JP2015131928A - Near-infrared curing composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared curing composition which is used as an ink or paint and which contains a near-infrared absorbent having sufficient near-infrared absorbency, excellent transparency, and little effect on a color tone.SOLUTION: The near-infrared curing composition contains at least one component selected from a resin and a polymerizable compound, and contains a near-infrared absorbent that contains at least a phosphonic copper salt represented in general formula (1) [In the formula, Ris a monovalent group represented by -CHCH-R, and Ris a hydrogen atom, an alkyl group or a fluorinated alkyl group]. The composition is used as an ink or paint.

Description

  The present invention relates to a near-infrared curable composition and use thereof, and particularly relates to a near-infrared curable composition used as an ink or a paint and use thereof.

In recent years, ultraviolet curable inks and ultraviolet curable paints that are cured by irradiating ultraviolet rays are used as inks and paints (see, for example, Patent Documents 1 and 2).
Ultraviolet curable inks and paints can be printed and applied without heating, and have been put to practical use in many fields in recent years.

However, ultraviolet curable inks and paints are highly dependent on the film thickness and color of the curing rate, and improvement has been desired.
In addition, when a composition that undergoes radical polymerization by ultraviolet irradiation is used as an ultraviolet curable ink or paint, polymerization (curing) is inhibited in the presence of oxygen, and cationic polymerization is performed by ultraviolet irradiation. When the composition is used, there is a problem that a strong acid is generated during the polymerization. In general, an ultraviolet absorber is used to increase the light resistance of the printed surface and the coated surface. However, when an ultraviolet absorber is used in an ultraviolet curable ink or paint, curing by ultraviolet irradiation is inhibited. There was a problem.

In order to solve these problems, near-infrared curable inks and paints that are cured by irradiation with near-infrared rays instead of ultraviolet rays have been proposed (for example, see Patent Document 3).
Near-infrared curable inks and paints generally contain near-infrared absorbers, but they have sufficient near-infrared absorptivity and have little effect on color tone when incorporated in inks or paints. Near-infrared curable inks and paints using an absorber are not known, and improvements have been desired.

  In addition, it has been proposed to use a specific tungsten oxide in order to increase the heat input amount of near infrared rays (see, for example, Patent Document 4).

JP 2009-57548 A JP 2012-140516 A Special table 2007-526379 Special table 2011-503274 gazette

  An object of this invention is to provide the near-infrared curable composition used as an ink or a coating material containing the near-infrared absorber which has sufficient near-infrared absorptivity and is excellent in transparency.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a near-infrared curable composition containing a near-infrared absorber containing a specific copper salt has a near-infrared absorber containing the specific copper salt. The present invention was completed by finding out that it can be suitably used as an ink or a paint because of its excellent transparency.

  That is, the near-infrared curable composition used as the ink or paint of the present invention becomes a polymer by polymerizing with a near-infrared absorber containing at least a phosphonic acid copper salt represented by the following general formula (1). And at least one component selected from compounds.

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. ]
The laminate of the present invention can be obtained by printing or coating the near infrared curable composition on a substrate, and then irradiating the near infrared curable composition with near infrared to cure.

  The three-dimensional modeled object of the present invention is obtained by injecting and curing the near-infrared curable composition by an optical modeling method using near-infrared rays.

  Since the near-infrared curable composition of the present invention contains a near-infrared absorbent having sufficient near-infrared absorptivity and excellent transparency, it is used as an ink or a paint.

6 is a transmission light spectrum of the laminate obtained in Example 7.

Next, the present invention will be specifically described.
The near-infrared curable composition of the present invention is at least one selected from a near-infrared absorber containing at least a phosphonic acid copper salt represented by the following general formula (1), a resin and a compound that becomes a polymer by polymerization. And used as ink or paint.

[Near-infrared absorber containing at least phosphonic acid copper salt represented by general formula (1)]
The near-infrared curable composition of this invention contains the near-infrared absorber containing the phosphonic acid copper salt represented by following General formula (1) at least.

  In the present invention, the near-infrared absorber containing at least the phosphonic acid copper salt represented by the following general formula (1) is also simply referred to as a near-infrared absorber.

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. ]
R ¹¹ in the general formula (1) is hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, etc. Is mentioned.

When manufacturing the near-infrared absorbing agent, wherein R ¹¹ is a large group of carbon number in the general formula (1), if it is long based molecular chain, because the dispersibility tends to decrease, as R ¹¹ Is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms.

  The near-infrared absorber used in the present invention contains at least the phosphonic acid copper salt represented by the general formula (1), and consists of only the phosphonic acid copper salt represented by the general formula (1). The near-infrared absorber which consists of a phosphonic acid copper salt represented by General formula (1) and another component may be sufficient.

  As the near-infrared absorber composed of the phosphonic acid copper salt represented by the general formula (1) and other components, for example, a dispersant is used in the production of the phosphonic acid copper salt represented by the general formula (1). A near-infrared absorber comprising a phosphonic acid copper salt represented by the general formula (1) and a dispersant, a fine particle comprising the phosphonic acid copper salt represented by the general formula (1), or a general formula (1) A near-infrared absorber in which fine particles comprising a phosphonic acid copper salt and a dispersant are coated with a resin, a fine particle comprising a phosphonic acid copper salt represented by the general formula (1), or a general formula (1) A near-infrared absorber in which fine particles comprising a phosphonic acid copper salt and a dispersant are coated with polysiloxane can be used. In addition, the near-infrared absorber coat | covered with the said resin or polysiloxane is also described as the near-infrared absorber consisting of the coated phosphonic acid copper salt. The near-infrared absorber composed of a coated phosphonic acid copper salt is at least one selected from a resin and a compound that becomes a polymer by polymerization because the phosphonic acid copper salt is covered with a resin or polysiloxane. It is possible to suppress the influence of components and other components on the phosphonic acid copper salt. For this reason, when using the component reactive with the phosphonic acid copper salt represented by General formula (1) as at least 1 type of component selected from resin and the compound which becomes a polymer by superposing | polymerizing, and another component It is preferable to use a near-infrared absorber made of a coated phosphonic acid copper salt.

The manufacturing method of the near-infrared absorber used for this invention is demonstrated below.
When the near-infrared absorber used in the present invention is other than a near-infrared absorber composed of a coated phosphonic acid copper salt, that is, a near-infrared absorber composed of an uncoated phosphonic acid copper salt, for example, the general formula (1 In the case of a near-infrared absorber comprising a phosphonic acid copper salt represented by formula (1), and a near-infrared absorber comprising a phosphonic acid copper salt represented by formula (1) and a dispersant, for example, it is produced by the following method. be able to.

As a method for producing the phosphonic acid copper salt represented by the general formula (1), a phosphonic acid compound represented by the following general formula (2) and a copper salt described later are preferably present in a solvent in a solvent. Mixing to obtain a reaction mixture (hereinafter also referred to as reaction step), removing a solvent in the reaction mixture to obtain fine particles of phosphonic acid copper salt (hereinafter also referred to as solvent removal step)
The method which has this is mentioned.

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. ]
R ¹¹ in the phosphonic acid compound represented by the general formula (2) is the same as R ¹¹ in the above general formula (1).

In addition, as a phosphonic acid compound represented by General formula (2), it may be used individually by 1 type, or 2 or more types may be used.
As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. The copper salt may be a copper salt other than the phosphonic acid copper salt represented by the general formula (1). Examples of the copper salt include copper of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous ethyl acetoacetate copper, anhydrous pyrophosphate, anhydrous naphthenic acid copper, and anhydrous copper citrate. Salt, hydrate or hydrate of copper salt of organic acid; copper salt of inorganic acid such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, hydrate of copper salt of inorganic acid Or a hydrate; copper hydroxide is mentioned. In addition, as a copper salt, you may use individually by 1 type, or may use 2 or more types.

As the copper salt, anhydrous copper acetate and copper acetate monohydrate are preferably used from the viewpoint of solubility and removal of by-products.
In producing the phosphonic acid copper salt represented by the general formula (1), a dispersant is preferably used. It is preferable to use a dispersant because the dispersibility of the phosphonic acid copper salt represented by the general formula (1) is improved. Examples of the dispersant include a phosphate ester compound, for example, at least one selected from a phosphate ester compound represented by the general formula (3a) and a phosphate ester compound represented by the general formula (3b). Examples thereof include a phosphoric acid ester compound, phosphoric acid in the phosphoric acid ester compound, that is, a compound obtained by neutralizing a hydroxyl group with a base. Examples of the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, and calcium hydroxide.

