult to make the ink layers adhere closely, and sufficient laminate strength cannot be obtained for laminating a plurality of ink layers. There is a problem.

  An object of this invention is to provide the image forming method which is excellent in the adhesiveness to a non-permeable base material, and can obtain high lamination strength.

  In order to solve the above problems, the present invention provides an image forming method for forming an image on a non-permeable substrate, wherein the surface treatment composition containing water, a water-soluble organic solvent, and urethane resin particles is used as the non-permeable material. A step of applying on a permeable substrate, a step of applying a non-white ink containing water, a water-soluble organic solvent and urethane resin particles, and a white color containing water, a water-soluble organic solvent, urethane resin particles and a white colorant. And a step of applying ink.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the adhesiveness to a non-permeable base material, and can provide the image forming method from which high laminate strength is obtained.

FIG. 7 is a perspective explanatory view of an example of a recording apparatus. It is a perspective explanatory view in an example of a main tank. It is a section explanatory view in an example of printed matter.

  Hereinafter, an image forming method, an image forming apparatus, and a printed material manufacturing method according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

  The present invention is an image forming method for forming an image on a non-permeable substrate, and a surface treatment composition containing water, a water-soluble organic solvent and urethane resin particles is applied to the non-permeable substrate. And a step of applying a non-white ink containing water, a water-soluble organic solvent and urethane resin particles, and a step of applying a white ink containing water, a water-soluble organic solvent, urethane resin particles and a white colorant. It is characterized by having.

By using a combination of the above-mentioned surface treatment composition, non-white ink, and white ink, excellent adhesion to a non-permeable substrate and high laminate strength can be obtained. This is because the urethane resin particles in the surface treatment composition have strong adhesion to the non-permeable substrate, and the non-white ink and the white ink also contain the urethane resin particles, thereby providing high adhesion between the ink layers. This is due to the fact that high laminate strength is obtained.
Details will be described below.

(Surface treatment composition)
The surface treatment composition contains water, a water-soluble organic solvent, and urethane resin particles, and may contain other components as necessary.

<Urethane resin particles>
When the composition for surface treatment contains urethane resin particles, high adhesion to the non-permeable substrate and the ink layer and high laminate strength can be obtained.
The polyurethane resin is a reactive product of polyisocyanate and polyol. A characteristic of the polyurethane resin is that it exhibits the performance of a soft segment made of a polyol component having a weak cohesive force and a hard segment made of a urethane bond having a strong cohesive force. The soft segment is soft and resistant to deformation of the base material such as stretching and bending. On the other hand, the hard segment has high adhesion to the substrate and is excellent in wear resistance.

Examples of the urethane resin include polyether-based urethane resin, polyester-based urethane resin, and polycarbonate-based urethane resin.
The type of urethane resin particles contained in the composition for surface treatment is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of adhesion and laminate strength intended by the present invention, polyisocyanate It is preferable to use a polyester-based urethane resin composed of polyester polyol.

  It is possible to obtain a surface treatment composition by mixing resin particles made of these resins with a material such as an organic solvent in a resin emulsion state in which water is used as a dispersion medium. As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used.

The glass transition temperature Tg of the urethane resin particles is preferably 25 ° C. or lower, and the lower limit is not particularly limited, but is preferably −30 ° C. or higher. When Tg is 25 ° C. or lower, the film-forming property of the resin is improved, and sufficient flexibility is ensured, so that the adhesion to the substrate becomes strong, which is preferable.
The Tg of the urethane resin particles can be measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku Corporation).

  The addition amount is preferably 0.5% by mass or more and 20% by mass or less as a solid content with respect to the total amount of the composition for surface treatment. When the content is 0.5% by mass or more, the resin can sufficiently cover the base material, so that the adhesion is improved. When the content is 20% by mass or less, the film thickness is not excessively increased, so that the adhesion is hardly lowered.

The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness. It is more preferably 200 nm or less and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-he Polyhydric alcohols such as sundiol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, ethylene glycol mono Polyhydric alcohol alkyl ethers such as ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as benzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- -Nitrogen-containing heterocyclic compounds such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, Amides such as N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, Examples thereof include ethylene carbonate.
In addition to functioning as a wetting agent, it is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because good drying properties can be obtained.

  The content of the organic solvent in the ink is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of the drying property and ejection reliability of the ink, 20 mass% or more and 60 mass% or less are more preferable.

  Further, when the surface treatment composition contains any one of 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol as the organic solvent, the film forming property of the resin is improved, Since adhesion improves, it is preferable.

