JP4642540B2 - Polymer compound, polymer antioxidant and recording medium to which the same is applied - Google Patents

Description

  The present invention is an antioxidant that effectively prevents discoloration of an image due to acidic gas or light in the atmosphere and bleeding of the image under high temperature and high humidity when recording with a printer or plotter using an ink jet recording method. The present invention relates to an agent and a recording medium suitable for long-term storage of an image to which the agent is applied.

  In the inkjet recording method, ink droplets adhere to a recording medium such as paper by various operating principles, and at the same time, the solvent component of the ink penetrates into the recording medium or evaporates, so that the color material component is covered. This is a recording method that deposits on a recording medium and records images, characters, and the like (hereinafter referred to as “images”). In addition, the ink jet recording system is characterized in that it has excellent high-speed printability, low noise, and flexibility in recording patterns, can easily perform multi-coloring, and does not require development and image fixing.

  In particular, an image formed by a multicolor ink jet method can obtain a recording that is inferior to an image by a multicolor printing by a plate making method or an image by a color photographic method. In recent years, it has rapidly spread as an image recording apparatus for various information devices because it has an advantage that the printing cost is lower than that of the printing technique and the photographic technique. For example, it is widely applied to fields that require full-color image recording, such as image design output in the design industry, production of color blocks in the printing field where photographic image quality is required, signboards and sample products that are frequently replaced. is there. Recently, personal computers and digital still cameras have become widespread, and there are many opportunities to output photographic images using an inkjet printer even in general households.

  However, images recorded by inkjet printers are not suitable for long-term storage of images because they are significantly discolored and discolored by acid gases and light in the atmosphere compared to multicolor printing and color photographic images by plate making. Is the current situation. Therefore, the demand for preventing fading and discoloration of an image is very strong, and many proposals have been made so far for improving its performance.

  For example, for the purpose of improving gas resistance, Patent Document 1 discloses a thioether compound, Patent Document 2 includes a hydrazide compound, Patent Document 3 and Patent Document 4 include a thiourea derivative, a thiosemicarbazide derivative, a thiocarbohydrazide derivative, and the like. A recording medium contained is disclosed. In Patent Document 5, one kind from thiourea derivative, thiosemicarbazide derivative and thiocarbohydrazide derivative and one kind from iodine, iodide, dithiocarbamic acid, thiocyanate and thiocyanate are included. A recording medium is disclosed.

  On the other hand, as a method for improving light resistance, Patent Document 6, Patent Document 7 and Patent Document 8 disclose a recording medium containing a phenolic antioxidant, a benzophenone-based or a benzotriazole-based ultraviolet absorber. ing.

  Patent Document 9 proposes a recording medium containing a hindered amine compound, and Patent Document 10 proposes a recording medium containing a hydrazide compound.

  Further, in Patent Document 11 and Patent Document 12, ascorbic acid, erythorbic acid, or sodium erythorbate is contained in the ink receiving layer, and in Patent Document 13, Patent Document 14, and Patent Document 15, flavonoids are contained in the ink receiving layer. A recording medium with improved gas resistance and light resistance is disclosed.

  However, methods for imparting gas resistance and light resistance to these conventionally known recording media do not necessarily have the effect, and it cannot be said that improvement of the characteristics is sufficient. In addition, the above-mentioned compounds are often insoluble in water, and cannot be added to aqueous coating liquids. Even if they are water-soluble, there is a problem that the water resistance and image bleeding under high temperature and high humidity are deteriorated. Therefore, it has been difficult to actually apply to a recording medium.