[Wherein R ²¹ , R ²² and R ²³ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ⁵ , n is an integer of 4 to 65, and R ⁵ is An alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms is shown. However, R ²¹ , R ²² and R ²³ may be the same or different. ]
In at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b), R ²¹ , R ²² and R ²³ is a monovalent group (polyoxyalkyl group) represented by — (CH ₂ CH ₂ O) _n R ⁵ . n is an integer of 4 to 65, and more preferably an integer of 6 to 45. When n is less than 4, when a near-infrared curable composition of the present invention is used to obtain a laminate or a three-dimensional modeled object, the near-infrared absorber affects the color tone of the near-infrared curable composition. May give. On the other hand, if n exceeds 65, the amount of the phosphoric acid ester compound necessary to prevent the near-infrared absorber from affecting the color tone of the near-infrared curable composition increases, resulting in high costs. There is.

R ⁵ is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms, and is an alkyl group having 12 to 20 carbon atoms. Is more preferable. When R ⁵ is a group having less than 6 carbon atoms, the near-infrared absorber may affect the color tone of the near-infrared curable composition. In addition, when R ⁵ is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound necessary for preventing the near-infrared absorber from affecting the color tone of the near-infrared curable composition increases. It causes high cost.

  When obtaining the phosphonic acid copper salt represented by the general formula (1), the phosphoric acid ester compound represented by the general formula (3a) and the phosphoric acid ester compound represented by the general formula (3b) Although at least one is preferably used, it is more preferable to use both the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b).

  When the phosphoric acid ester compound represented by the general formula (3a) and the phosphoric acid ester compound represented by the general formula (3b) are used, a laminate manufactured using the near-infrared curable composition of the present invention, There is a tendency that the color tone and heat resistance of the three-dimensional model are excellent, which is preferable. When both the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) are used, the phosphate ester compound represented by the general formula (3a) The ratio of the phosphoric acid ester compound represented by the general formula (3b) is not particularly limited, but is usually 10:90 to 90:10 in molar ratio ((3a) :( 3b)).

  Moreover, as a phosphate ester compound represented by the said general formula (3a), it may be used individually by 1 type, or 2 or more types may be used, and the phosphate ester compound represented by the said General formula (3b) May be used alone or in combination of two or more.

  Further, as the phosphate ester compound dispersant, other phosphate esters can be used. Examples of other phosphate esters include phosphate triesters, and these phosphate triesters may be used alone or together with the specific phosphate ester compound.

  As at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b), commercially available phosphoric acid Ester compounds such as DLP-8, DLP-10, DDP-8, DDP-10, TDP-8, TDP-10 (manufactured by Nikko Chemicals Co., Ltd.), Prisurf A219B, Prisurf A210B (all Ichiko Pharmaceutical Co., Ltd.) can also be used. Moreover, the phosphoric acid in these phosphate ester compounds, ie, the compound which neutralized the hydroxyl group with the appropriate base can also be used. Examples of the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

  Further, the phosphonic acid compound represented by the general formula (2) is preferably 0.4 mol or more, more preferably 0.5 to 1.5 mol per 1 mol of copper in the copper salt. Preferably, it is 0.7-1.2 mol. Within the said range, since the color tone and heat resistance of a laminated body and a three-dimensional molded item are especially excellent, it is preferable. The phosphonic acid compound represented by the general formula (2) is preferably used in an amount of 5 mol or more, more preferably 8 to 100 mol, particularly preferably 10 to 80 mol, per mol of the dispersant. When the amount is less than 5 mol, the near-infrared absorption characteristics of the near-infrared curable composition may deteriorate or the heat resistance may decrease.

  Examples of the solvent include alcohols such as methanol and ethanol, tetrahydrofuran (THF), dimethylformamide (DMF), water, and the like, and ethanol, THF, or DMF is preferable from the viewpoint of satisfactory reaction. The reaction step is preferably performed at room temperature to 60 ° C, more preferably 20 to 40 ° C, and preferably 0.5 to 50 hours, more preferably 1 to 30 hours.

  In the reaction step, the phosphonic acid compound represented by the general formula (2) and the copper salt react with each other, and by the reaction, a particulate phosphonic acid copper salt that does not dissolve in the solvent (general formula (1) A phosphonic acid copper salt represented by the following formula: At least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) acts as a good dispersant during the reaction. Therefore, the phosphonic acid copper salt can maintain high dispersibility and suppress aggregation.

  In the reaction step, not only the reaction between the phosphonic acid compound represented by the general formula (2) and the copper salt, but also, for example, the phosphate ester compound represented by the general formula (3a) and the general formula (3b) At least one type of phosphate ester compound selected from the phosphate ester compounds represented by) may react with a part of the copper salt. Further, a part of the raw material may remain without reacting.

  In the method for producing fine particles composed of the phosphonic acid copper salt, the fine particles composed of the phosphonic acid copper salt are usually obtained by removing at least a part of the solvent from the reaction mixture.

In the solvent removal step, at least a part of the solvent is removed from the reaction mixture. In the solvent removal step, in addition to the solvent, the liquid components in the reaction mixture may be removed together.
In the solvent removal step, at least a part of the solvent is usually removed by heating the reaction mixture, but the heating condition is usually room temperature to 70 ° C, preferably 40 to 60 ° C. The solvent removal step may be performed under normal pressure or under reduced pressure. When the solvent removal step is performed under reduced pressure, heating may not be performed or the heating temperature may be low.

  In addition, after the solvent removal step, for the purpose of removing impurities contained in the phosphonic acid copper salt fine particles, the phosphonic acid copper salt fine particles are dispersed in the dispersion medium, and then the dispersion medium is removed. A process may be provided.

  The phosphonic acid copper salt usually has an average particle diameter of 1 to 1000 nm. When the average particle size is 1-1000 nm, the near-infrared absorbent can be dispersed in the near-infrared curable composition without being unevenly distributed. The average particle diameter is 5 to 300 nm from the viewpoint of not having an adverse effect on dispersibility in at least one component selected from a resin and a compound that becomes a polymer by polymerization and the color tone of the near-infrared curable composition. It is more preferable.

  Next, when the near-infrared absorber used in the present invention is a near-infrared absorber composed of a coated phosphonate copper salt, for example, fine particles composed of a phosphonate copper salt represented by the general formula (1) or general A near-infrared absorber in which fine particles comprising a phosphonic acid copper salt represented by the formula (1) and a dispersant are coated with a resin, a fine particle comprising a phosphonic acid copper salt represented by the general formula (1) or the general formula (1 In the case of a near-infrared absorber in which fine particles composed of a phosphonic acid copper salt represented by formula (1) and a dispersant are coated with polysiloxane, it can be produced, for example, by the following method.

  First, production of a near-infrared absorber in which fine particles comprising a phosphonic acid copper salt represented by the general formula (1) or fine particles comprising a phosphonic acid copper salt represented by the general formula (1) and a dispersant are coated with a resin. A method will be described.

  The near-infrared absorber coated with the resin can be obtained by coating fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt with a resin. In order to produce the near infrared absorber, the following monomers are usually used to obtain a resin.

  From the viewpoint of moldability, the resin is preferably formed using a monofunctional monomer as at least a part of the monomer. Examples of the monofunctional monomer include a monofunctional aromatic vinyl compound and a monofunctional (meta) ) Acrylic acid esters and α-olefins may be mentioned, and these may be used alone or in combination of two or more.

  Examples of the monofunctional aromatic vinyl compound include styrene, α-methylstyrene, ethylstyrene, tert-butylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene.

  Examples of the monofunctional (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, and tert-butyl methacrylate. , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isodecyl acrylate, isodecyl methacrylate, n-lauryl acrylate, n-lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, n-stearyl acrylate, n-stearyl methacrylate, isobornyl Acrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate Rate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate. As the monofunctional (meth) acrylic acid ester, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like are preferable.

  As the α-olefin, an α-olefin having 4 to 18 carbon atoms is usually used, and examples thereof include 1-butene, 1-propene, 1-hexene, 1-octene and 1-decene.

The resin is preferably formed using a crosslinking agent as at least a part of the monomer from the viewpoint of heat resistance of the near infrared absorber.
A cross-linking agent is a compound having at least two functional groups capable of radical polymerization in one molecule, and examples thereof include polyfunctional aromatic vinyl compounds and polyfunctional (meth) acrylic esters. It may be used or two or more kinds may be used.

In the present invention, “(meth) acrylic acid” means “methacrylic acid” and “acrylic acid”.
Examples of the polyfunctional aromatic vinyl compound include divinylbenzene, diisopropenylbenzene, and trivinylbenzene.

  Examples of the polyfunctional (meth) acrylic acid ester include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane, tricyclodecane dimethanol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate .

As the crosslinking agent, ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like are preferable.
The resin is preferably formed using a crosslinking agent and a monofunctional (meth) acrylic ester as monomers.

  It is preferable to use 1 part by mass or more of the crosslinking agent and 99 parts by mass or less of the monofunctional monomer per 100 parts by mass of the monomer used for producing the resin, and 5 to 99 parts by mass of the crosslinking agent and the monofunctional monomer. It is more preferable to use 1 to 95 parts by mass, and it is particularly preferable to use 10 to 90 parts by mass of the crosslinking agent and 10 to 90 parts by mass of the monofunctional monomer.

  As a method for producing a near-infrared absorber in which fine particles comprising a copper phosphonate represented by the general formula (1) or fine particles comprising a copper phosphonate represented by the general formula (1) and a dispersant are coated with a resin Although there is no particular limitation, for example, the monomer is polymerized in the presence of the fine particles composed of the above-mentioned copper phosphonate, to obtain a polymer composed of the fine particles composed of the phosphonic copper salt and the resin, and if necessary, the polymer By pulverizing, a near-infrared absorber coated with a resin is obtained.

  The method for polymerizing the monomer is not particularly limited, and it is carried out by a polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization or the like. Among these, bulk polymerization that allows easy polymerization is preferable. In addition, since the polymer obtained by bulk polymerization is obtained in the form of a bulk (lumb), a near-infrared absorber coated with a resin can be obtained by pulverizing the polymer.

  As a specific example of a method for producing a near-infrared absorber coated with a resin, fine particles of a near-infrared absorber composed of an uncoated phosphonic acid copper salt obtained by the aforementioned method are dispersed in a monomer, and copper Examples include a method of obtaining a near-infrared absorber coated with a powdered resin by obtaining a salt-containing monomer, bulk polymerization of the copper salt-containing monomer, obtaining a polymer, and pulverizing the polymer. .

  As a method for obtaining the copper salt-containing monomer, after dispersing fine particles comprising a near-infrared absorber comprising an uncoated phosphonic acid copper salt in a dispersion medium, obtaining a dispersion, and adding the monomer to the dispersion And a method of obtaining a copper salt-containing monomer by removing the dispersion medium.

  As the dispersion medium, those capable of dispersing fine particles made of the phosphonic acid copper salt are used, and usually low-boiling organic substances are used. For example, methylene chloride, acetone, methanol, chloroform and the like are used.

  Examples of a method for dispersing fine particles comprising a non-coated phosphonic acid copper salt in a near-infrared absorber in a dispersion medium include, for example, fine particles comprising a non-coated phosphonic acid copper salt and a near-infrared absorbent comprising a non-coated phosphonic acid copper salt. And a method of dispersing fine particles composed of the near-infrared absorber composed of the uncoated phosphonic acid copper salt in a dispersion medium by a method such as ultrasonic irradiation, homogenizer, stirring, warming stirring and the like.

  The monomer is then preferably dissolved by adding the aforementioned monomer to the dispersion. Next, by removing the dispersion medium, it is possible to obtain a copper salt-containing monomer in which fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt are dispersed.

The method for removing the dispersion medium is not particularly limited, and examples thereof include removal of the dispersion medium by reduced pressure and removal by a combination of heating and reduced pressure.
In addition, when adding a monomer to a dispersion liquid, after adding a part of monomer to a dispersion liquid and removing a dispersion medium, you may add the remaining monomer further and may mix.

  In this way, a copper salt-containing monomer in which fine particles made of a near-infrared absorber made of an uncoated phosphonic acid copper salt are dispersed in the monomer can be obtained. In addition, as the ratio of the amount of the fine particles composed of uncoated phosphonic acid copper salt composed of a near-infrared absorber and the monomer, the amount of fine particles composed of uncoated near-infrared absorbent composed of phosphonic acid copper salt is 1 mass. The monomer is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass with respect to parts. If the amount of the monomer is less than 0.01 parts by mass, the fine particles composed of the phosphonic acid copper salt may not be coated. If the amount of the monomer is more than 20 parts by mass, the resin used together with the near infrared absorber and There exists a possibility of affecting the physical property of at least 1 type of component selected from the compound used as a polymer by superposing | polymerizing.

  In addition, when manufacturing a near-infrared absorber, the method of carrying out bulk polymerization of a copper salt containing monomer as mentioned above is mentioned, but in bulk polymerization, in order to polymerize a monomer suitably, it is usually a radical polymerization initiator. Is preferably added at the same time as or after the monomer is added to the dispersion to obtain a copper salt-containing monomer containing a radical polymerization initiator.

  The radical polymerization initiator is not particularly limited, and for example, an organic peroxide polymerization initiator or an azo radical polymerization initiator can be used. The radical polymerization initiator is usually used in an amount of 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the monomer.

  When bulk polymerization of the copper salt-containing monomer to obtain a polymer, for example, the copper salt-containing monomer is injected into a mold, a test tube, or the like, and usually a polymerization temperature of 20 to 200 ° C. and a polymerization time of 1 to 40 hours. Polymerization takes place at

  A near-infrared absorber coated with a resin can be obtained by pulverizing the polymer obtained by the bulk polymerization. A method for pulverizing the polymer is not particularly limited, and for example, a sand mill, a jet mill, a ball mill, an attritor, a vibration mill or the like can be used.

  The near-infrared absorber coated with a resin can be produced, for example, by the above-described method, and is a powder in which fine particles composed of an uncoated near-infrared absorber composed of a phosphonic acid copper salt are coated with a resin. is there. As an average particle diameter of the near-infrared absorber coat | covered with the obtained resin, it is preferable that it is 0.05-100 micrometers, and it is more preferable that it is 0.05-50 micrometers. Within the said range, since the near-infrared absorber used for this invention is excellent in transparency, it is preferable.

  In the present invention, being coated with a resin means that at least a part of the surface of fine particles made of a near-infrared absorber made of an uncoated phosphonic acid copper salt is covered with a resin, As the near-infrared absorber coated with a resin, it is preferable that the entire surface of fine particles made of an uncoated near-infrared absorber made of a phosphonic acid copper salt is covered with a resin.

  Next, a near-infrared absorber in which fine particles composed of copper phosphonate represented by the general formula (1) or fine particles composed of copper phosphonate represented by the general formula (1) and a dispersant are coated with polysiloxane. A manufacturing method will be described.

  The near-infrared absorber coated with the polysiloxane can be obtained by coating fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt with polysiloxane.

  The polysiloxane constituting the near-infrared absorber is not particularly limited as long as it can coat fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt.

  The polysiloxane is preferably formed from at least one silicon-based compound selected from alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof.

  The said alkoxysilane may be used individually by 1 type, or may use 2 or more types. Alkoxysilane generally has a structure in which an alkoxy group is bonded to a silicon atom, but as an alkoxysilane, a quaternary alkoxysilane in which four alkoxy groups are bonded to a silicon atom, or a tertiary in which three alkoxy groups are bonded. Any of these alkoxysilanes and secondary alkoxysilanes in which two alkoxy groups are bonded may be used. Further, primary alkoxysilane bonded with one alkoxy group may be used as a part of alkoxysilane.

  Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, octyltriethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, 2-cyanoethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxy Examples include cyclopropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. As the alkoxysilane, tetramethoxysilane or the like is preferable.

  In general, an alkoxysilane easily undergoes hydrolysis / condensation reaction in the presence of an acid or an alkali. Further, when the hydrolyzate of alkoxysilane or alkoxysilane is heated, a condensation reaction occurs. As the silicon compound, alkoxysilane, a hydrolyzate of alkoxysilane, and a mixture of these condensates may be used.

In particular, it is preferable to use a condensate because it is easy to handle.
A commercial product may be used as the condensate. Examples of commercially available products include methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.), and the like. It is done.

  The near-infrared absorber coated with the polysiloxane is a powder in which fine particles comprising a near-infrared absorber composed of the uncoated phosphonic acid copper salt are coated with polysiloxane, and the production method is not particularly limited. However, for example, in the presence of fine particles made of a near-infrared absorber made of the uncoated phosphonic acid copper salt, the silicon compound is hydrolyzed / condensed to form a polysiloxane so that the coating is performed. A near-infrared absorber composed of a non-phosphoric acid copper salt and a reaction product composed of polysiloxane are obtained, and the reaction product is pulverized to obtain a near-infrared absorber coated with the polysiloxane.

  The reaction conditions for the hydrolysis / condensation are usually 10 to 250 ° C., more preferably room temperature to 100 ° C. for the implementation. In order to accelerate the reaction, a catalyst such as an acid or a base may be used. Moreover, when performing drying, it is 10-250 degreeC normally, Preferably it is carried out at 50 to 200 degreeC.