<Water>
The water content in the surface treatment composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 90% by mass or less from the viewpoint of drying property and ejection reliability. 20 mass% to 60 mass% is more preferable.

<Multivalent metal salt>
The composition for surface treatment may contain a polyvalent metal salt. The polyvalent metal salt rapidly aggregates the pigment in the ink after landing, suppresses color bleeding, and improves color developability.

  Examples of the polyvalent metal compound include, but are not limited to, titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, and nickel. Examples thereof include compounds and salts thereof (polyvalent metal salts).

Among these polyvalent metal compounds, one or more selected from the group consisting of calcium compounds, magnesium compounds, and nickel compounds is preferable because pigments can be effectively aggregated, and alkaline earth metals such as calcium and magnesium are preferable. Is more preferable.
The polyvalent metal compound is preferably ionic. In particular, when the polyvalent metal compound is a calcium salt, the stability of the reaction solution becomes better.

Specific examples of the polyvalent metal compound include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, magnesium sulfate, barium sulfate, zinc sulfide, zinc carbonate, aluminum silicate, and calcium silicate. , Magnesium silicate, aluminum hydroxide and the like.
Among these, calcium acetate is preferable for the purpose of preventing the strength of the pre-coating layer (layer formed from the surface treatment composition) from deliquescent.

  When the concentration of the polyvalent metal ion relative to the entire surface treatment composition is 0.05 to 0.5 mol / kg, it is preferable because particularly excellent storage stability is obtained and color bleeding is suppressed. is there.

<Surfactant>
As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.
There is no restriction | limiting in particular in silicone type surfactant, According to the objective, it can select suitably. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as an aqueous surfactant. In addition, as the silicone surfactant, a polyether-modified silicone surfactant can be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylate. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.
Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
These may be used alone or in combination of two or more.

  The content of the surfactant in the surface treatment composition is not particularly limited and can be appropriately selected according to the purpose, but is excellent in wettability, ejection stability, and image quality is improved. 0.001 mass% or more and 5 mass% or less are preferable, and 0.05 mass% or more and 5 mass% or less are more preferable.

<Other additives>
Examples of other additives include antifoaming agents, antiseptic / antifungal agents, and rustproofing agents.

<<< antifoaming agent >>>
There is no restriction | limiting in particular as an antifoamer, For example, a silicone type antifoamer, a polyether type | system | group antifoamer, a fatty-acid ester type | system | group antifoamer etc. are mentioned. These may be used alone or in combination of two or more. Among these, a silicone type antifoaming agent is preferable from the viewpoint of excellent foam breaking effect.

<< antiseptic and antifungal agent >>
The antiseptic / antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<< rust preventive agent >>
There is no restriction | limiting in particular as a rust preventive agent, For example, acidic sulfite, sodium thiosulfate, etc. are mentioned.

(Non-white ink and white ink)
Next, the non-white ink and the white ink in the present invention will be described.
The non-white ink includes water, a water-soluble organic solvent, and urethane resin particles, and the white ink includes water, a water-soluble organic solvent, urethane resin particles, and a white colorant.
Hereinafter, unless otherwise specified, when “ink” is described, non-white ink and white ink are not distinguished from each other, and a description common to both is given.

<Urethane resin particles>
In particular, by adding urethane resin particles to the ink of the present invention, high adhesion between the surface treatment composition and the ink can be obtained. In general, polyester urethane resins are often used as adhesives for laminating. In this case, the inclusion of urethane resin in the ink improves compatibility with the adhesive, resulting in higher laminate strength. It is done.

  There is no restriction | limiting in particular as a kind of urethane resin particle contained in ink, According to the objective, it can select suitably. For example, what is mentioned by the composition for surface treatment can be used. From the viewpoint of adhesion to the surface treatment composition and compatibility with the laminating adhesive, it is preferable to use a polyester-based urethane resin composed of a polyisocyanate and a polyester polyol.

  As described above, it is preferable to use a polyester urethane resin also in the surface treatment composition, and it is more preferable that the urethane resin particles in the surface treatment composition and the ink are made of a polyester urethane resin. In this case, adhesion and laminate strength can be further improved.

The volume average particle size of the urethane resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 200 nm or less are more preferable, and 10 nm or more and 100 nm or less are particularly preferable.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

  The content of the urethane resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of fixability and ink storage stability, the content is 1% by mass or more and 30% by mass with respect to the total amount of ink. % Or less is preferable, and 5 mass% or more and 20 mass% or less are more preferable.

  As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used.

