JPWO2009063654A1 - Non-aqueous inkjet ink and inkjet recording method - Google Patents

Abstract

The present invention has printability (rubbing resistance, alcohol wiping resistance) on a plastic recording medium such as polyvinyl chloride, is excellent in safety, can be used without problems of odor, and particularly has high glossiness and optical density. An excellent non-aqueous inkjet ink and an inkjet recording method using the same are provided. This non-aqueous inkjet ink includes at least a pigment, a fixing resin, a compound (A) composed of one or more compounds selected from the group of compounds represented by the following general formulas (1) and (2), and the following general formula [I And a polyallylamine derivative represented by the formula: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3]

Description

  The present invention relates to a novel non-aqueous inkjet ink and inkjet recording method.

  In recent years, the inkjet recording method can be easily and inexpensively created images, and thus has been applied to various printing fields such as photographs, various printing, marking, and special printing such as color filters.

  As the ink-jet ink used in such an ink-jet recording method, water-based ink mainly containing water, non-volatile solvent which does not volatilize at room temperature, oil-based ink which does not substantially contain water, solvent which volatilizes at room temperature A non-aqueous ink that is substantially free of water, a hot melt ink that heats and melts solid ink at room temperature, an actinic ray curable ink that cures with actinic rays such as light after printing, and the like. There are inkjet inks, and they are properly used depending on the application.

  On the other hand, plastic recording media such as polyvinyl chloride and polyethylene are used as recording media for outdoor postings that require long-term weather resistance and printed materials that require adhesion to curved objects. Recording media made of soft polyvinyl chloride are used in a wide range of applications. There are many methods for printing on soft polyvinyl chloride, but there is an inkjet recording method as a method suitable for the production of a small variety of products because there is no need to prepare a plate and the time to finish is short.

  When ink jet recording is performed on soft polyvinyl chloride, as an ink jet ink to be used, a non-aqueous ink containing a large amount of cyclohexanone or the like has been conventionally used. For example, an ink jet ink containing cyclohexanone is disclosed ( Patent Document 1). This cyclohexanone has a high solubility in soft polyvinyl chloride, and since the pigment in the ink-jet ink enters into the soft polyvinyl chloride, good scratch resistance and glossiness can be obtained. However, cyclohexanone has been designated as a first type organic solvent, which is not only a problem in safety, but also has a drawback that a local exhaust device is required when handling inkjet ink containing cyclohexanone.

On the other hand, non-aqueous inks characterized by not containing cyclohexanone have been developed and sold. For example, as a solvent for dissolving polyvinyl chloride, a non-aqueous ink containing a solvent such as N-methylpyrrolidone or amide is disclosed in place of cyclohexanone having the above-described problems (Patent Document 2,). 3). Also, non-aqueous inks to which a fixing resin such as vinyl chloride-vinyl acetate copolymer or acrylic is added for the purpose of improving image fastness such as scratch resistance are disclosed (see Patent Documents 4 and 5). With these configurations, it has been possible to obtain an ink jet ink that can suppress odor to some extent and can form an image having a certain degree of scratch resistance against polyvinyl chloride. However, there is a demand for higher image quality for recent ink jet printers, and there is a need for a system for forming ink jet images having both glossiness and high optical density.
Japanese translation of PCT publication No. 2002-526631 JP 2005-15672 A Japanese Patent Laid-Open No. 2005-60716 JP 2005-36199 A WO2004 / 007626 specification

  The present invention has been made in view of the above problems, and has an object of having printability (rubbing resistance, alcohol wiping resistance) on a plastic recording medium such as polyvinyl chloride, excellent safety, and odor. It is an object of the present invention to provide a non-aqueous ink jet ink excellent in gloss and high optical density, and an ink jet recording method using the same.

  The above object of the present invention is achieved by the following configurations.

  1. At least a pigment, a fixing resin, a compound (A) comprising at least one compound selected from the group of compounds represented by the following general formulas (1) and (2), and a polyallylamine represented by the following general formula [I] A non-aqueous ink-jet ink comprising a derivative.

[Wherein, R ¹ and R ² each represent a substituent having 1 to 6 carbon atoms, and R ¹ and R ² may be bonded to form a ring. ]

[Wherein, R ³ and R ⁴ each represent a substituent having 1 to 6 carbon atoms, and R ³ and R ⁴ may be bonded to form a ring. ]

[Wherein, X and Y each independently represent a hydrogen atom, a polymerization initiator residue or a chain transfer catalyst residue, and R ₁ represents a free amino group, NH ₃ ⁺ -OCOR ₂ or NHCOR ₂ . R ₂ represents a residue obtained by removing a carboxyl group from any of a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid. n represents an integer of 2 to 1,000. However, at least one of n R ₁ 's represents NHCOR ₂ . ]
2. 2. The non-aqueous inkjet ink according to 1 above, wherein the content of the compound (A) is 1.5% by mass or more and 30% by mass or less.

  3. 3. The non-aqueous inkjet ink according to 1 or 2 above, comprising a solvent (B) composed of one or more compounds selected from the compound group represented by the following general formulas (3) and (4).

[Wherein, R ⁵ and R ⁶ each represent a methyl group or an ethyl group, and OX ¹ represents an oxyethylene group or an oxypropylene group. ]

[Wherein, R ⁷ and R ⁸ each represent a methyl group or an ethyl group, and OX ² represents an oxyethylene group or an oxypropylene group. ]
4). 4. The non-aqueous ink jet ink as described in 3 above, wherein the content of the solvent (B) is 50% by mass or more and 90% by mass or less.

  5. 5. Said 3 or 4 characterized in that the solvent (B) is at least one selected from diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol diacetate and propylene glycol diacetate. Non-aqueous inkjet ink.

  6). 6. The non-aqueous inkjet ink according to any one of 1 to 5, wherein the fixing resin is a resin synthesized by a solution polymerization method.

  7. The fixing resin has a vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer having a number average molecular weight in the range of 10,000 to 30,000. 7. The non-aqueous inkjet ink according to any one of 1 to 6 above, which is at least one selected from a polymer and a vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer.

  8). 8. An inkjet recording method for recording an image on a recording medium using the non-aqueous inkjet ink according to any one of 1 to 7, wherein the recording medium does not contain polyvinyl chloride or a plasticizer. An ink jet recording method comprising at least one selected from a recording medium comprising a material and a non-absorbing inorganic base material as a constituent element.

  According to the present invention, it has printability (rubbing resistance, alcohol wiping resistance) on a plastic recording medium such as polyvinyl chloride, is excellent in safety, can be used without problems of odor, and is particularly glossy and highly optical. It was possible to provide a non-aqueous ink jet ink excellent in density and an ink jet recording method using the same.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of studying various solvents and combinations thereof for the non-aqueous ink jet ink in view of the above problems, the present inventor has found at least pigments, fixing resins, and compounds represented by the general formulas (1) and (2). A non-aqueous inkjet ink comprising a compound (A) comprising at least one selected compound and a polyallylamine derivative represented by the above general formula [I] is made of plastic such as polyvinyl chloride. It has been found that it has printability (rubbing resistance, alcohol wiping resistance) for recording media, is safe and can be used without problems of odor, and in particular, can realize non-aqueous inkjet inks with excellent gloss and high optical density. It was.