  The method for pulverizing the reaction product is not particularly limited, but the reaction product can be pulverized using an agate mortar, sand mill, jet mill, ball mill, attritor, vibration mill or the like.

As a ratio of the amount of the fine particles composed of the non-coated phosphonic acid copper salt used for obtaining the near-infrared absorber coated with the polysiloxane and the silicon compound, The silicon-based compound is preferably used in an amount of 0.3 to 20 parts by mass in terms of SiO _{2 with} respect to 1 part by mass of copper in the fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt. It is more preferable to use 5 to 15 parts by mass. If the amount of the silicon-based compound used is less than the above range, the coating is insufficient and may not be obtained as a solid and may not be suitable for implementation. If it exceeds the above range, it is necessary to obtain a workability reduction and an infrared absorption effect. The amount added may be unsuitable for implementation.

In addition, although it is possible to use compounds having various structures as the silicon compound, the mass part in terms of SiO ₂ is obtained. The amount of silicon atoms of the silicon compound is determined, and the silicon compound It is a mass part when it is assumed that it is a silicon dioxide which has a silicon atom.

  The near-infrared absorber coated with the polysiloxane can be produced, for example, by the above-described method, and the fine particles comprising the near-infrared absorber composed of the uncoated phosphonic acid copper salt are coated with the polysiloxane. Powder. The average particle diameter of the near-infrared absorber coated with the obtained polysiloxane is preferably 0.01 to 100 μm, more preferably 0.03 to 50 μm, particularly 0.05 to 1 μm. preferable. Within the said range, since the near-infrared absorber used for this invention is excellent in transparency, it is preferable.

  In the present invention, the term “coated with polysiloxane” means that at least a part of the surface of the fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt is covered with polysiloxane. This means that as the near-infrared absorber coated with polysiloxane, the entire surface of the fine particles made of the near-infrared absorber made of the uncoated phosphonic acid copper salt is preferably covered with polysiloxane.

[At least one component selected from a resin and a compound that becomes a polymer by polymerization]
The near-infrared curable composition of the present invention includes at least one component selected from a resin and a compound that becomes a polymer by polymerization.

  The resin is not particularly limited as long as it is generally contained in ink or paint, and a thermosetting resin or a thermoplastic resin may be used. In addition, when using the near-infrared thermosetting composition of this invention as an ink, a thermoplastic resin is not normally used.

  Examples of the thermosetting resin include epoxy resins, urethane resins, polyaromatic resins, acrylic resins, urea resins, melamine resins, phenol resins, resorcinol resins, ester resins, polyimide resins, and silicone resins.

  Examples of the thermoplastic resin include vinyl acetate resin (PVAc), polyvinyl alcohol resin (PVA), ethylene vinyl acetate resin (EVA), vinyl chloride resin (PVC), acrylic resin (PA), polyamide, cellulose resin, and polyvinylpyrrolidone. (PVP), polystyrene (PS), cyanoacrylate resin, polyvinyl acetal resin, polyolefin resin, ionomer resin, acrylonitrile-butadiene-styrene (ABS) resin, ester resin, PLA resin (polylactic acid).

  In the near-infrared curable composition of the present invention, the type of resin can be appropriately selected according to the material of the substrate to be printed or applied, the use of the three-dimensional structure, and the purpose. For example, when the substrate is glass, the resin is preferably an ionomer resin, a polyvinyl acetal resin, an ethylene vinyl acetate resin, an acrylic resin, an epoxy resin, or a silicone resin from the viewpoint of satisfactory coating or printing. In the case of polyethylene terephthalate, polyolefin resin, ethylene vinyl acetate resin, acrylic resin, epoxy resin, and silicone resin are preferable from the viewpoint of satisfactory coating or printing. Moreover, in order to obtain a three-dimensional molded item, it is preferable to use an acrylic resin, an epoxy resin, a silicone resin, an ABS resin, or a PLA resin (polylactic acid) as the resin.

  In general, the resin is at least one resin selected from ionomer resins, ethylene vinyl acetate resins, polyolefin resins, epoxy resins, silicone resins, acrylic resins, polyvinyl acetal resins, ABS resins, and PLA resins. To preferred.

  The ionomer resin is not particularly limited, and various ionomer resins can be used. Examples of the ionomer resin include ethylene ionomers, styrene ionomers, perfluorocarbon ionomers, telechelic ionomers, polyurethane ionomers, and the like, and ethylene ionomers having excellent strength, hardness, durability, transparency, and adhesiveness may be used. preferable.

  As the ethylene ionomer, an ionomer of an ethylene / unsaturated carboxylic acid copolymer is preferably used because of its excellent transparency and toughness. The ethylene / unsaturated carboxylic acid copolymer is a copolymer having at least a structural unit derived from ethylene and a structural unit derived from unsaturated carboxylic acid, and may have a structural unit derived from another monomer.

As said unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, etc. are mentioned, Acrylic acid and methacrylic acid are preferable, and methacrylic acid is especially preferable.
Examples of the other monomers include acrylic acid esters, methacrylic acid esters, and 1-butene.

  The ethylene / unsaturated carboxylic acid copolymer preferably has 75 to 99 mol% of structural units derived from ethylene, assuming that the total structural units of the copolymer are 100 mol%, and 78 to 97 mol%. It is more preferable to have 1-25 mol% of the structural unit derived from unsaturated carboxylic acid, and it is more preferable to have 3-22 mol%. Within the above range, mechanical properties such as tensile properties are excellent, which is preferable.

  The ionomer of the ethylene / unsaturated carboxylic acid copolymer is an ionomer resin obtained by neutralizing or crosslinking at least a part of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer with a metal ion. The degree of neutralization of the carboxyl group is usually 5 to 100%, preferably 10 to 90%.

  Examples of the ion source in the ionomer resin used in the present invention include alkali metals such as lithium, sodium, potassium, rubidium, and cesium, and polyvalent metals such as magnesium, calcium, and zinc, and sodium and zinc are preferable.

There is no limitation in particular as a manufacturing method of ionomer resin used for this invention, It can manufacture with a conventionally well-known manufacturing method, and may use a commercial item.
The ethylene vinyl acetate resin (EVA) is not particularly limited as long as it has a molecular weight and an ethylene-vinyl acetate composition ratio used in the coating material. Moreover, it can manufacture with a conventionally well-known manufacturing method, and may use a commercial item.

  As the polyolefin resin, polyethylene, polypropylene, polybutene and copolymers of α-olefins having 2 to 4 carbon atoms such as ethylene, propylene and butene are preferable. The polyolefin resin is not particularly limited as long as it has a molecular weight and a composition ratio as contained in the paint. Moreover, it can manufacture with a conventionally well-known manufacturing method, and may use a commercial item.

As the polyvinyl acetal resin, it is preferable to use polyvinyl butyral (PVB) from the viewpoints of adhesiveness, dispersibility, transparency, heat resistance, light resistance, and the like.
The polyvinyl acetal resin may be a blend obtained by combining two or more kinds according to necessary physical properties, or may be a polyvinyl acetal resin obtained by combining acetaldehyde during acetalization and acetalizing. The molecular weight, molecular weight distribution, and degree of acetalization of the polyvinyl acetal resin are not particularly limited, but the degree of acetalization is generally 40 to 85%, and the preferred lower limit is 60% and the upper limit is 75%.

  The polyvinyl acetal resin can be obtained by acetalizing a polyvinyl alcohol resin with an aldehyde. The polyvinyl alcohol resin is generally obtained by saponifying polyvinyl acetate, and a polyvinyl alcohol resin having a saponification degree of 80 to 99.8 mol% is generally used. The preferable lower limit of the viscosity average polymerization degree of the polyvinyl alcohol resin is 200, and the upper limit is 3000. A more preferred lower limit is 500 and an upper limit is 2200. The viscosity average polymerization degree and saponification degree of the polyvinyl alcohol resin can be measured based on, for example, JISK 6726 “Testing method for polyvinyl alcohol”.

  The aldehyde is not particularly limited, and examples thereof include aldehydes having 1 to 10 carbon atoms, and more specifically, for example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutylartaldehyde. N-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, n-valeraldehyde and the like are preferable. More preferred is butyraldehyde having 4 carbon atoms.

  The epoxy resin may be any resin having an epoxy group in the molecule, and is not particularly limited. However, bisphenol type epoxy resins such as bisphenol A type and bisphenol F type, epoxy resins having an alicyclic molecular structure, etc. Is mentioned. These react with acid anhydrides and amines by heating to form a cured product. The epoxy resin is not particularly limited as long as it has a molecular weight and a composition ratio as contained in the ink or paint. Moreover, it can manufacture with a conventionally well-known manufacturing method, and may use a commercial item.