<Water, organic solvent>
The water and the organic solvent contained in the ink can have the same configuration as the above-described surface treatment composition.

<Colorant>
The standard of whiteness of white ink is ISO-2469 (JIS-8148). Generally, when the value is 70 or more, it is used as a white colorant.
White particles having a hollow structure may be used for the white ink, and examples of the white particles having a hollow structure include hollow resin particles and inorganic hollow particles.

  Examples of the resin composition of the hollow resin particles include acrylic resins, styrene-acrylic resins, acrylic resins such as cross-linked styrene-acrylic resins, urethane resins, maleic resins, and the like.

  Examples of the material of the inorganic hollow particles include white oxides of metals such as silicon, aluminum, titanium, strontium, and zirconium, nitrides, oxynitrides, and various inorganic compounds such as glass and silica.

  Examples of the non-white ink include color ink, black ink, gray ink, clear ink, and metallic ink. The clear ink means an ink that does not contain a colorant and mainly comprises resin particles, an organic solvent, and water.

  Examples of the color ink include cyan ink, magenta ink, yellow ink, light cyan ink, light magenta ink, red ink, green ink, blue ink, orange ink, and violet ink.

  The non-white ink may contain a colorant other than white, and the colorant used in the non-white ink is not particularly limited as long as it exhibits a non-white color, and is appropriately selected according to the purpose. And dyes and pigments. These may be used alone or in combination of two or more.

  Among these, a pigment is preferable. Examples of the pigment include inorganic pigments and organic pigments.

As the inorganic pigment, for example, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, it is manufactured by a known method such as a contact method, a furnace method, or a thermal method. And carbon black. These may be used individually by 1 type and may use 2 or more types together.
Of these pigments, those having good affinity with the solvent are preferably used.
In addition, hollow resin particles and inorganic hollow particles can also be used in non-white ink.

  As the pigment, for black, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11) And organic pigments such as aniline black (CI Pigment Black 1). These may be used individually by 1 type and may use 2 or more types together.

  For color, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155; I. Pigment orange 5, 13, 16, 17, 36, 43, 51; C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; I. Acid Red 52, 80, 82, 249, 254, 289; I. Acid Blue 9, 45, 249; C.I. I. Acid Black 1, 2, 24, 94; C.I. I. Food black 1, 2; I. Direct yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173; I. Direct Red 1, 4, 9, 80, 81, 225, 227; I. Direct blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202; I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195; I. Reactive red 14, 32, 55, 79, 249; I. Reactive black 3, 4, 35 etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the colorant used for the metallic ink include fine powder obtained by finely pulverizing a metal simple substance, an alloy, or a metal compound. More specifically, it consists of any one or more of a group of simple metals consisting of aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, silicon, copper, or platinum, Alternatively, an alloy obtained by combining these groups of metals may be used. Moreover, what is obtained by finely pulverizing any one or a plurality of oxides, nitrides, sulfides, and carbides of the group of simple metals or alloys thereof.

  The content of the colorant in the ink is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass from the viewpoints of improvement in image density, good fixability and ejection stability. It is as follows.

<< Pigment dispersion >>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the colorant. Further, it is also possible to produce an ink by mixing a pigment, other water, a dispersant, and the like into a pigment dispersion and mixing a material such as water or an organic solvent.

In order to obtain an ink by dispersing a pigment, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing, a dispersing agent is used. Method, etc.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of making it dispersible in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon) Is mentioned.
As a method for coating the surface of the pigment with a resin and dispersing it, a method in which the pigment is included in microcapsules and dispersible in water can be mentioned. This can be paraphrased as a resin-coated pigment. In this case, it is not necessary that all pigments blended in the ink are coated with a resin, and within a range where the effects of the present invention are not impaired, uncoated pigments and partially coated pigments are dispersed in the ink. It may be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant or high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and naphthalenesulfonic acid Na formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

The pigment dispersion can be obtained by dispersing water, a pigment, a pigment dispersant, and other components as required, and adjusting the particle size. For dispersion, a disperser may be used.
The particle size of the pigment in the pigment dispersion is not particularly limited, but for the non-white pigment in the non-white ink, the dispersion stability of the pigment is good, and the image quality such as ejection stability and image density is also high. The volume average particle size is preferably 30 to 110 nm.
Moreover, it is preferable that the average volume particle diameter is 200-1000 nm about the hollow resin particle in a white ink from the point from which high dispersion stability and high whiteness are obtained. About an inorganic hollow particle, it is preferable that an average volume particle diameter is 10-200 nm from the point from which high dispersion stability and high whiteness are obtained.
The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

  The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1% by mass. % To 50% by mass is preferable, and 0.1% to 30% by mass is more preferable.