  Although the detailed mechanism is unknown and only an estimate, the compound (A) composed of one or more compounds selected from the compound group represented by the general formulas (1) and (2) and the general formula [I ], The pigment is uniformly dispersed in a fine state to increase the color development efficiency per fixed amount of pigment and improve the smoothness of the coating film surface of the ink formed on the recording medium. Presumed to be. In addition, the dissolution stability of the fixing resin in the ink is improved, the ink is printed on a recording medium, the devitrification of the fixing resin after drying is suppressed, and the scattering of reflected light on the image surface is also suppressed. Presumed to have been obtained. With the above effects, it is presumed that the glossiness and optical density targeted by the present invention are improved.

  Hereinafter, the configuration of the non-aqueous inkjet ink of the present invention will be specifically described.

  The non-aqueous inkjet ink of the present invention (hereinafter also referred to as inkjet ink or ink) is one or more selected from pigments, fixing resins, sulfoxides represented by the general formulas (1) and (2), or a sulfone compound group. And a polyallylamine derivative represented by the above general formula [I].

[Compounds represented by general formulas (1) and (2)]
Next, details of the compounds represented by the general formulas (1) and (2) according to the present invention will be described.

In the general formula (1), R ¹ and R ² each represent a substituent having 1 to 6 carbon atoms, such as a linear or branched alkyl such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Groups, alkyl groups substituted with heteroatoms such as hydroxyethyl group, acetyl group, and acetonyl group, cyclic groups such as cyclohexyl group and phenyl group, or aromatic substituents, and R ¹ and R ² are They may be the same or different, and R ¹ and R ² may be bonded to each other to form a ring.

In the general formula (2), R ³ and R ⁴ each represent a substituent having 1 to 6 carbon atoms, for example, a linear or branched alkyl such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Groups, alkyl groups substituted with heteroatoms such as hydroxyethyl group, acetyl group, and acetonyl group, cyclic groups such as cyclohexyl group and phenyl group, or aromatic substituents, and further R ³ and R ⁴ are They may be the same or different, and R ³ and R ⁴ may be bonded to each other to form a ring.

  Examples of the compound represented by the general formulas (1) and (2) include dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, diphenyl sulfoxide, tetraethylene sulfoxide, dimethyl sulfone, methyl ethyl sulfone, and methyl-isopropyl sulfone. , Methyl-hydroxyethyl sulfone, sulfolane and the like.

  The content of the compound (A) in the inkjet ink is preferably 1.5% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and particularly preferably 5% by mass. % Or more and 15% by mass or less. When the content of the compound (A) is 1.5% or more, the solubility of the ink in polyvinyl chloride is sufficient, and scratch resistance and alcohol wiping resistance against polyvinyl chloride can be obtained. Moreover, if it is 3 mass% or more, the abrasion resistance with respect to polyvinyl chloride and alcohol wiping resistance are favorable, and if it is 30 mass% or less, stable emission without causing abnormalities of the inkjet head due to long-term use. It can be performed.

[Compound represented by general formula [I]]
Next, details of the polyallylamine derivative represented by the general formula [I] according to the present invention will be described.

  The polyallylamine derivative according to the present invention includes, for example, one or more compounds selected from three compounds of polyallylamine and polyester having a free carboxyl group, polyamide or a co-condensate of ester and amide (polyesteramide). It can be obtained by reacting with a compound.

  More specifically, this polyallylamine derivative includes, for example, a polyallylamine having a polymerization degree of 2 to 1,000, a polyester having a free carboxyl group, represented by the following general formula [II] or [III], and the following general One of the polyamides represented by the formula [IV] or [V] can be used alone or in combination of two or more, and can be prepared as a raw material.

In the general formula [II], R ₃ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and a represents an integer of 2 to 100.

In the general formula [III], R ₄ represents a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ₅ is a straight chain having 2 to 20 carbon atoms. It represents a chain or branched alkylene group or a residue obtained by removing two hydroxyl groups from polyalkylene glycol, and b represents an integer of 2 to 100. Further, the chain may have an ether bond.

In the general formula [IV], R ₆ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and c represents an integer of 2 to 100.

In the general formula [V], R ₄ represents a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ₇ is a straight chain having 2 to 20 carbon atoms. A chain or branched alkylene group is represented, and d represents an integer of 2 to 100.

  The polyallylamine derivative according to the present invention is a polyester in which the repeating components of the general formula [II] and the general formula [III] are randomly polymerized on the polyallylamine, the repeating of the general formula [IV] and the general formula [V]. Manufactured by reacting a polyamide in which components are randomly polymerized, and further a polyester amide in which the repeating components of general formula [II] or general formula [III] and general formula [IV] or general formula [V] are randomly polymerized. be able to.

  The polyallylamine used for the production of the polyallylamine derivative according to the present invention is obtained by polymerizing allylamine in the presence of a polymerization initiator and, in some cases, in the presence of a chain transfer catalyst.

  The polymerization initiator is not particularly limited, and polymerization initiators usually used in this field, for example, ketone peroxides such as methyl ethyl ketone, diacyl peroxides such as benzoyl peroxide, diisopropyl peroxydicarbonate, etc. Peroxydicarbonates such as 1, peroxyketals such as 1,1-bis (t-butylperoxy) cyclohexane, hydroperoxides such as t-butylhydroperoxide, t-butylperoxypivalate, etc. Peroxyesters, other azobisisoptylonitrile, hydrogen peroxide, ferrous salt and the like can be mentioned. Furthermore, a polymerization initiator described in JP-B-2-14364 may be used.

  Examples of the chain transfer catalyst include alkyl mercaptans such as lauryl mercaptan, thiocarboxylic acids such as mercaptoacetic acid, 2-mercaptopropionic acid and 3-mercaptopropionic acid, butyl thioglycolate, 2-ethylhexyl thioglycolate and the like. However, it is not limited to these.

  The number average molecular weight of the polyallylamine used in the present invention is not particularly limited as long as it is 150 to 100,000, but 600 to 20,000 is more preferable.

  The reason why the number average molecular weight of the polyallylamine used in the present invention is preferably 150 to 100,000 is that if the average molecular weight is 150 or more, the adsorptive power to the pigment is sufficient and the pigment dispersion becomes easy, and the number average molecular weight is 100,000 or less. For example, the occurrence of aggregation between pigments is suppressed, and pigment dispersion becomes easy.

  The polyallylamine can of course be used as a commercial product, and as such a commercial product, for example, “PA-1L”, “PA-1LV”, “PAA-1.4L” manufactured by Nitto Boseki Co., Ltd., “PAA-10C”, “PAA-15”, “PAA-15B”, “PAA-L”, “PAA-H”, “PAA-1L-15C” and the like can be mentioned.

  Moreover, polyallylamine of arbitrary molecular weight can be prepared using the method described in Japanese Patent Publication No. 2-14364.

  Examples of the polyester used for the preparation of the polyallylamine derivative according to the present invention include compounds represented by the general formula [II] or the general formula [III]. In addition, polyesters in which the repeating components of the general formulas [II] and [III] are randomly polymerized may be used.

  The polyester represented by the general formula [II] can be prepared using a hydroxycarboxylic acid represented by the following general formula [VI] or a lactone represented by the following general formula [VII] as a raw material.