  The silicone resin is not particularly limited as long as it has an organopolysiloxane structure, and examples thereof include a polyorganosiloxane resin having a vinyl group at the terminal. These undergo an addition reaction by heating and the action of a catalyst to form a cured product. In addition, the silicone resin is not particularly limited as long as it has a molecular weight and a composition ratio that are contained in ink or paint. Moreover, it can manufacture with a conventionally well-known manufacturing method, and may use a commercial item.

  As the acrylic resin, those conventionally used for ink and paint can be used without limitation. An acrylic resin is a resin having a structural unit derived from an acrylic ester or a methacrylic ester. Examples of the acrylic ester and methacrylic ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-, i-, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth). C1-C24 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid such as acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate Is mentioned.

  In addition, the acrylic resin may have a structural unit derived from a monomer other than an acrylic ester or a methacrylic ester. For example, the alkoxy group-containing unsaturated unit having 1 to 24 carbon atoms such as methoxymethyl acrylate and methoxyethyl acrylate. Hydroxyl-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; carboxyl-containing unsaturated monomers such as acrylic acid and methacrylic acid; styrene And a structural unit derived from (meth) acrylamide, vinyl acetate or the like. Moreover, various modification | denaturation may be performed as an acrylic resin. The acrylic resin can be produced by a conventionally known production method, and a commercially available product may be used.

  The compound that becomes a polymer by the polymerization is not particularly limited as long as it is generally contained in inks and paints, and it is generally preferable to use monomers, oligomers, etc. contained in inks and paints. .

  The compound that becomes a polymer by the polymerization is not particularly limited, and a silicon-based compound that becomes polysiloxane by polymerization may be used, and monomers and oligomers described later may be used.

  As the silicon-based compound that becomes polysiloxane by the polymerization, it is preferable to use at least one silicon-based compound selected from alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof.

  The at least one silicon-based compound selected from alkoxysilanes, hydrolysates of alkoxysilanes, and condensates thereof includes the above-mentioned [near infrared including a phosphonic acid copper salt represented by the general formula (1) It is preferable to use those described in the section of [Absorbent].

In the present invention, polysiloxane means a compound having a chain of siloxane bonds (Si—O—Si), and silica (SiO ₂ ) is also included in polysiloxane.

  Although there is no limitation in particular as said monomer and oligomer, For example, although the monomer and oligomer which become the above-mentioned resin by superposing | polymerizing can be used, you may use another monomer and oligomer.

These monomers and oligomers may be used alone or in combination of two or more.
Examples of the monomer include monomers containing an ethylenically unsaturated group (group having a carbon / carbon double bond) such as acrylic acid ester, methacrylic acid ester, and α-olefin, a monomer having a hydroxyl group, and a carboxyl group. Examples thereof include monomers, monomers having an epoxy group, monomers having an amino group, monomers having an isocyanate group, and monomers having an imidazole group. The monomer may have one of the aforementioned functional groups or may have two or more.

  Examples of these monomers include epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, and polyol acrylate.

Moreover, as the oligomer, it is possible to use one in which several hundred or less of the above-described monomers are bonded.
When the near-infrared curable composition of the present invention is used in an ink, examples of the monomer and oligomer include urethane acrylate, urethane methacrylate, epoxy acrylate, epoxy methacrylate, bisphenol A ethaethylene glycol diacrylate, and bisphenol A tetraethylene glycol. Dimethacrylate, bisphenol F polyethylene glycol diacrylate, bisphenol F polyethylene glycol dimethacrylate, tricyclodecane dimethylol diacrylate, tricyclodecane dimethylol dimethacrylate, trimethylolpropane tripropoxytriacrylate, trimethylolpropane tripropoxytrimethacrylate, ditri Methylolpropane tetraacrylate, ditrimethylo Rupropanetetramethacrylate, trimethylolpropane polyethoxytriacrylate, trimethylolpropane polyethoxytrimethacrylate, hydroxypivalate neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate Ethylenic unsaturation such as dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tripentaerythritol acrylate ester, tetrapentaerythritol acrylate ester, tripentaerythritol methacrylate ester, tetrapentaerythritol methacrylate ester Monomers containing groups and It is preferable to use these oligomers.

  When the near-infrared curable composition of the present invention is used in an ink, examples of the resin include epoxy resins such as bisphenol A type and phenol novolac type, epoxy resins such as epoxidized soybean oil, epoxidized rosin, and epoxidized polybutadiene. Epoxy acrylates, epoxy methacrylates, urethane modified products of the above-mentioned epoxy acrylates and methacrylates, and acrylic acid esters and methacrylic acid esters of fatty acid-modified Alkit resins, which are the reaction products of resin with acrylic acid and methacrylic acid. It is preferable to use a saturated group-containing resin.

  In addition, as the at least one component selected from the resin and the compound that becomes a polymer by polymerization, either the resin alone or the compound that becomes the polymer by polymerization can be used, or the resin and the polymerization can be used. You may use the compound used as a polymer. Moreover, as said resin, only 1 type may be used or 2 or more types may be used, and only 1 type or 2 types or more may be used as a compound which becomes a polymer by superposing | polymerizing. Good.

[Near-infrared curable composition]
The near-infrared curable composition of the present invention is at least selected from a near-infrared absorber containing at least the phosphonic acid copper salt represented by the general formula (1), a resin, and a compound that becomes a polymer by polymerization. A kind of ingredient. Moreover, the near-infrared curable composition of this invention is used as an ink or a coating material.

  Since the near-infrared curable composition of the present invention is cured by irradiation with near infrared rays, printing or coating is performed on a substrate, and then the near-infrared curable composition is irradiated with near infrared rays to be cured. A layer made of ink or paint can be formed on the material, and a laminate is obtained. Moreover, a three-dimensional molded item can also be obtained by injecting and curing a near-infrared curable composition by an optical modeling method using near infrared rays as light for curing.

  The amount of the near-infrared absorbent containing at least the phosphonic acid copper salt represented by the general formula (1) contained in the near-infrared curable composition of the present invention is at least the phosphonic acid copper represented by the general formula (1). It is usually 0.001 to 30 parts by mass, preferably 0.001 to 30 parts by mass per 100 parts by mass in total of the near-infrared absorber containing a salt and at least one component selected from a resin and a compound that becomes a polymer by polymerization. It is 01-20 mass parts, More preferably, it is 0.1-10 mass parts. Further, the amount of at least one component selected from a resin and a compound that becomes a polymer by polymerization is usually 70 to 99.999 parts by mass, preferably 80 to 99.99 parts by mass, and more preferably. Is 90-99.9 parts by mass.

  In addition, the near-infrared curable composition of this invention is components other than the above-mentioned near-infrared absorber, resin, and at least 1 type of component selected from the compound which becomes a polymer by superposing | polymerizing (it is hereafter described as another component). Is usually included.

  Examples of other components include a polymerization initiator, a curing agent, a polymerization inhibitor, a plasticizer, a dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, silica, a polymer, a solvent, a dispersion medium, and a fluorescent whitening. Agents, colorants (for example, pigments, dyes) and the like.

  Inks and paints usually contain colorants that absorb visible light and make the composition a desired color. Therefore, the near-infrared curable composition of the present invention usually contains colorants such as pigments and dyes. As the colorant, conventionally known ones can be used depending on the use of the ink or paint. For example, inorganic pigments (for example, titanium dioxide pigment, iron oxide pigment), light interference pigments, carbon black, organic Examples include pigments (for example, azo pigments, phthalocyanine pigments, isoindoline pigments), organic dyes, and inorganic dyes. In addition, only 1 type may be contained in the near-infrared curable composition, and the colorant may be contained 2 or more types.

  In the near infrared curable composition of the present invention, the colorant is usually 0.01 to 80% by mass, preferably 0.1 to 60% by mass, more preferably 1 to 100% by mass in the composition. Contains 50% by mass.

  Unlike the ultraviolet curable composition, the near-infrared curable composition of the present invention does not cause any problems during curing even when an ultraviolet absorber is included. Furthermore, it is preferable to use an ultraviolet absorber as the other component because it is possible to improve the light resistance of a laminate obtained by using a near-infrared curable composition or a three-dimensional structure.

  When the near-infrared curable composition of this invention contains a ultraviolet absorber, a ultraviolet absorber is normally 0.001-80 mass% in the composition 100 mass% normally, Preferably it is 0.01. -60 mass%, More preferably, it contains 1-50 mass%.