  The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

<Other ingredients>
As in the case of the surface treatment composition, the ink in the present invention may contain a surfactant, other additives and the like as necessary, and the specific examples described in the surface treatment composition can be used.

<Example of ink production method>
The ink in the present invention is produced, for example, by dispersing or dissolving the above-described constituents in an aqueous medium, and further stirring and mixing as necessary. The stirring and mixing can be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like.

<Ink physical properties>
There is no restriction | limiting in particular as a physical property of an ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, pH, etc. are the following ranges.
The viscosity at 25 ° C. of the ink is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less from the viewpoint of improving the printing density and character quality and obtaining good discharge properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. Measurement conditions are 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample liquid amount 1.2 mL, rotation speed 50 rpm, and measurement is possible for 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12 and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

(recoding media)
The recording medium (sometimes referred to as a base material) used in the present invention can be used without any particular limitation, and can be plain paper, glossy paper, special paper, cloth, etc. Can be used particularly preferably.
The non-permeable base material in the present invention refers to a base material having a surface having low water permeability, absorbability and / or adsorptivity, and is a material which does not open to the outside even if there are many cavities inside. Is also included. More quantitatively, it refers to a base material having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.

  Among the non-permeable substrates, particularly good adhesion to a resin film such as a polypropylene film (OPP film), a polyethylene terephthalate film (PET film), a nylon film (ONY film) is obtained.

Examples of the polypropylene film include Toyobo P-2002, P-2161, P-4166, SUNTOX PA-20, PA-30, PA-20W, Futamura Chemical FOA, FOS, FOR, and the like. It is done.
Examples of the polyethylene terephthalate film include Toyobo E-5100 and E-5102, Toray P60 and P375, Teijin DuPont Films G2, G2P2, K, and SL.
Examples of the nylon film include Harden films N-1100, N-1102, and N-1200 manufactured by Toyobo Co., Ltd., ON, NX, MS, and NK manufactured by Unitika.

(Image forming method and image forming method)
The image forming method of the present invention is an image forming method for forming an image on a non-permeable substrate, wherein the composition for surface treatment containing water, a water-soluble organic solvent and urethane resin particles is used as the non-permeable substrate. A step of applying on top, a step of applying a non-white ink containing water, a water-soluble organic solvent and urethane resin particles, and a white ink containing water, a water-soluble organic solvent, urethane resin particles and a white colorant. And a process.

  The image forming apparatus of the present invention is an image forming apparatus for forming an image on a non-permeable substrate, and the surface treatment composition containing water, a water-soluble organic solvent and urethane resin particles is used as the non-permeable substrate. A means for applying on, a means for applying a non-white ink containing water, a water-soluble organic solvent and urethane resin particles, and a white ink containing water, a water-soluble organic solvent, urethane resin particles and a white colorant And means.

  As the surface treatment composition, non-white ink, and white ink, those described above can be used. Further, the method for applying the surface treatment composition, the non-white ink, and the white ink is not particularly limited and can be appropriately changed, but an ink jet recording method is preferably used. Besides the ink jet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method and the like can be mentioned.

  The image forming method of the present invention preferably includes a step of modifying the surface of the non-permeable substrate (surface modification step). By performing the surface modification step, unevenness when the surface treatment composition is applied to the non-permeable substrate can be suppressed, and adhesion can be further improved.

  Examples of the surface modification include corona discharge treatment, streamer discharge treatment, atmospheric pressure plasma treatment, flame treatment, and ultraviolet irradiation treatment. These treatment methods can be carried out using a known apparatus.

  Among the above treatment methods, corona discharge treatment and streamer discharge treatment are preferable. These are preferably used because they are superior in discharge output stability compared to atmospheric pressure plasma treatment, flame treatment and ultraviolet irradiation treatment, and can perform surface treatment uniformly on the recording surface.

  In the image forming method of the present invention, it is preferable to perform the heat treatment after applying the ink. By performing the heat treatment, the residual solvent in the ink coating film is reduced, and the adhesion can be further improved.

  That is, the image forming method of the present invention includes a heat treatment step (1) in which heat treatment is performed after applying the non-white ink, and a heat treatment step (2) in which heat treatment is performed after the white ink is applied. Preferably it is. It is more preferable to have both the heat treatment step (1) and the heat treatment step (2), but the above effect can be expected even with either one.