  More specifically, it can be produced by adding a polymerization catalyst to hydroxy acid, lactone, or a mixture of hydroxy acid and lactone and heating. The reaction temperature is 120 to 220 ° C, preferably 160 to 210 ° C. The reaction time is 0.5 to 72 hours. At this time, when carried out in a nitrogen stream, a polymer having a high degree of polymerization can be obtained. At this time, if a polymerization initiator is used, the reaction can be easily controlled. In addition, when lactone is used as a raw material, monocarboxylic acid can be used as a polymerization initiator at a ratio of 0 to 0.5 mol with respect to 1 mol of lactone.

In the above general formula [VI] and general formula [VII], R ₃ represents a linear or branched alkylene group having 2 to 20 carbon atoms.

  Examples of the hydroxycarboxylic acid represented by the general formula [VI] include ricinoleic acid, ricinolenic acid, a mixture of 9 and 10-hydroxystearic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, and lactic acid. Etc. Examples of the lactone represented by the general formula [VII] include ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methylcaprolactone, 2- And methyl caprolactone.

  Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide. Quaternary ammonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphorus In addition to quaternary phosphonium salts such as phonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, organic compounds such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate In addition to alkali metal alcoholates such as carboxylates, sodium alcoholates and potassium alcoholates, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride, and the like.

  Examples of the polymerization initiator include aliphatic monocarboxylic acids such as acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isononanoic acid, and arachidic acid, Examples thereof include monocarboxylic acids such as benzoic acid and aromatic monocarboxylic acids such as p-butylbenzoic acid.

The polyester of the general formula [III] can be prepared by reacting a diol represented by HO—R ₅ —OH with a dibasic acid represented by HO—CO—R ₄ —COOH.

In the formula, R ₄ represents a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ₅ is a linear or branched group having 2 to 20 carbon atoms. It represents a residue obtained by removing two hydroxyl groups from a branched alkylene group or polyalkylene glycol.

  More specifically, it can be produced by adding a polymerization catalyst to an equimolar mixture of the diol and dibasic acid and heating. At this time, it is preferable to add the dibasic acid slightly in excess. The reaction temperature is 120 to 220 ° C, more preferably 160 to 210 ° C. The reaction time is 0.5 to 72 hours. At this time, when carried out in a nitrogen stream, one having a high degree of polymerization can be obtained. At this time, it is preferable to use a polymerization initiator in that the reaction can be easily controlled.

  Examples of the diol include ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and other alkylene glycols, diethylene glycol, dipropylene glycol, Examples include diols containing an ether bond such as triethylene glycol. Examples of dibasic acids include dibasic acids having an unsaturated bond such as maleic anhydride and fumaric acid, aromatic dibasic acids such as phthalic anhydride and terephthalic acid, and saturated dibasic acids such as adipic acid and sebacic acid. Dibasic acids can be mentioned.

  The polymerization catalyst and polymerization initiator used for the reaction may be the same as those used for the production of the polyester represented by the general formula [II].

  The polyester in which the repeating components of the general formula [II] and the general formula [III] are randomly polymerized is obtained by adding a polymerization catalyst to a mixture of hydroxy acid, lactone, or an equimolar mixture of the diol and dibasic acid. It can be manufactured by heating. The reaction conditions are the same as the conditions for the preparation of the general formula [II].

  The polyester in which the repeating components of the general formula [II] and the general formula [III] are polymerized in a block form can be obtained by preliminarily preparing the polyester of the [II] and the general formula [III], followed by dehydration condensation. it can.

  The molecular weight of the polyester used in the present invention may be in the range of 300 to 20,000, but 1,000 to 10,000 is preferable from the viewpoint of pigment dispersion performance. If the molecular weight is 300 or more, the length of the dispersant side chain is sufficient, and a good dispersion effect can be obtained. If the molecular weight is 20,000 or less, the length of the dispersant side chain is excessively long. Without being too much, aggregation of the pigments can be prevented, and a decrease in fluidity can be suppressed. In order to obtain such a molecular weight polyester, it is necessary to set the molar ratio of the polymerization initiator and the raw material hydroxy acid, lactone, diol, dibasic acid, and observe the acid value of the reaction product in the middle. This is made possible by setting an appropriate reaction time.

  Examples of the polyamide used for the preparation of the polyallylamine derivative according to the present invention include compounds represented by the general formula [IV] or the general formula [V]. In addition to this, the repeating components of the general formula [IV] and the general formula [V] may be randomly polymerized.

The polyamide represented by the general formula [IV] is prepared using a lactam represented by the following general formula [VIII] or an aminocarboxylic acid represented by H ₂ N—R ₆ —COOH as a raw material. R ₆ represents a linear or branched alkylene group having 2 to 20 carbon atoms.

More specifically, it can be produced by heating a lactam represented by the general formula [VIII], an aminocarboxylic acid represented by H ₂ N—R ₆ —COOH, or a mixture of a lactam and an aminocarboxylic acid. The polycondensation reaction is preferably performed under a nitrogen stream, and the reaction temperature is 150 to 210 ° C. If it is 250 degrees C or less, coloring can be suppressed, and if it is 110 degrees C or more, sufficient reaction rate can be obtained. The reaction time is 0.5-72. At this time, if a polymerization initiator is used, the reaction can be easily controlled. Furthermore, the reaction time can be shortened by adding a polymerization catalyst. Molecular weight can be measured by oxidation. When lactam is used as a raw material, the polymerization initiator monocarboxylic acid can be used at a ratio of 0 to 0.5 mole per mole of lactam.

  Examples of the lactam include ε-caprolactam, ω-laurolactam, and aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid. Moreover, the thing similar to what was used for manufacture of polyester can be used for a polymerization catalyst and a polymerization initiator.

The polyamide of the general formula [V] is a dibasic acid represented by the HO—CO—R ₄ —COOH and H ₂ N—R ₇ —NH ₂ (R ₇ is a straight chain having 2 to 20 carbon atoms). Represents a branched or branched alkylene group). The dibasic acid used here is the same as that used in the production of the polyester, and examples of the diamine include ethylenediamine, 1,4-diaminobutane, hexamethylenediamine and the like.

  The reaction conditions and the like in the production of the general formula [V] polyamide are the same as the production conditions of the polyamide represented by the general formula [IV].

  In order to produce a polyamide in which the repeating components of the general formula [IV] and the general formula [V] are randomly polymerized, the lactam and aminocarboxylic acid used in the production of the general formula [IV] and the general formula [V], respectively, are used. It can manufacture by applying the polymerization conditions of the polyamide demonstrated above using an acid, a dibasic acid, and diamine.

  The ester and amide cocondensate (polyesteramide) used in the preparation of the polyallylamine derivative according to the present invention is any of the hydroxycarboxylic acids, lactones, dibasic acids and diols used in the production of the polyesters and polyamides. One or more selected from one or more selected from aminocarboxylic acid, lactam, dibasic acid and diamine can be prepared by applying the above polymerization conditions for polyamide.

  Further, it can be prepared by precondensing polyester and polyamide obtained by the above preparation method and further co-condensing them. The polymerization conditions are the same as above, and the reaction can be terminated at the desired degree of polymerization by observing the acid value of the reaction product.

  The reaction between the polyallylamine and the polymer introduced into the side chain will be described in detail. One mole of polyallylamine having n amino groups is a polyester, polyamide or ester / amide cocondensate having a free carboxyl group (polyesteramide). 1) or more of the compounds are mixed at a ratio of 1 mol or more and preferably 2 mol or more and 2 nmol or less from the viewpoint of pigment dispersibility. At this time, different types of polyesters, polyamides or co-condensates of esters and amides (polyester amides) may be reacted simultaneously. A polymerization catalyst may be used for the reaction, and examples of the polymerization catalyst used include those described above for the production of polyester. Moreover, it does not matter at all even if solvents, such as xylene and toluene, are used for reaction.