  The other components may be added together with at least one component selected from a near-infrared absorber, a resin and a compound that becomes a polymer by polymerization when obtaining a near-infrared curable composition, It may be added when producing the above-mentioned near-infrared absorber, or may be added when producing at least one component selected from a resin and a compound that becomes a polymer by polymerization. Further, for example, when at least one component selected from the aforementioned resin and a compound that becomes a polymer by polymerization is a component derived from a commercially available ink or paint, Components other than at least one component selected from the resin contained in the polymer and a compound that becomes a polymer by polymerization, for example, a polymerization initiator, a curing agent, and a coloring agent are also included in the near-infrared curable composition as the other components. May be.

When the said other component is contained, it is normally contained in 0.01-80 mass% normally in 100 mass% of near-infrared curable compositions, Preferably it is 0.1-50 mass%.
Using the near infrared curable composition of the present invention as an ink or paint, it is possible to obtain a laminate by printing or coating on a substrate, then irradiating the near infrared curable composition with near infrared rays and curing. It is. Moreover, it is possible to obtain a three-dimensional molded item by injecting and curing the near infrared curable composition of the present invention by an optical modeling method using near infrared rays.

  Both near-infrared curable compositions are irradiated with near-infrared rays when obtaining the laminate or three-dimensional model. As a phenomenon that occurs by being irradiated with near infrared rays, it varies depending on the type of at least one component selected from a resin and a compound that becomes a polymer by polymerization, but in any case, the near infrared absorber is, They are common in that they absorb near-infrared rays and generate heat. For example, when at least one component selected from a resin and a compound that becomes a polymer by polymerization is a thermoplastic resin, after the thermoplastic resin is melted by the near-infrared absorbent that generates heat by irradiation with near-infrared rays, By stopping the infrared irradiation, the thermoplastic resin is solidified. In addition, at least one component selected from a resin and a compound that becomes a polymer by polymerization is a thermosetting resin, or a compound that becomes a polymer by polymerization (for example, a silicon compound that becomes polysiloxane by polymerization, Alternatively, in the case of a monomer or oligomer, the thermal energy of the near-infrared absorber that generates heat by irradiation with near-infrared rays is used as the reaction energy, the thermosetting reaction of the thermosetting resin, the polymerization (hydrolysis / heavy polymerization) of the silicon compound. Condensation), polymerization of monomers and oligomers occurs.

  The method for producing the near-infrared curable composition of the present invention is not particularly limited. For example, at least one component selected from the near-infrared absorber (or dispersion thereof), a resin, and a compound that becomes a polymer by polymerization. And a method of mixing with other components used as necessary, the near-infrared absorber, the resin, and at least one component selected from a compound that becomes a polymer by polymerization and other components used as necessary And dissolving or dispersing in a dispersion medium at least one component selected from the above-mentioned near-infrared absorber, resin, and a compound that becomes a polymer by polymerization and other components used as necessary. It is possible to produce the dispersion medium by removing the dispersion medium as necessary. In addition, when at least one component selected from a resin and a compound that becomes a polymer by polymerization is derived from a commercially available ink or paint, a commercially available ink, paint, or near-infrared absorber (Or a dispersion thereof). As the dispersion medium, methylene chloride, chloroform, toluene, methanol, ethanol or the like can be used.

The property of the near-infrared curable composition of the present invention is not particularly limited as long as it can be used as an ink or a paint, and may be any of solution, dispersion, paste, solid and the like.
[Laminate]
The laminate of the present invention can be obtained by printing or applying a near-infrared curable composition on a substrate, and then irradiating the near-infrared curable composition with near-infrared radiation and curing it. That is, the laminate of the present invention has a two-layer structure of layers obtained by curing a base material layer and a near-infrared curable composition.

  Conventionally, ultraviolet curable inks and paints have been used as inks and paints that are cured by irradiation with light. When these inks and paints are cured, ultraviolet rays are irradiated, and it has been difficult to contain ultraviolet absorbers that inhibit curing in these inks and paints. On the other hand, since the near-infrared curable composition is cured by irradiation with near infrared rays, the laminate of the present invention can easily contain an ultraviolet absorber in the near-infrared curable composition. For this reason, it is easy to obtain a laminate having excellent light resistance as the laminate of the present invention.

  Examples of the substrate constituting the laminate of the present invention include metal, glass, ceramics, tile, concrete, paper, cardboard, wood, plastic and the like. Examples of the plastic include ABS resin, PET resin, polycarbonate, nylon, acrylic resin, hard vinyl chloride, saturated polyethylene, polypropylene, polyacetal, and polyimide.

  In order to obtain the laminate of the present invention, first, a near-infrared curable composition is printed or applied on a substrate. However, the printing or application method is not particularly limited, and conventionally, printing of ink or paint or The method used for coating can be employed.

  In order to obtain the laminate of the present invention, after performing printing or coating, the near-infrared curable composition printed or coated on the substrate is irradiated with near-infrared rays, and the near-infrared curable composition is cured. Let

  A light source for performing near-infrared irradiation is not particularly limited, and a near-infrared laser, a near-infrared light emitting diode (NIR-LED), a halogen lamp, a xenon lamp, or the like can be used.

The near-infrared laser is not particularly limited as long as it can emit near-infrared rays as laser light, and a semiconductor laser, a YAG laser, or the like can be used.
Near-infrared irradiation varies depending on the type of light source, the area of the printed or applied near-infrared curable composition, etc., but it may be performed in one place, and the irradiation position is changed sequentially to a plurality of places. You may go. When performing near-infrared irradiation to a plurality of places, even if the irradiation is performed while changing the position of the substrate on which the near-infrared curable composition is sequentially printed or applied, or while changing the position of the light source, You may carry out, changing the position of the base material and light source by which the near-infrared curable composition was printed or apply | coated.

Moreover, it is preferable that it is 0.01-100W, and, as for the output of the near infrared ray at the time of irradiating a near-infrared curable composition, it is more preferable that it is 0.1-50W. The irradiation energy per unit area of the near-infrared point to be irradiated on the near-infrared-curable composition is preferably 0.01~10000mW / mm ^2, a 0.1~1000mW / mm ² Is more preferable.

  The irradiation time of the near infrared ray varies depending on the output of the near infrared ray, but is usually 1 to 600 seconds per place, preferably 2 to 300 seconds. By using the above-mentioned near infrared curable composition, it can be cured in a short time.

  The laminate of the present invention can be selected by appropriately selecting the type and shape of the base material and the composition of the near-infrared curable composition, so that automobile parts, household appliance parts, parts around toiletries, parts around bathrooms, other industrial parts, It can be used for various applications such as food packaging materials and synthetic paper.

[Three-dimensional model]
The three-dimensional structure of the present invention is obtained by injecting and curing a near infrared curable composition by an optical modeling method using near infrared rays.

Examples of the optical modeling method include an inkjet optical modeling method and a hot melt lamination method.
The inkjet stereolithography method and the hot melt lamination method are stereolithography methods adopted in 3D printers and the like. In the conventional ink jet stereolithography or hot melt lamination method, ultraviolet rays are often used as the irradiated light, but near infrared rays are used as the irradiated light when obtaining the three-dimensional modeled object of the present invention. In the case where the irradiated light is ultraviolet light, it has been difficult for the composition as a raw material to contain an ultraviolet absorber that inhibits curing. Since it is near-infrared, it is easy to contain a ultraviolet absorber in a near-infrared curable composition. For this reason, it is easy to obtain a three-dimensional model having excellent light resistance as the three-dimensional model.

  Inkjet stereolithography using near-infrared rays is performed by ejecting fine droplets of a near-infrared curable composition from a nozzle so as to draw a predetermined shape pattern by an inkjet method, and irradiating near-infrared rays to form a cured thin film. This is a method of stereolithography.

  Specifically, the optical modeling apparatus used in the inkjet optical modeling method using near infrared rays can be moved on a plane stage for optical modeling of a target three-dimensional model and on a plane at least parallel to the plane stage. At least one ink jet nozzle and a light source for irradiating the near-infrared curable composition with near-infrared rays (curing light). As a method of manufacturing a three-dimensional structure, a near-infrared curable composition from an inkjet nozzle with a desired pattern according to cross-sectional shape data obtained by dividing the shape of a target three-dimensional structure into a plurality of cross-sectional shapes based on CAD data or the like After discharging a thing and forming the thin layer (near infrared curable composition layer) which consists of the same composition, near infrared rays are irradiated from a light source, this thin layer is hardened, and a hardened layer is formed. Next, a near-infrared curable composition is supplied onto the cured layer from an inkjet nozzle according to the following cross-sectional shape. By repeating the above, it is possible to laminate a hardened layer corresponding to each cross-sectional shape to form a target three-dimensional object.