  The heating temperature in the heat treatment step is not particularly limited and can be appropriately changed. For example, 50 to 130 ° C. is preferable. In addition, the heating time in the heat treatment step is not particularly limited and can be appropriately changed. For example, 1 to 120 seconds is preferable, and 1 to 30 seconds is more preferable.

The image forming method of the present invention is suitably used for various recording apparatuses using an ink jet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier complex machine, and a three-dimensional modeling apparatus.
In the present invention, the recording apparatus and the recording method are an apparatus capable of ejecting ink, various treatment liquids, and the like to a recording medium, and a method of performing recording using the apparatus. The recording medium means a medium on which ink or various processing liquids can be temporarily attached.
The recording apparatus can include not only a head portion that ejects ink but also means for feeding, transporting, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, a means for heating and drying the printing surface and the back surface of the recording medium. Although it does not specifically limit as a heating means and a drying means, For example, a warm air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, what forms patterns, such as a geometric pattern, etc. includes what forms a three-dimensional image.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise specified.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, for example, a continuous paper wound up in a roll shape as a recording medium. Also included are continuous paper printers.
An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective view of the apparatus. FIG. 2 is an explanatory perspective view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial type image forming apparatus. A mechanism unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), yellow (Y) is packaged, for example, an aluminum laminate film It is formed by a member. The ink storage unit 411 is stored in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. Thus, the ink discharge ports 413 of the main tank 410 and the discharge heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and ink can be discharged from the discharge heads 434 to the recording medium.

The recording apparatus can include not only a portion that ejects ink but also a device called a pre-processing device or a post-processing device. The composition for surface treatment may be applied using a pretreatment device, and the white ink may be applied using a posttreatment device.
As one mode of the pretreatment device and the posttreatment device, as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y), a pretreatment liquid and a posttreatment liquid are included. There is a mode in which a liquid container and a liquid discharge head are added, and a pretreatment liquid and a posttreatment liquid are discharged by an ink jet recording method.
As another aspect of the pretreatment apparatus and the posttreatment apparatus, there is an aspect in which, for example, a pretreatment apparatus or a posttreatment apparatus other than the ink jet recording method is provided by a blade coating method, a roll coating method, or a spray coating method.

(Method for producing printed matter and printed matter)
The method for producing a printed matter of the present invention is a method for producing a printed matter in which an image is formed on a non-permeable substrate, wherein the composition for surface treatment containing water, a water-soluble organic solvent and urethane resin particles is used for the non-penetrating method. White ink containing water, water-soluble organic solvent, urethane resin particles, and white colorant And a step of imparting.

  FIG. 3 shows a cross-sectional view of an example of the printed material in the present invention. In the printed material in the present embodiment, a pre-coating layer 2, a non-white ink layer 3, and a white ink layer 4 are formed in this order on a substrate 1. The pre-coat layer 2 is a layer made of the surface treatment composition, the non-white ink layer 3 is a layer made of the non-white ink, and the white ink layer 4 is a layer made of the white ink.

  In the printed matter of the present embodiment, the thickness of each layer is not particularly limited, and can be changed as appropriate. For example, the pre-coating layer 2 is preferably 0.1 to 0.5 μm, the non-white ink layer 3 is preferably 0.5 to 3 μm, and the white ink layer 4 is preferably 1 to 4 μm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. In the examples, “part” represents “part by mass”, and “%” represents “% by mass” unless otherwise specified.

(Preparation of urethane resin particle emulsion)
<Preparation of polyester urethane resin emulsion A>
In a reaction vessel into which a stirrer, a reflux condenser, and a thermometer were inserted, 1,500 g of polylite OD-X-2420 (manufactured by DIC, polyester polyol), 220 g of 2,2-dimethylolpropionic acid (DMPA), and N -1,347 g of methylpyrrolidone (NMP) was charged in a nitrogen atmosphere and heated to 60 ° C to dissolve DMPA.
Next, 1,445 g of 4,4′-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) are added and heated to 90 ° C., and a urethanization reaction is performed over 5 hours. Obtained. The reaction mixture was cooled to 80 ° C., and 4,340 g was extracted from the mixture in which 149 g of triethylamine was added and mixed, and added to a mixed solution of 5,400 g of water and 15 g of triethylamine with vigorous stirring.
Next, 1,500 g of ice was added, and 626 g of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction, and the solvent was distilled off so that the solid content concentration became 30% by mass. The resin emulsion thus obtained was dispersed with a paint conditioner (manufactured by Red Devil Corp., speed adjustable within the range of 50 to 1,425 rpm), and a polyester-based urethane resin emulsion having a solid content concentration of 40.0% by mass and Tg of 10 ° C. A was obtained.
In addition, Tg was measured by DSC (Thermo plus Thermo plus EVO2 / DSC).