  At this time, the reaction of polyallylamine with a polyester having a free carboxyl group, a polyamide or an ester-amide cocondensate (polyesteramide) is a salt formation via the former free amino group and the latter terminal free carboxyl group. Or it is an acid amide bond formation reaction. In addition, when polyester or polyesteramide is used, ester-amide exchange reaction occurs simultaneously depending on the type of polyester or polyesteramide used by these esters and the amino group of the side chain of polyallylamine, and depending on the reaction conditions. . In this reaction, whether a salt or an acid amide bond is formed depends on the reaction conditions.

  Although the acid amide bond forming reaction and the salt forming reaction proceed simultaneously, the acid amide bond forming reaction is preferably performed at 90 to 210 ° C, preferably 100 to 210 ° C. When it is 250 ° C. or higher, the reaction product is colored, and when it is 90 ° C. or lower, the reaction time is prolonged. Further, when the reaction is carried out in a nitrogen stream, a product with low coloration is obtained.

  On the other hand, 20-140 degreeC is preferable as reaction temperature which performs salt formation.

The polyallylamine derivative according to the present invention is an acid amide in which the terminal carboxyl group of the polyester, polyamide or co-condensate of ester and amide (polyesteramide) is 2 mol or more with respect to the polyallylamine having n amino groups. What performed formation reaction is preferable at the point of pigment dispersibility. In particular, in the general formula [I], in the n R ₁ , those having a residue in the form of an acid amide bond represented by NHCOR ₂ in a range of 60 to 95% are preferable, and still more preferable. Are preferably present in a range of 65 to 90% of residues in a form linked by an acid amide bond.

  This is because, when less than 60% of amino groups of polyallylamine are covalently bonded via an amide bond, aggregation of pigments occurs, resulting in insufficient viscosity reduction effect and defects in coating film appearance. Cannot be used as a dispersant. In addition, when 96% or more of amino groups of polyallylamine are covalently bonded via an amide bond, the functional group that adsorbs to the pigment is insufficient, making it difficult to contribute to pigment dispersion, resulting in a viscosity reduction effect. It becomes deficient in the shortage and the appearance of the coating film and cannot be used as a dispersant.

  In the polyallylamine derivative according to the present invention, in order to bind the amino group of polyallylamine by a covalent bond within the above range, polyallylamine and polyester having a carboxyl group at one end, polyamide or ester-amide cocondensate (polyesteramide) The amine value A immediately after mixing at least one) and the amine value B after completion of the reaction are measured, and these changes can be calculated by the following equation 1.

(Formula 1)
Ratio of covalent bond of amino group of polyallylamine derivative = {(amine value A-amine value B) / amine value A} × 100
The amine value immediately after mixing may be measured, but since the reaction does not proceed immediately after mixing, the amine value of polyallylamine used as a raw material should be calculated from the mass of the polymer and polyallylamine used in the reaction. You can also. In addition, even if the amino group of polyallylamine and the carboxyl group of the polymer introduced into the side chain form a salt, it does not affect the desired amine value.

  Furthermore, the polyallylamine derivative according to the present invention has a mass ratio of 1/5 to 1/30 of polyallylamine and polyester, polyamide or ester / amide cocondensate (polyesteramide) having a carboxyl group at one end. When the amine value (mgKOH / g) of the obtained polyallylamine derivative is 5 to 30, the performance is further improved. If the amine value is 5 or more, sufficient adsorptive power to the pigment is obtained and the pigment dispersion is good, and if it is 30 or less, aggregation of pigments can be prevented.

  The acid value (mgKOH / g) of the polyallylamine derivative according to the present invention is preferably 2.5 to 50 in terms of pigment dispersion.

  In addition, the molecular weight of the polyallylamine derivative according to the present invention obtained by the above reaction is preferably 2000 to 100,000 when used as a pigment dispersant.

  In addition, the polyallylamine derivative according to the present invention is obtained by polymerizing the above polyester with any one or more of hydroxycarboxylic acid, lactone, dibasic acid and diol, aminocarboxylic acid, lactam, dibasic acid and diamine. It can also be prepared by using conditions.

  The polyallylamine derivative represented by the general formula [I] according to the present invention is preferably added in the range of 10% by mass to 200% by mass with respect to the pigment.

[Compounds Represented by General Formulas (3) and (4)]
The ink-jet ink of the present invention can contain a non-aqueous solvent, but includes a solvent (B) composed of one or more compounds selected from the compound group represented by the general formulas (3) and (4). It is preferable to contain.

In the general formula (3), R ⁵ and R ⁶ each represent a methyl group or an ethyl group, and OX ¹ represents an oxyethylene group or an oxypropylene group.

In the general formula (4), R ⁷ and R ⁸ each represent a methyl group or an ethyl group, and OX ² represents an oxyethylene group or an oxypropylene group.

  Specific compounds represented by the general formulas (3) and (4) according to the present invention include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol diacetate, propylene Examples thereof include glycol diacetate.

  Among these, the component of the solvent (B) is preferably at least one selected from diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol diacetate and propylene glycol diacetate. The quick-drying property of the ink when printed on vinyl can be further improved. Among them, a particularly preferable solvent (B) is one containing diethylene glycol diethyl ether and ethylene glycol diacetate in a ratio of at least 1: 1 to 10: 1.

  The content of the solvent (B) in the ink-jet ink is preferably 50% by mass or more and 90% by mass or less, and by using such a solvent configuration, quick drying property and emission stability at the time of printing polyvinyl chloride. In addition, the ink odor can be reduced.

[Other solvents]
In the inkjet ink of the present invention, in addition to the compound (A) and the solvent (B) according to the present invention, a conventionally known solvent may be contained within a range that does not impair the object effects of the present invention. Examples of the solvent include alkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, and alkylene glycols such as ethylene glycol dibutyl ether and tetraethylene glycol dimethyl ether. Examples include dialkyl ethers and alkylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate.

[Fixing resin]
Next, the fixing resin according to the present invention will be described.

  In the ink-jet ink of the present invention, various fixing resins (hereinafter also simply referred to as resins) are added in order to improve fixability when recording on a plastic recording medium such as polyvinyl chloride.

  Examples of the resin to be added include acrylic resins, polyester resins, polyurethane resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, and the like.

  Specifically, acrylic resins such as John Crill (manufactured by Johnson Polymer Co., Ltd.), ESREC P (manufactured by Sekisui Chemical Co., Ltd.), polyester resins such as Elitel (manufactured by Unitika Ltd.), Byron (manufactured by Toyobo), Toyobo Co., Ltd.), NT-Hilamic (Daiichi Seika Co., Ltd.), Crisbon (Dainippon Ink Chemical Co., Ltd.), Nipporan (Nihon Polyurethane Co., Ltd.) and other polyurethane resins, SOLBIN (Nisshin Chemical Co., Ltd.) (Nissin Chemical Industry Co., Ltd.), Saran Latex (Asahi Kasei Chemicals Co., Ltd.), Sumielite (Sumitomo Chemical Co., Ltd.), Sekisui PVC (Sekisui Chemical Co., Ltd.), UCAR (Dow Chemical Co., Ltd.) Can be mentioned.