  In the hot melt lamination method using near infrared rays, the melted near infrared ray curable composition is discharged little by little from the tip of a thin nozzle and the nozzle (or cradle) is moved in the main scanning direction (X direction). The objective is to solidify the discharged near-infrared curable composition by irradiating near-infrared rays from a light source simultaneously with or after the discharge while placing the discharged near-infrared curable composition in a linear shape. When reaching the end determined by the dimension of the three-dimensional structure (the dimension in the main scanning direction at the layer and the position in the sub-scanning direction), the nozzle (or the cradle) is moved in the sub-scanning direction (Y direction) by a predetermined minute distance. Next, the process of moving in the opposite direction (−X direction) along the main scanning direction is performed until the sub-scanning range determined by the dimensions of the target three-dimensional object (the layer and the dimension in the sub-scanning direction) Repeatedly To form a layer. Next, the second layer is formed by performing the same processing with the direction intersecting the main scanning direction of the first layer as the main scanning direction. This is a method of forming a three-dimensional model by repeating this process to a range determined by the height of the target three-dimensional model. The near-infrared irradiation in the hot melt laminating method may be performed at another timing, and specifically, may be performed to bring the near-infrared curable composition before discharge into a molten state. .

The light source is not particularly limited, and a near infrared laser, a near infrared light emitting diode (NIR-LED), a halogen lamp, a xenon lamp, or the like can be used.
The near-infrared laser is not particularly limited as long as it can emit near-infrared rays as laser light, and a semiconductor laser, a YAG laser, or the like can be used.

Moreover, it is preferable that it is 0.01-100W, and, as for the output of the near infrared ray at the time of irradiating a near-infrared curable composition, it is more preferable that it is 0.1-50W. The irradiation energy per unit area of the near-infrared point to be irradiated on the near-infrared-curable composition is preferably 0.01~10000mW / mm ^2, a 0.1~1000mW / mm ² Is more preferable.

  The irradiation time of the near infrared ray varies depending on the output of the near infrared ray, but is usually 1 to 600 seconds per place, preferably 2 to 300 seconds. By using the above-mentioned near infrared curable composition, it can be cured in a short time.

  The three-dimensional modeled object of the present invention can be obtained as various three-dimensional modeled objects such as prototypes and mockups of products and parts, architectural models, preoperative examination models, etc., by appropriately selecting the composition of the near infrared curable composition. Is possible.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
In all of the examples and comparative examples, a laser device (JenLas fiber ns 40-advanced) (manufactured by Jena Optic) was used. The apparatus had an output power of 40 W (maximum value), a center wave length of 1062 nm, and a beam diameter of 1.15 mm.

  In Examples 1 to 6 and Comparative Examples 1 to 4, the laser beam is irradiated with an irradiation distance of 3 cm, and the beam diameter at the time of irradiation of the irradiation object is about 8 mm (seven times expansion). The test was performed under the following conditions. The irradiation energy after expansion was about 1.5W.

  In Examples 7 to 14, the laser beam was irradiated under the conditions that the irradiation distance to the irradiation object was 3 cm and the beam diameter at the time of irradiation to the irradiation object was about 8 mm (seven times expansion). . The irradiation energy after expansion was about 2.6W.

[Production Example 1] (Production of butylphosphonic acid copper salt / phosphate dispersing agent)
In the flask, 19.92 g of butylphosphonic acid, 7.5 g of a phosphoric acid dispersant, and 99.61 g of ethanol were added and dissolved (solution A).

In a reaction vessel, 30.00 g of copper (II) acetate monohydrate and 1650 g of ethanol were added and dissolved, and solution A was added dropwise with stirring at room temperature.
After 1 hour, the solvent was distilled off, 300 g of toluene was added to the resulting solid, and sonication was performed. Toluene was distilled off, 300 g of toluene was added to the obtained solid, and sonication was performed.

  In the obtained copper salt dispersion, 11.25 g (butylphosphonic acid copper salt: dispersing agent: toluene = 1: 0.25: 10) was weighed into a reaction vessel, and diluted by adding 20 g of toluene. While stirring at room temperature, 0.0208 g of an ethanol solution of butylphosphonic acid (10 g) was added dropwise.

  After 4 hours, the solvent was distilled off, and 20 g of toluene was added to the obtained solid (butyl phosphonic acid copper salt / phosphoric acid-based dispersant) (near-infrared absorber), followed by ultrasonic treatment. Toluene is distilled off, 20 g of toluene is added to the resulting solid, and ultrasonic treatment is performed, and toluene containing butylphosphonic acid copper salt / phosphoric acid dispersant (near infrared absorber) as copper salt fine particles A dispersion was obtained. The average particle diameter of the copper salt fine particles in the dispersion was 53 nm. In addition, the average particle diameter was measured using ELSZ-2 (made by Otsuka Electronics Co., Ltd.).

[Example 1]
25 parts by mass of a one-component thermosetting of 75 parts by mass of a toluene dispersion (1.5 parts by mass of butylphosphonic acid copper salt / phosphoric acid-based dispersant) containing the near-infrared absorber obtained in Production Example 1 The ink was added to a mold ink (medium) and mixed with a spatula to prepare a copper salt-containing thermosetting ink (near infrared irradiation ink 1).

  The composition of the commercially available one-component thermosetting ink (medium) is as follows: silica 0-10%, synthetic resin 30-60%, diethylene glycol monoethyl ether acetate 10-20%, petroleum naphtha 1-5%, trimethylbenzene 1 -5%, ethylene glycol monobutyl ether acetate 1-10%, ethyl acetate 1-5%, xylene less than 0.3%, ethylbenzene less than 0.3%, described as not cured unless heated to 150 ° C for 30 minutes or more Has been.

  When the near-infrared irradiation type ink 1 is applied onto glass and laser light is irradiated from the coated surface toward the near-infrared irradiation type ink 1, the near-infrared irradiation type ink 1 is about 2 minutes after irradiation. It was confirmed to be cured. Moreover, the film thickness of the cured ink was 0.1 mm, and it did not peel off when adhered to the glass.

[Example 2]
25 parts by mass of a one-component thermosetting of 75 parts by mass of a toluene dispersion (1.5 parts by mass of butylphosphonic acid copper salt / phosphoric acid-based dispersant) containing the near-infrared absorber obtained in Production Example 1 The ink was added to a mold ink (white) and mixed with a spatula to prepare a copper salt-containing thermosetting ink (near infrared irradiation ink 2).

  The composition of the commercially available one-component thermosetting ink (white) is as follows: silica 0-10%, titanium oxide 30-40%, synthetic resin 30-60%, diethylene glycol monoethyl ether acetate 10-20%, petroleum naphtha 1 -5%, trimethylbenzene 1-5%, ethylene glycol monobutyl ether acetate 1-10%, ethyl acetate 1-5%, xylene less than 0.3%, ethylbenzene less than 0.3%, at 150 ° C for 30 minutes or more It is stated that it will not cure unless heated.

  When the near-infrared irradiation type ink 2 is applied onto glass and laser light is irradiated from the coated surface toward the near-infrared irradiation type ink 2, the near-infrared irradiation type ink 2 is about 2 minutes after irradiation. It was confirmed to be cured. Moreover, the film thickness of the cured ink was 0.1 mm, and it did not peel off when adhered to the glass.

Example 3
25 parts by mass of a one-component thermosetting of 75 parts by mass of a toluene dispersion (1.5 parts by mass of butylphosphonic acid copper salt / phosphoric acid-based dispersant) containing the near-infrared absorber obtained in Production Example 1 It was added to the mold ink (red) and mixed with a spatula to prepare a copper salt-containing thermosetting ink (near infrared irradiation ink 3).

  The composition of the commercially available one-component thermosetting ink (red) is as follows: pigment 0-40%, synthetic resin 30-60%, diethylene glycol monoethyl ether acetate 10-20%, petroleum naphtha 1-5%, trimethylbenzene 1 -5%, ethylene glycol monobutyl ether acetate 1-10%, ethyl acetate 1-5%, xylene less than 0.3%, ethylbenzene less than 0.3%, described as not cured unless heated to 150 ° C for 30 minutes or more Has been.

  When the near-infrared irradiation type ink 3 was applied on a glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 3, the near-infrared irradiation type ink 3 was irradiated in about 2 minutes after irradiation. It was confirmed to be cured. Moreover, the film thickness of the cured ink was 0.1 mm, and it did not peel off when adhered to the glass.

Example 4
25 parts by mass of a one-component thermosetting of 75 parts by mass of a toluene dispersion (1.5 parts by mass of butylphosphonic acid copper salt / phosphoric acid-based dispersant) containing the near-infrared absorber obtained in Production Example 1 The ink was added to a mold ink (purple) and mixed with a spatula to prepare a copper salt-containing thermosetting ink (near infrared irradiation ink 4).