<Preparation of polyester urethane resin emulsion B>
As polyester urethane resin emulsion B, Superflex 210 (Daiichi Kogyo Seiyaku Co., Ltd., Tg 41 ° C.) was used.

<Preparation of polyether-based urethane resin emulsion C>
In the preparation of the polyester-based urethane resin emulsion A, instead of using Polylite OD-X-2420, the solid content concentration is the same except that it is changed to Hiflex D2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyether polyol). A polyether urethane resin emulsion C having a mass of 30% by mass and a Tg of 18 ° C. was obtained.

<Preparation of polycarbonate urethane resin emulsion D>
In a simple pressure reactor equipped with a stirrer and a heater, 287.9 parts of crystalline polycarbonate diol of Mn 2,000 (Duranol T6002, manufactured by Asahi Kasei Chemicals), 3.6 parts of 1,4-butanediol, DMPA 8. 9 parts, 98.3 parts hydrogenated MDI (diphenylmethane diisocyanate) and 326.2 parts acetone were charged while introducing nitrogen.
Then, it heated at 90 degreeC and urethanation reaction was performed over 8 hours, and the prepolymer was manufactured. After cooling the reaction mixture to 40 ° C., 6.8 parts of triethylamine was added and mixed, and further 568.8 parts of water was added and emulsified with a rotor-stator type mechanical emulsifier to obtain an aqueous dispersion. . 28.1 parts of 10% ethylenediamine aqueous solution was added to the obtained aqueous dispersion with stirring, and the mixture was stirred at 50 ° C. for 5 hours to carry out chain elongation reaction.
Thereafter, acetone was removed at 65 ° C. under reduced pressure, and the water content was adjusted to obtain a polycarbonate urethane resin emulsion D having a solid concentration of 40% by mass and Tg-20 ° C.

(Preparation of acrylic resin emulsion)
<Preparation of acrylic resin emulsion E>
As the acrylic resin emulsion E, Boncoat CF-6140 (manufactured by DIC, Tg 12 ° C.) was used.

(Preparation of composition for surface treatment)
<Surface Treatment Composition Preparation Example 1>
After mixing with the following formulation, the mixture was stirred and filtered through a 5 μm filter (Sartorius Mini-Salto) to obtain the composition for surface treatment of Composition Preparation Example 1 for surface treatment.

1,2-propanediol 10 parts Emulgen LS-106 (surfactant manufactured by Kao Corporation) 1 part calcium acetate monohydrate 1.76 parts polyester-based urethane resin emulsion A (as solids) 10 parts Proxel LV (Avicia) Preservative) 0.1 part Ion-exchanged water 77.14 parts

<Surface Treatment Composition Preparation Examples 2-7>
Surface treatment compositions of Surface Preparation Composition Preparation Examples 2 to 7 were obtained in the same manner as in Surface Treatment Composition Preparation Example 1 with the formulation shown in Table 1.

  In Table 1, the contents of emulsions A to E represent solid contents.

(Preparation of ink)
<Preparation of pigment dispersion>
<< Preparation of Black Pigment Dispersion >>
Carbon black manufactured by Tokai Carbon Co., Ltd .: 100 g of Seast SP (SRF-LS) is added to 3000 mL of 2.5N (standard) sodium hypochlorite solution, stirred at a temperature of 60 ° C. and a speed of 300 rpm, and allowed to react for 10 hours. Then, an oxidation treatment was performed to obtain a pigment having a carboxylic acid group added to the surface of carbon black.
The reaction solution was filtered, and the carbon black separated by filtration was neutralized with a sodium hydroxide solution and subjected to ultrafiltration.
Subsequently, ultrafiltration using a dialysis membrane is performed using the pigment dispersion and ion-exchanged water, and further, ultrasonic dispersion is performed to concentrate the pigment solid content to 20%. Got.

<< Preparation of Cyan Pigment Dispersion >>
In the preparation of the black dispersion, cyan having a volume average particle diameter of 75 nm was similarly used except that the color material used was changed to a copper phthalocyanine pigment (CI Pigment Blue 15: 4, trade name: LX4033) manufactured by Toyo Ink Co., Ltd. A pigment dispersion was obtained.

<< Preparation of magenta pigment dispersion >>
In the preparation of the black dispersion, a magenta pigment dispersion having a volume average particle diameter of 73 nm was obtained in the same manner except that Pigment Red 122 manufactured by Sun Chemical was used.