  The fixing resin acts as a binder that adheres a coloring material such as a pigment to the recording medium after printing. The larger the molecular weight of the fixing resin, the better the adhesion and durability. In addition, the smaller the molecular weight, the lower the viscosity of the ink. However, the lower the viscosity, the lower the energy required for ejecting the ink during printing, so that the inkjet head is not burdened and it is easier to eject stably. Therefore, if the number average molecular weight is 10,000 or more, the fixability after printing is sufficiently exhibited, and if it is 30000 or less, it does not impose a load on the ejection of the ink, which is preferable.

  Particularly preferred fixing resins have a number average molecular weight in the range of 10,000 to 30,000, and compositions include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate- At least one resin selected from vinyl alcohol copolymer and vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer, vinyl chloride-vinyl acetate copolymer and vinyl chloride-vinyl acetate-maleic anhydride copolymer These vinyl chloride-vinyl acetate copolymers and vinyl chloride-vinyl acetate-maleic anhydride copolymers may be mixed with acrylic resins, polyester resins, polyurethane resins, etc. May be used.

  By adding these fixing resins to the ink of the present invention, the emission stability, scratch resistance and alcohol wiping resistance can be improved in a balanced manner.

  The alcohol wiping resistance referred to in the present invention is resistance to disturbance such as image peeling when wiping the surface of the image with ethanol or a mixed solvent of ethanol and water. Wipe off dirt on the image surface with alcohol for posters for outdoor use. It is a user need for that.

  As a method for synthesizing the fixing resin according to the present invention, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and the like can be applied without particular limitation. Among them, the solution polymerization method is preferable.

  The solution polymerization method is one of the methods used for radical polymerization of a monomer having a vinyl group. The monomer and initiator are dissolved in a solvent in which the polymer to be generated is soluble, and the polymerization is performed by heating. Is the method.

  The fixing resin synthesized by the solution polymerization method has high solubility even if it has a relatively high molecular weight, and more resin can be contained in the ink, so that the scratch resistance can be improved.

  The content of the fixing resin in the ink of the present invention is preferably 1 to 10% by mass. When the content is 1% by mass or more, the image weather resistance when recorded on polyvinyl chloride is enhanced, and when the content is 10% by mass or less, the ink ejection from the inkjet head is easily stabilized, and more preferable. The range of content is 3-7 mass%.

[Pigment]
Next, the pigment according to the present invention will be described.

  In the non-aqueous ink jet ink of the present invention, the weather resistance of the recorded matter recorded on a plastic recording medium such as polyvinyl chloride can be enhanced by using a pigment as a coloring material.

  As the pigment that can be used in the present invention, conventionally known pigments can be used without particular limitation. For example, organic pigments such as insoluble pigments and lake pigments, and inorganic pigments such as carbon black can be preferably used.

  The insoluble pigment is not particularly limited, for example, azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, Dioxazine, thiazole, phthalocyanine, diketopyrrolopyrrole and the like are preferable.

  Specific pigments that can be preferably used include the following pigments.

  Examples of the magenta or red pigment include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 12, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48 (Ca), C.I. I. Pigment red 48 (Mn), C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57 (Ca), C.I. I. Pigment red 57: 1, C.I. I. Pigment red 112, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 184, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 222, C.I. I. Pigment red 254, C.I. I. Pigment violet 19 and the like.

  Examples of the pigment for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 15: 3, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 130, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 213, C.I. I. And CI Pigment Yellow 214.

  Examples of the pigment for green or cyan include C.I. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

In addition to the above, when red, green, blue and intermediate colors are required, the following pigments are preferably used alone or in combination. I. Pigment Red 209, 224, 177, 194;
C. I. Pigment Orange 43;
C. I. Vat Violet 3;
C. I. Pigment Violet 19, 23, 37;
C. I. Pigment Green 36, 7;
C. I. Pigment Blue 15: 6;
Etc. are used.

  Examples of black pigments include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like.

  The content of these pigments in the ink of the present invention is preferably 2 to 10% by mass. In order to reduce the graininess of the image, a light color ink may be used. In this case, the pigment content is preferably 1/5 to 1/2 with respect to the dark color ink.

  The pigment according to the present invention is preferably used after being dispersed by a disperser together with a pigment derivative having a basic group according to the present invention, a dispersant, and other additives necessary for various desired purposes. As the disperser, conventionally known dispersers such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used.

  The average particle size of the pigment dispersion used in the ink of the present invention is preferably 10 nm or more and 200 nm or less, and more preferably 50 nm or more and 150 nm or less. By making the average particle size 10 nm or more, aggregation of pigment particles is less likely to occur, and by making the average particle size 200 nm or less, it becomes easy to suppress the phenomenon that the pigment settles when stored over a long period of time. By setting the average particle size in the above range, it becomes easy to obtain an ink having good storage stability.

  The particle size of the pigment dispersion can be measured by a commercially available particle size measuring device using a light scattering method, an electrophoresis method, a laser Doppler method or the like. It is also possible to obtain a particle image with a transmission electron microscope on at least 100 particles and perform statistical processing on the image using image analysis software such as Image-Pro (manufactured by Media Cybernetics). Is possible.

  In the ink of the present invention, the polyallylamine derivative represented by the general formula [I] according to the present invention is used as a pigment dispersant, but it is conventionally known as long as the object effects of the present invention are not impaired. These pigment dispersants can be used together.

  Examples of pigment dispersants that can be used in combination include surfactants and polymer dispersants. Polymer dispersing agents include (meth) acrylic resins, styrene- (meth) acrylic resins, hydroxyl group-containing carboxylic acid esters, salts of long-chain polyaminoamides and high molecular weight acid esters, salts of high molecular weight polycarboxylic acids, long Salt of chain polyaminoamide and polar acid ester, high molecular weight unsaturated acid ester, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, Examples thereof include polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, stearylamine acetate, and pigment derivatives.

  Specifically, Jonkrill (manufactured by Johnson Polymer), Anti-Terra-U (manufactured by BYK Chemie), Disperbyk (manufactured by BYK Chemie), Efka (manufactured by Efka CHEMICALS), Floren (manufactured by Kyoeisha Chemical), Disparon (manufactured by Enomoto Kasei Co., Ltd.), demol (manufactured by Kao Co., Ltd.), homogenol, Emulgen (manufactured by Kao Co., Ltd.), Solspers (manufactured by Avicia Co., Ltd.), Nikkor (manufactured by Nikko Chemical Co., Ltd.) and the like.

[Other additives]
In addition to the above description, the inkjet ink of the present invention is publicly known depending on the purpose of improving the emission stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other various performances as necessary. Various additives such as a viscosity modifier, a specific resistance modifier, a film forming agent, an ultraviolet absorber, an antioxidant, a discoloration inhibitor, an antifungal agent, and a rust inhibitor can be appropriately selected and used.

[Inkjet recording method]
The ink-jet head used when forming an image by discharging the ink-jet ink of the present invention may be an on-demand system or a continuous system. In addition, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method (for example, thermal ink jet) Any ejection method such as a mold, a bubble jet (registered trademark) mold, or the like may be used.

  In the ink jet recording method using the ink jet ink of the present invention, for example, an ink jet recorded image is obtained by ejecting ink from an ink jet head based on a digital signal and adhering it to a recording medium by a printer loaded with the ink jet ink. . In order to quickly and surely dry the ink adhered to the recording medium, a method of forming an image by increasing the surface temperature of the recording medium is preferable.