  The composition of the commercially available one-component thermosetting ink (purple) is as follows: pigment 0-40%, synthetic resin 30-60%, diethylene glycol monoethyl ether acetate 10-20%, petroleum naphtha 1-5%, trimethylbenzene 1 -5%, ethylene glycol monobutyl ether acetate 1-10%, ethyl acetate 1-5%, xylene less than 0.3%, ethylbenzene less than 0.3%, described as not cured unless heated to 150 ° C for 30 minutes or more Has been.

  When the near-infrared irradiation type ink 4 is applied on glass and laser light is irradiated from the coated surface toward the near-infrared irradiation type ink 4, the near-infrared irradiation type ink 4 is about 2 minutes after irradiation. It was confirmed to be cured. Moreover, the film thickness of the cured ink was 0.1 mm, and it did not peel off when adhered to the glass.

Example 5
25 parts by mass of a one-component thermosetting of 75 parts by mass of a toluene dispersion (1.5 parts by mass of butylphosphonic acid copper salt / phosphoric acid-based dispersant) containing the near-infrared absorber obtained in Production Example 1 The ink was added to a mold ink (indigo) and mixed with a spatula to prepare a copper salt-containing thermosetting ink (near infrared irradiation ink 5).

  The composition of the commercially available one-component thermosetting ink (indigo) is as follows: copper and its compound 1-10%, synthetic resin 30-60%, diethylene glycol monoethyl ether acetate 10-20%, petroleum naphtha 1-5%, 1-5% trimethylbenzene, 1-10% ethylene glycol monobutyl ether acetate, 1-5% ethyl acetate, less than 0.3% xylene, less than 0.3% ethylbenzene, and cures if not heated to 150 ° C for 30 minutes or more It is stated not to.

  When the near-infrared irradiation type ink 5 was applied onto glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 5, the near-infrared irradiation type ink 5 was about 1 minute after irradiation. It was confirmed to be cured. Moreover, the film thickness of the cured ink was 0.1 mm, and it did not peel off when adhered to the glass.

Example 6
25 parts by mass of a one-component thermosetting of 75 parts by mass of a toluene dispersion (1.5 parts by mass of butylphosphonic acid copper salt / phosphoric acid-based dispersant) containing the near-infrared absorber obtained in Production Example 1 The ink was added to the mold ink (black) and mixed with a spatula to prepare a copper salt-containing thermosetting ink (near infrared irradiation ink 6).

  The composition of the commercially available one-component thermosetting ink (black) is as follows: carbon black 1-10%, synthetic resin 30-60%, diethylene glycol monoethyl ether acetate 10-20%, petroleum naphtha 1-5%, trimethylbenzene. 1-5%, ethylene glycol monobutyl ether acetate 1-10%, ethyl acetate 1-5%, xylene less than 0.3%, ethylbenzene less than 0.3%, unless cured at 150 ° C for 30 minutes or more Have been described.

  When the near-infrared irradiation type ink 6 was applied on a glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 6, the near-infrared irradiation type ink 6 took about 1 minute from irradiation. It was confirmed to be cured. Moreover, the film thickness of the cured ink was 0.1 mm, and it did not peel off when adhered to the glass.

[Comparative Examples 1-4]
The one-component thermosetting ink used in Examples 1 to 4 was coated on glass without adding the toluene dispersion containing the near-infrared absorbent obtained in Production Example 1, and the coating surface was directed to a commercial ink. However, it was not cured.

  In Comparative Example 1, one-component thermosetting ink (medium), in Comparative Example 2, one-component thermosetting ink (white), in Comparative Example 3, one-component thermosetting ink (red), and in Comparative Example 4, one solution. Liquid thermosetting ink (purple) was used.

Example 7
In a vial, 0.8 g pentaerythritol triacrylate, 0.7 g urethane acrylate, 0.1 g ethoxylated bisphenol A diacrylate, 0.04 g perbutyl-O (polymerization initiator), 0.5 g production example Weigh the toluene dispersion containing the near-infrared absorber obtained in 1 (copper butylphosphonate / 0.03 g of phosphoric acid-based dispersant) and mix with a spatula to prepare a thermosetting ink containing copper salt (near infrared) Irradiation ink 7) was prepared.

  When the near-infrared irradiation type ink 7 is applied onto glass and laser light is irradiated from the coated surface toward the near-infrared irradiation type ink 7, the near-infrared irradiation type ink 7 is about 1 minute after irradiation. It was confirmed to be cured. The cured ink film was 0.27 mm and colorless.

  A transmitted light spectrum of a laminate obtained by applying and curing the near infrared radiation type ink 7 on glass was obtained. The transmitted light spectrum was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the measurement was performed in the wavelength range of 2500 nm to 180 nm. A transmitted light spectrum at a wavelength of 300 to 2100 nm is shown in FIG.

  It can be seen from the transmitted light spectrum that the obtained laminate is excellent in visible light transmittance. This is partly because the near-infrared absorber used in the present invention is excellent in transparency (excellent in visible light transmission).

Example 8
10 parts by weight of PC Cyan 2P (manufactured by Nippon Kayaku Co., Ltd., color filter dye) was added to and mixed with 100 parts by weight of the near-infrared irradiation type ink 7 to prepare near-infrared irradiation type ink 8.

  When the near-infrared irradiation type ink 8 is applied on glass and laser light is irradiated from the coated surface toward the near-infrared irradiation type ink 8, the near-infrared irradiation type ink 8 is about 1 minute after irradiation. It was confirmed to be cured.

Example 9
10 parts by mass of PC Green FOP (manufactured by Nippon Kayaku Co., Ltd., color filter dye) was added to and mixed with 100 parts by mass of the near-infrared irradiation type ink 7 to prepare near-infrared irradiation type ink 9.

  When the near-infrared irradiation type ink 9 is applied onto glass and laser light is irradiated from the coated surface toward the near-infrared irradiation type ink 9, the near-infrared irradiation type ink 9 is about 1 minute after irradiation. It was confirmed to be cured.

Example 10
10 parts by weight of PC Yellow 42P (manufactured by Nippon Kayaku Co., Ltd., color filter dye) was added to and mixed with 100 parts by weight of the near-infrared irradiation type ink 7 to prepare near-infrared irradiation type ink 10.

  When the near-infrared irradiation type ink 10 was applied onto glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 10, the near-infrared irradiation type ink 10 was about 5 minutes after irradiation. It was confirmed to be cured.

Example 11
10 parts by mass of PC Magenta 10P (manufactured by Nippon Kayaku Co., Ltd., water-soluble dye) was added to and mixed with 100 parts by mass of the near-infrared irradiation type ink 7 to prepare near-infrared irradiation type ink 11.

  When the near-infrared irradiation type ink 11 was applied on glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 11, the near-infrared irradiation type ink 11 was about 5 minutes after irradiation. It was confirmed to be cured.

Example 12
10 parts by mass of a benzophenone-based ultraviolet absorber was added to 100 parts by mass of the near-infrared irradiation type ink 7 and mixed to prepare a near-infrared irradiation type ink 12.

  When the near-infrared irradiation type ink 12 was applied onto glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 12, the near-infrared irradiation type ink 12 was about 2 minutes after irradiation. It was confirmed to be cured.

Example 13
10 parts by weight of PC Magenta 10P (manufactured by Nippon Kayaku Co., Ltd., water-soluble dye) and 10 parts by weight of a triazole-based ultraviolet absorber are added to and mixed with 100 parts by weight of the near-infrared irradiation type ink 7, and near-infrared rays are added. Irradiation type ink 13 was produced.

  When the near-infrared irradiation type ink 13 was applied onto glass and laser light was irradiated from the coated surface toward the near-infrared irradiation type ink 13, the near-infrared irradiation type ink 13 was about 5 minutes after irradiation. It was confirmed to be cured.

Example 14
The operation of applying the near-infrared irradiation type ink 7 on the glass and irradiating laser light from the coated surface toward the near-infrared irradiation type ink 7 is repeated five times, and the near-infrared irradiation type ink 7 is repeatedly applied. As a result, the near-infrared irradiation type ink 7 could be laminated and cured to a thickness of 5 mm.

Claims (3)

A near-infrared absorber containing at least a phosphonic acid copper salt represented by the following general formula (1):
A near-infrared curable composition used as an ink or paint comprising a resin and at least one component selected from a compound that becomes a polymer by polymerization.

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. ]   A laminate obtained by printing or coating the near-infrared curable composition according to claim 1 on a substrate, and then irradiating the near-infrared curable composition with near-infrared rays and curing the composition.   A three-dimensional structure obtained by injecting and curing the near-infrared curable composition according to claim 1 by an optical modeling method using near-infrared rays.

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