<< Preparation of Yellow Pigment Dispersion >>
In the preparation of the black dispersion, a yellow pigment dispersion having a volume average particle diameter of 82 nm was similarly obtained except that the color material used was changed to a yellow pigment (Pigment Yellow 74, trade name: Yellow No. 46) manufactured by Dainichi Seika Kogyo Co., Ltd. Got the body.

<< Preparation of white pigment dispersion >>
25 g of titanium oxide STR-100W (manufactured by Sakai Chemical Industry Co., Ltd.), 5 g of pigment dispersant TEGO Dispers 651 (manufactured by Evonik) and 70 g of water are mixed, and 0.3 mmΦ in a bead mill (Research Lab, manufactured by Shinmaru Enterprises Co., Ltd.). Zirconia beads were dispersed at a filling rate of 60% and 8 m / s for 5 minutes to obtain a white pigment dispersion having a volume average particle size of 285 nm.

<Ink preparation method>
The ink was prepared by mixing and stirring according to the formulations described in Tables 2 and 3, and filtering the non-white ink through a 0.2 μm polypropylene filter and the white ink through a 0.5 μm polypropylene filter. In addition, FS-300 (DuPont fluorine-type surfactant) was used for surfactant.

  In Tables 2 and 3, the content of the pigment dispersion and the content of the emulsions A to E represent the solid content.

Example 1
As shown in Table 4, the following evaluation was performed using the surface treatment composition, non-white ink, and white ink.

<Print part adhesion evaluation>
Non-white ink and white ink are filled in an inkjet printer (IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), and the surface is pre-corona-treated with OPP film (Toyobo Pylen P2102), PET film (Toyobo Spet E5100), ONY film ( For the Harden N1100 manufactured by Toyobo Co., Ltd. After the surface treatment composition was applied and dried in step 1, a non-white ink solid image was printed and dried at 80 ° C. for 2 minutes. Thereafter, a white ink solid image was similarly printed on the non-white ink solid image and dried at 80 ° C. for 2 minutes. The solid part of the printed image was subjected to a cross-cut peel test using a cloth adhesive tape (123LW-50 manufactured by Nichiban Co., Ltd.), and evaluated according to the following criteria. The range up to B is an allowable range.
[Evaluation criteria]
A: No peeling is observed in any of the 100 squares.
B: Some of the 100 squares were peeled off by 1 or more and 5 or less.
C: Some of the 100 cells are peeled off by 6 or more.

<Lamination strength evaluation>
In the same manner as the evaluation of the adhesion of the printed part, a non-white ink solid image and a white ink solid image are printed on the OPP film, PET film, and ONY film, and the adhesive for dry lamination (main agent TM-320 / curing agent CAT- 13B (manufactured by Toyo Morton Co., Ltd.) was applied with a bar coater, and CPP (Pyrene P1128 manufactured by Toyobo Co., Ltd.) was bonded thereto, followed by aging at 40 ° C for 48 hours. After the obtained printed material was cut into a width of 15 mm, the peel strength was measured by T-type peeling (peeling speed: 300 mm / min). Evaluation was made according to the following criteria. The range up to B is an allowable range.
[Evaluation criteria]
A: A strength of 3 N / 15 mm or more and less than 5 N / 15 mm is obtained.
B: Strength of 1N / 15mm or more and less than 3N / 15mm is obtained.
C: Only strength of less than 1 N / 15 mm can be obtained.

(Examples 2 to 11)
In Example 1, evaluation was performed in the same manner except that the surface treatment composition, the non-white ink, and the white ink were changed as shown in Tables 4 and 5.

(Example 12)
In Example 1, each film was evaluated in the same manner except that the corona treatment was not performed.

(Example 13)
In Example 1, the evaluation was performed in the same manner except that the heat treatment was not performed after the non-white ink printing.

(Example 14)
In Example 1, the evaluation was performed in the same manner except that the heat treatment was not performed after printing the white ink.

(Comparative Examples 1-3)
In Example 1, evaluation was performed in the same manner except that the surface treatment composition, the non-white ink, and the white ink were changed as shown in Table 6.

(Comparative Example 4)
In Comparative Example 1, the evaluation was performed in the same manner except that the surface treatment composition was not applied.

  In Tables 4 to 6, the heat treatment (1) represents the heat treatment after the non-white ink printing, and the heat treatment (2) represents the heat treatment after the white ink printing.