  The surface temperature is adjusted according to the durability of the recording medium and the drying property of the ink used, but is preferably 40 to 100 ° C. In particular, when polyvinyl chloride is used as the recording medium, increasing the surface temperature improves the wettability of the ink with respect to the surface of the recording medium. Therefore, it is more preferable to record at a higher surface temperature.

  Depending on the brand of the recording medium made of polyvinyl chloride, there may be a difference in wettability and ink drying, so the surface temperature may be adjusted according to the characteristics of each medium.

  When recording is performed by increasing the surface temperature of the recording medium, it is preferable to mount a heater on the ink jet recording apparatus, and by heating the recording medium before or during transport of the recording medium, the surface temperature of the recording medium alone by the ink jet recording apparatus Can be adjusted.

〔recoding media〕
In the inkjet recording method of the present invention, when an image is recorded on a recording medium using the non-aqueous inkjet ink of the present invention, polyvinyl chloride, a resin base material not containing a plasticizer, and a non-absorbing material are used as the recording medium. It is characterized by using at least one recording medium selected from recording media having an inorganic base material as a constituent element.

  Specific examples of polyvinyl chloride, which is one of the recording media used in the ink jet recording method of the present invention, include SOL-371G, SOL-373M, SOL-4701 (manufactured by Big Technos Co., Ltd.), glossy PVC (Co., Ltd.). Systemgraph Co., Ltd.), KSM-VS, KSM-VST, KSM-VT (above, manufactured by Kimoto Co., Ltd.), J-CAL-HGX, J-CAL-YHG, J-CAL-WWWG (above, Showa Co., Ltd.) (Made in Osaka), BUS MARK V400 F vinyl, LITEcal V-600F vinyl (above, made by Flexcon), FR2 (made by Hanwha), LLBAU13713, LLSP20133 (above, made by Sakurai), P-370B, P-400M ( As described above, manufactured by Kambo Plus Co., Ltd.), S02P, S12 , S13P, S14P, S22P, S24P, S34P, S27P (above, manufactured by Grafityp), P-223RW, P-224RW, P-249ZW, P-284ZC (above, manufactured by Lintec Corporation), LKG-19, LPA- 70, LPE-248, LPM-45, LTG-11, LTG-21 (above, manufactured by Shinsei Co., Ltd.), MPI3023 (manufactured by Toyo Corporation), Napoleongros glossy PVC (manufactured by Futaki Electronics Co., Ltd.) , JV-610, Y-114 (above, manufactured by ICC Corporation), NIJ-CAPVC, NIJ-SPVCGT (above, manufactured by Nichie Corporation), 3101 / H12 / P4, 3104 / H12 / P4, 3104 / H12 / P4S, 9800 / H12 / P4, 3100 / H12 / R2, 3101 / H12 / R2, 3104 / H12 / R2, 1445 / H14 / P3, 1438 / One Way Vision (manufactured by Inetrcoat), JT5129PM, JT5728P, JT5822P, JT5829P, JT5829R, JT5829PM, JT5829PM, JM59t MPI1005, MPI1900, MPI2000, MPI2001, MPI2002, MPI3000, MPI3021, MPI3500, MPI3501 (above, manufactured by Avery), AM-101G, AM-501G (above, manufactured by Ginichi Co., Ltd.), FR2 (Hanfa Japan Co., Ltd.), AY-15P, AY-60P, AY-80P, DBSP137GGH, DBSP137GGL SJT-V200F, SJT-V400F-1 (above, manufactured by Hiraoka Orizome Co., Ltd.), SPS-98, SPSM-98, SPSH-98, SVGL-137, SVGS-137, MD3-200 MD3-301M, MD5-100, MD5-101M, MD5-105 (manufactured by Metamark), 640M, 641G, 641M, 3105M, 3105SG, 3162G, 3164G, 3164M, 3164XG, 3164XM, 3165G, 3165SG, 3165M, 3169M, 3451SG, 3551G, 3551M, 3631, 3641M, 3651G, 3651M, 3651SG, 3951G, 3641M (manufactured by Orafol), SVTL-HQ130 (manufactured by Lamy Corporation), S 300 GWF, SPCLEARAD vinyl (above, made by Catalina), RM-SJR (made by Ryoyo Corporation), Hi Lucky, New Lucky PVC (above, made by LG), SIY-110, SIY-310, SIY-320 ( As described above, Sekisui Chemical Co., Ltd., PRINT MI Frontlit, PRINT XL Light weight banner (hereinafter, manufactured by Endutex), RIJET 100, RIJET 145, RIJET 165 (above, manufactured by Ritrama), NM-SG, NM-SM NEIEI KAKO Co., Ltd.), LTO3GS (Lukio Co., Ltd.), Easy Print 80, Performance Print 80 (above, Jetgraph Co., Ltd.), DSE 550, DSB 550, DSE 80 0G, DSE 802/137, V250WG, V300WG, V350WG (above, manufactured by Hexis), Digital White 6005PE, 6010PE (above, made by Multifix), and the like.

  Moreover, as a recording medium having a resin base material containing no plasticizer or a non-absorbing inorganic base material as a constituent element, the following various base materials are used as constituent elements, and one kind of base material is used alone, or a plurality of kinds are used. These substrates can be used in combination. Examples of the resin base material containing no plasticizer used in the present invention include ABS resin, polycarbonate (PC) resin, polyacetal (POM) resin, polyamide (PA) resin, polyethylene terephthalate (PET) resin, polyimide (PI). Examples thereof include a resin, an acrylic resin, a polyethylene (PE) resin, a polypropylene (PP) resin, and a hard polyvinyl chloride (PVC) resin that does not contain a plasticizer.

  These resins are characterized by not containing a plasticizer, but there are no particular restrictions on other properties such as thickness, shape, color, softening temperature, and hardness.

  The recording medium used in the present invention is preferably ABS resin, PET resin, PC resin, POM resin, PA resin, PI resin, hard PVC resin containing no plasticizer, acrylic resin, PE resin, or PP resin. More preferred are ABS resin, PET resin, PC resin, PA resin, hard PVC resin not containing plasticizer, and acrylic resin.

  Moreover, as a non-absorbing inorganic base material used for this invention, a metal plate, such as a glass plate, iron, and aluminum, a ceramic plate etc. are mentioned, for example. These inorganic substrates are characterized by not having an ink-absorbing layer on the surface. These non-absorbing inorganic base materials are not particularly limited with respect to other properties such as thickness, shape, color, softening temperature, and hardness.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

  Further, the pigment dispersant and fixing resin described below were used after diluting the low boiling point solvent by distillation under reduced pressure and diluting with an organic solvent used for dispersion so that the solid content was 20% by mass. Hereinafter, the amounts of the pigment dispersant and the fixing resin used represent solid content conversion values.

Example 1
<< Preparation of pigment dispersant >>
According to the method described in JP-A-9-169821, using a 10% by weight aqueous solution of polyallylamine having a number average molecular weight of about 3000 and a polyester raw material compound, changing the mixing ratio, the number averages shown in Table 1 Pigment dispersants 1 to 5 according to the present invention having molecular weight, oxidation, and amine value were prepared.

  In the following ink preparation, as a comparative example, commercially available Solspers 32000 (manufactured by Lubrizol, polyethyleneimine polymer dispersant) was used as the pigment dispersant 6.

<Preparation of ink>
[Preparation of Ink 1]
<Preparation of pigment dispersion 1>
C. I. Pigment Blue 15: 3 (hereinafter abbreviated as PB15: 3), 10 parts of Pigment Dispersant 1, 5.0 parts of Compound (A), 10 parts of dimethyl sulfoxide (S-2), and Solvent (B) 60 parts of diethylene glycol diethyl ether and 15 parts of ethylene glycol diacetate are mixed and dispersed using a horizontal bead mill (System Zeta Mini, manufactured by Ashizawa) filled with zirconia beads having a diameter of 0.5 mm by volume. After that, zirconia is dispersed. The beads dispersion 1 was obtained by removing the beads.

<Preparation of resin solution 1>
10 parts of dimethyl sulfoxide (S-2) as compound (A), 65 parts of diethylene glycol diethyl ether and 15 parts of ethylene glycol diacetate as solvent (B), vinyl chloride synthesized by solution polymerization method as fixing resin A resin solution 1 was prepared by mixing and dissolving 10 parts of a vinyl acetate copolymer (trade name VYHD, number average molecular weight 22000, manufactured by Dow Chemicals).

<Preparation of ink>
While stirring 50 parts of the resin solution 1, 50 parts of the pigment dispersion 1 was added and mixed, and then filtered through a 0.8 μm filter to obtain ink 1.

[Preparation of inks 2 to 40]
In the preparation of the ink 1, the kind of pigment, the kind and addition amount of the pigment dispersant, the kind and addition amount of the compound (A), the kind and addition amount of the solvent (B), the kind and addition amount of other solvents 2. Inks 2 to 40 were prepared in the same manner except that the changes were made as described in Table 3.

  In addition, the detail of each additive described by the abbreviation in Table 2 and Table 3 is as follows. In addition, the numerical value of content of Table 2 and Table 3 is the mass%.

[Pigment]
PB15: 3 C.I. I. Pigment Blue 15: 3
PY150 C.I. I. Pigment Yellow 150
PR122 C.I. I. Pigment Red 122
CB carbon black [fixing resin]
PVC: Solution polymerization vinyl chloride-vinyl acetate copolymer (trade name VYHD, manufactured by Dow Chemicals)
[Compound (A)]
S-1: Di-n-propyl sulfoxide S-2: Dimethyl sulfoxide S-3: Di-n-butyl sulfoxide S-4: Diphenyl sulfoxide S-5: Tetramethylene sulfoxide S-6: Dimethyl sulfone S-7: Di -N-propyl sulfone S-8: methyl isopropyl sulfone S-9: methyl hydroxyethyl sulfone S-10: sulfolane [solvent (B)]
DEGDEE: Diethylene glycol diethyl ether EGDAc: Ethylene glycol diacetate DEGDME: Diethylene glycol dimethyl ether PGDAc: Propylene glycol diacetate DPGDEE: Dipropylene glycol diethyl ether DPGDME: Dipropylene glycol dimethyl ether [Other solvents]
EGBEAc: ethylene glycol monobutyl ether acetate NMP: N-methylpyrrolidone << Evaluation of ink >>
Each ink prepared above was evaluated for odor resistance according to the following method.

[Evaluation of odor resistance]
About 1 to 50 of each of the inks 1 to 40 were put into a 500 ml polyethylene bottle, and the odor evaluation was performed by 10 subjects. Five points were determined to be almost odorless, and 5 points were determined to be very unpleasant odors. Points were assigned at each stage, and odor resistance was evaluated according to the following criteria.

A: The average score of 10 subjects is 4.0 points or more. ○: The average score of 10 subjects is 3.0 points or more and less than 4.0 points. Δ: The average score of 10 subjects is 2.0 points or more and less than 3.0 points ×: The average score of 10 subjects is less than 2.0 points << Evaluation of formed image >>
[Image formation]
Each ink is supplied to an on-demand type ink jet printer equipped with a piezo head having a nozzle diameter of 28 μm, a drive frequency of 15 kHz, a nozzle number of 512, a minimum liquid amount of 14 pl, a nozzle density of 180 dpi, and a heater having a maximum recording density of 1440 × 1440 dpi. Was loaded. Next, each ink was ejected, and a solid image of 10 cm × 10 cm was recorded on JT5929PM (manufactured by Mactac) which is a recording medium made of polyvinyl chloride. During printing, the recording medium was heated from the back side, and the heater temperature was set so that the surface temperature of the recording medium during image recording was 45 ° C. The surface temperature of the recording medium was measured using a non-contact thermometer (IT-530N type, manufactured by Horiba, Ltd.).

[Evaluation of image]
According to the above method, each image created from the inks 1 to 40 was evaluated according to the following method. In all cases, the performance of Δ or higher was regarded as an acceptable level.

<Evaluation of glossiness>
Using a handy gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd., the glossiness at a light projecting / receiving angle of 60 degrees is measured for a solid image recorded on polyvinyl chloride, and the glossiness is evaluated according to the following criteria. went. The glossiness represents the reflectance of each measurement sample when the reflectance when the standard plate attached to the gloss meter is measured is 100.

A: Glossiness is 80 or more, and it can be seen that the gloss is extremely excellent even by visual observation. B: Glossiness is 75 or more and less than 80, and the gloss is good by visual observation. Δ: Glossiness is high. It is found that the glossiness is acceptable by visual observation at 70 or more and less than 75. ×: The glossiness is less than 70 and it is determined that the glossiness is insufficient by visual observation. <Measurement of optical density>
For each solid image recorded on polyvinyl chloride, using an optical densitometer 938 spectrodensitometer manufactured by X-rite, the optical reflection density of cyan is used for the ink using PB15: 3 as the pigment, and PY150 is used as the pigment. The yellow optical reflection density was measured for the ink used, the magenta optical reflection density was measured for the ink using PR122 as the pigment, and the VIS optical reflection density was measured for the ink using carbon black as the pigment. A higher concentration is preferred.

  As is apparent from the results shown in Table 4, the ink having the constitution defined in the present invention has an odor resistance of the ink, and glossiness and optical properties particularly when an image is recorded on polyvinyl chloride compared to the comparative example. It can be seen that the concentration is excellent.

Example 2
<Preparation of ink>
[Preparation of Inks 41 to 62]
In the preparation of ink 1 described in Example 1, the type of pigment, the type of pigment dispersant, the type and amount of fixing resin, the type and amount of compound (A), the type and addition of solvent (B) Inks 41 to 62 were prepared in the same manner except that the amounts and other solvent types and addition amounts thereof were changed as shown in Table 5.

  In addition, the detail of each additive described by the abbreviation in Table 5 is as follows. In addition, the numerical value of content of Table 5 is the mass%.

(Pigment dispersant)
Pigment dispersant 7 Polyester raw material: 12-HS (12-hydroxystearic acid) / CL (ε-caprolactone) = 1/25 (molar ratio), number average molecular weight Mn of polyallylamine derivative: 2750, acid value: 19 mgKOH / g , Amine value: 16 mg KOH / g
[Fixing resin]
mPVC: solution polymerization vinyl chloride-vinyl acetate-maleic anhydride copolymer (trade name VMCC, manufactured by Dow Chemicals)
sPVC: suspension polymerization vinyl chloride-vinyl acetate copolymer (trade name SOLBIN TAO, manufactured by Nissin Chemical Co., Ltd.)
[Other solvents]
TEGDME: Tetraethylene glycol dibutyl ether DPGMEAc: Dipropylene glycol monomethyl ether acetate DEGDBE: Diethylene glycol dibutyl ether Except for the pigment dispersant, the fixing resin, and other solvents, details of each additive abbreviated in Table 5 are as follows. The same as in the first embodiment.