  Examples 1 to 4 are preferred examples of the present invention, and the adhesiveness and laminate strength were evaluated as A for all the substrates.

  Examples 5 to 8 are examples in which the surface treatment composition, the non-white ink, and the urethane resin particles in the white ink are not polyester urethane resins. In Examples 5 and 6, since the urethane resin particles in the ink are not ester-based, the affinity with the adhesive is not sufficient, and the laminate strength is lowered. However, since it is B evaluation, it can be said that there is no problem in use. In Examples 7 and 8, since the urethane resin particles in the surface treatment composition are not ester-based, adhesion with the OPP film is not sufficient, and thus the adhesion is evaluated as B, but it can be said that there is no problem in use.

  Example 9 is an example where the Tg of the urethane resin particles in the surface treatment composition is greater than 25 ° C. In Example 9, since the Tg is high, the film formation is not sufficient, and the adhesion and laminate strength of the OPP film are evaluated as B, but it can be said that there is no problem in use.

  Examples 10 and 11 are examples in which the content of the urethane resin in the surface treatment composition deviates from 0.5 mass% to 20 mass% with respect to the surface treatment composition. Since the amount of urethane resin particles in the composition for surface treatment of Example 10 is small, the film is not sufficiently covered, and the amount of urethane resin particles in Example 11 is large, so that the film thickness is too thick and the adhesion, Although the laminate strength has decreased, it can be said that it is at a level that does not cause any problems in use because it is evaluated as B.

  Example 12 is an example in which the surface modification treatment of the substrate is not performed. In this case, unevenness at the time of coating the surface treatment composition occurs, and since there is no function to increase the adhesion, the laminate strength is lowered. However, since it is B evaluation, it can be said that there is no problem in use.

  Examples 13 and 14 are examples in which no heat treatment is performed after ink printing. When the heat treatment is not performed after ink printing, the effect of the resin in the ink does not progress rapidly, and thus the adhesion and the laminate strength are lowered. However, since it is B evaluation, it can be said that there is no problem in use.

  Comparative Examples 1 to 3 are examples in which the resin in the surface treatment composition, the non-white ink, and the white ink is not a urethane resin. Moreover, the comparative example 4 is an example when not providing the composition for surface treatment. Comparative examples 1-4 are C evaluation by evaluation of adhesiveness and laminate strength, and it turns out that sufficient adhesiveness to three types of base materials of OPP, PET, and ONY cannot be secured.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Pre-coating layer 3 Non-white ink layer 4 White ink layer 400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y Black (K), cyan (C), magenta (M), yellow (Y) main tanks for each color 411 ink storage portion 413 ink discharge port 414 storage container case 420 mechanism portion 434 discharge head 436 supply tube

JP2015-71738A JP 2008-246837 A

Claims (8)

An image forming method for forming an image on a non-permeable substrate,
Providing a surface treatment composition comprising water, a water-soluble organic solvent and urethane resin particles on the non-permeable substrate;
Providing a non-white ink containing water, water-soluble organic solvent and urethane resin particles;
And a step of applying a white ink containing water, a water-soluble organic solvent, urethane resin particles, and a white colorant.   The image forming method according to claim 1, wherein the urethane resin particles contained in the surface treatment composition, the non-white ink, and the white ink are made of a polyester-based urethane resin.   3. The image forming method according to claim 1, wherein the urethane resin particles contained in the surface treatment composition have a glass transition temperature Tg of 25 ° C. or lower.   The urethane resin particle contained in the said composition for surface treatment is 0.5-20 mass% with respect to the said composition for surface treatment, The image formation in any one of Claims 1-3 characterized by the above-mentioned. Method.   The image forming method according to claim 1, further comprising a step of modifying the surface of the non-permeable substrate.   The image forming method according to claim 1, wherein the non-permeable substrate is a resin film. An image forming apparatus for forming an image on a non-permeable substrate,
Means for applying a surface treatment composition comprising water, a water-soluble organic solvent and urethane resin particles on the non-permeable substrate;
Means for applying a non-white ink comprising water, a water-soluble organic solvent and urethane resin particles;
An image forming apparatus comprising: a white ink containing water, a water-soluble organic solvent, urethane resin particles, and a white colorant. A method for producing a printed material having an image formed on a non-permeable substrate,
Providing a surface treatment composition comprising water, a water-soluble organic solvent and urethane resin particles on the non-permeable substrate;
Providing a non-white ink containing water, water-soluble organic solvent and urethane resin particles;
And a step of applying a white ink containing water, a water-soluble organic solvent, urethane resin particles and a white colorant.