<Evaluation of ink>
For each of the inks prepared as described above, evaluation of emission was performed according to the following method, and odor resistance was evaluated by the same method as in Example 1.

(Evaluation of light emission)
Piezo-type head having a nozzle diameter of 28 μm, a drive frequency of 15 kHz, a nozzle number of 512, a minimum liquid amount of 14 pl, and a nozzle density of 180 dpi (where dpi represents the number of dots per 2.54 cm), and Japanese Patent Application Laid-Open No. 2002-363469 Using the strobe light emission type ink flight observation device shown in FIG. 2, the ejection cycle and the light emission cycle are synchronized, and the flight status of each ink is monitored by a CCD camera, and the emission property in an environment of 23 ° C. and 55% RH is observed. Evaluation was made according to the following criteria.

A: Ink droplets are ejected normally, and no abnormalities such as bending, missing, or speed variation occur even if the ejection is resumed after stopping for 3 minutes. O: The ink droplets are ejected normally and emitted. No problem occurs even after restarting after stopping for 1 minute, but there is a nozzle that bends and has a speed variation when restarting after stopping for 3 minutes. Δ: Ink droplets are ejected normally, but ejection There are nozzles that bend and vary in speed when restarted after being stopped for 1 minute. ×: There are nozzles that are difficult to normally eject ink droplets and cause bending, and many nozzles when ejection is resumed after stopping for 1 minute. Bending, speed variation, and missing parts <Evaluation of formed image>
Each image was formed from the inks 41 to 62 in the same manner as described in Example 1, and the glossiness and optical hardness were evaluated in the same manner as in the method described in Example 1. A performance of △ or higher was regarded as an acceptable level.

  Table 6 shows the results obtained as described above.

  As is apparent from the results shown in Table 6, the ink having the configuration defined in the present invention has a larger amount of ink in the ink without affecting the light emission by using a resin synthesized by a solution polymerization method as a fixing resin. It can be seen that a resin can be contained, and the glossiness and optical density are further improved.

Example 3
Using the inks 1 and 37 to 40 prepared in Example 1, images were formed using the recording media shown in Table 7 instead of polyvinyl chloride as the recording media, and the method described in Example 1 was used. Similarly, glossiness and optical density were evaluated, and the results obtained are shown in Table 7. A performance of △ or higher was regarded as an acceptable level.

  The details of each recording medium described in abbreviations in Table 7 are as follows.

PET: Polyethylene terephthalate sheet PP: Polypropylene sheet ABS: Acrylonitrile, butadiene, styrene copolymer sheet PC: Polycarbonate sheet POM: Polyoxymethylene resin sheet PA: Polyacrylate PI: Polyimide PVC: Polyvinyl chloride PE: Polyethylene

  As is apparent from the results shown in Table 7, using the ink of the present invention, an image was formed on a recording medium composed of polyvinyl chloride, a resin base material containing no plasticizer and a non-absorbing inorganic base material. It can be seen that excellent glossiness and optical density are exhibited even if it is carried out.

Example 4
<< Preparation of pigment dispersant >>
According to the method described in JP-A-9-169821, pigment dispersants 8 and 9 were prepared using polyallylamine, a polyamide raw material compound, or a polyesteramide raw material compound.

Pigment dispersant 8: Polyamide raw material, hexamethylenediamine / adipic acid = 2/3 (molar ratio), number average molecular weight Mn of polyallylamine derivative: 10500, amine value: 36 mgKOH / g
Pigment dispersant 9: raw material of polyesteramide, hexamethylenediamine / adipic acid / ethylene glycol = 7/11/2 (molar ratio), number average molecular weight Mn of polyallylamine derivative: 10500, amine value 39 mgKOH / g
<Preparation of ink>
In the preparation of the ink 1 described in Example 1, the inks 63 and 64 were prepared in the same manner except that the pigment dispersants 8 and 9 were used instead of the pigment dispersant 1 used for the preparation of the pigment dispersion 1. Prepared.

<Evaluation of ink>
The inks 63 and 64 prepared above were evaluated for odor resistance according to the method described in Example 1.

<Evaluation of formed image>
[Image formation]
The inks 63 and 64 prepared above were subjected to image formation according to the method described in Example 1.

[Evaluation of image]
According to the above method, each image created from the inks 63 and 64 was evaluated for glossiness and optical density according to the method described in Example 1, and the obtained results are shown in Table 8. In all cases, the performance of Δ or higher was regarded as an acceptable level.

  As is apparent from the results shown in Table 8, it can be seen that the ink having the constitution defined in the present invention is excellent in the odor resistance of the ink, the glossiness when an image is recorded on polyvinyl chloride, and the optical density. .

Claims (8)

At least a pigment, a fixing resin, a compound (A) composed of one or more compounds selected from the group of compounds represented by the following general formulas (1) and (2), and a polyallylamine represented by the following general formula [I] A non-aqueous ink-jet ink comprising a derivative.

[Wherein, R ¹ and R ² each represent a substituent having 1 to 6 carbon atoms, and R ¹ and R ² may be bonded to form a ring. ]

[Wherein, R ³ and R ⁴ each represent a substituent having 1 to 6 carbon atoms, and R ³ and R ⁴ may be bonded to form a ring. ]

[Wherein, X and Y each independently represent a hydrogen atom, a polymerization initiator residue or a chain transfer catalyst residue, and R ₁ represents a free amino group, NH ₃ ⁺ -OCOR ₂ or NHCOR ₂ . R ₂ represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid. n represents an integer of 2 to 1,000. However, at least one of n R ₁ 's represents NHCOR ₂ . ]   2. The non-aqueous inkjet ink according to claim 1, wherein the content of the compound (A) is 1.5% by mass or more and 30% by mass or less. The solvent (B) comprising one or more compounds selected from the group of compounds represented by the following general formulas (3) and (4) is contained. Non-aqueous inkjet ink.

[Wherein, R ⁵ and R ⁶ each represent a methyl group or an ethyl group, and OX ¹ represents an oxyethylene group or an oxypropylene group. ]

[Wherein, R ⁷ and R ⁸ each represent a methyl group or an ethyl group, and OX ² represents an oxyethylene group or an oxypropylene group. ]   The non-aqueous inkjet ink according to claim 3, wherein the content of the solvent (B) is 50% by mass or more and 90% by mass or less.   4. The solvent according to claim 3, wherein the solvent (B) is at least one selected from diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol diacetate and propylene glycol diacetate. Or the non-aqueous inkjet ink of a 4th term | claim.   6. The non-aqueous inkjet ink according to claim 1, wherein the fixing resin is a resin synthesized by a solution polymerization method.   The fixing resin has a vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer having a number average molecular weight in the range of 10,000 to 30,000. The non-aqueous inkjet ink according to any one of claims 1 to 6, wherein the non-aqueous inkjet ink is at least one selected from a polymer and a vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer. .   An inkjet recording method for recording an image on a recording medium using the non-aqueous inkjet ink according to any one of claims 1 to 7, wherein the recording medium is polyvinyl chloride, plastic An ink jet recording method comprising at least one selected from recording media comprising a resin base material containing no agent and a non-absorbing inorganic base material as a constituent element.