Japanese Patent Laid-Open No. 1-115677 Japanese Patent Laid-Open No. 61-154989 Japanese Patent Publication No. 4-34953 Japanese Patent Laid-Open No. 7-314883 Japanese Patent Laid-Open No. 8-25796 JP-A-57-74192 JP-A-57-87989 Japanese Patent Laid-Open No. 60-72785 JP-A 61-146591 Japanese Patent Laid-Open No. 61-154989 JP-A-7-195824 JP-A-8-15077 JP 2001-71627 A JP 2001-139850 A JP 2001-301315 A

  The present invention has been made in view of the above-described actual circumstances, and is a polymer antioxidant that effectively prevents image discoloration and discoloration due to acidic gas and light in the atmosphere and image bleeding under high temperature and high humidity. It is an object of the present invention to provide a recording medium suitable for long-term storage of a polymer compound and an image to which the polymer compound is applied.

  The inventors of the present invention provide an antioxidant that effectively prevents discoloration and discoloration of an image due to acidic gas and light in the atmosphere and bleeding of the image under high temperature and high humidity, and a recording medium suitable for long-term storage of an image. As a result of various studies for obtaining the ink-receiving layer, the ink-receiving layer of the recording medium in which one or more ink-receiving layers are provided on at least one surface of the support using a polymer compound having a specific structure as an antioxidant It has been found that the above-mentioned problems can be solved by including the compound therein, and the present invention has been completed.

（式中ｎは１または２を表す。また、Ｒ ₁ はメチレン基、エチレン基、またはプロピレン基を表す。）

（式中ｎは１または２を表す。また、Ｒ ₂ およびＲ ₃ はそれぞれ独立で水素原子、水酸基を表し、Ｒ ₂ およびＲ ₃ は同一であっても異なっていてもよい。）

（式中ｎは０または１を表す。）

（式中ｎは１または２を表す。また、Ｒ ₄ は硫黄原子または酸素原子を表し、Ｒ ₅ は硫黄原子または−ＳＯ ₂ −を表し、Ｒ ₄ およびＲ ₅ は同一ではなく、それぞれ異なる基で構成される。）

（式中Ｒ ₆ およびＲ ₇ はそれぞれ独立で水素原子を表し、Ｒ ₆ およびＲ ₇ は同一であっても異なっていてもよい。）

（式中Ｒ ₈ は水酸基を表す。） That is, the present invention provides at least one sulfur-containing organic compound (A) (hereinafter referred to as “Compound A”) selected from compounds having two or more active hydrogen groups represented by the following general formulas (7) to (12). At least of a polyisocyanate compound (B) having two or more isocyanate groups (hereinafter referred to as “compound B”) and an amine compound (C) having two or more active hydrogen groups (hereinafter referred to as “compound C”). A high molecular weight antioxidant (hereinafter referred to as “antioxidant”) characterized in that three kinds of compounds are reacted and at least a part of the amino group in the resulting product is cationized with an acid. A molecular compound is provided.

(In the formula, n represents 1 or 2. R ₁ represents a methylene group, an ethylene group, or a propylene group.)

(In the formula, n represents 1 or 2. R ₂ and R ₃ each independently represent a hydrogen atom or a hydroxyl group, and R ₂ and R ₃ may be the same or different.)

(Wherein n represents 0 or 1)

(In the formula, n represents 1 or 2, R ₄ represents a sulfur atom or an oxygen atom, R ₅ represents a sulfur atom or —SO ₂ —, and R ₄ and R ₅ are not the same and are different groups. Composed of)

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, and R ₆ and R ₇ may be the same or different.)

(In the formula, R ₈ represents a hydroxyl group.)

In the present invention, the content of the amine compound (C) contained in the product is 5.5 to 18.5% in molar ratio; the acid is phosphoric acid and / or a monovalent acid; Is a monovalent acid, the monovalent acid is a hydroxy acid; the sulfur-containing organic compound (A) contains at least one sulfide group in the molecule; and the sulfur-containing organic compound (A) is 3 or more active hydrogen groups and at least one is a hydroxyl group; the sulfur-containing organic compound (A) contained in the product accounts for 10 to 65% by mass of the amine compound (C) The content is 5.5 to 18.5% in terms of molar ratio; the antioxidant is preferably at least one kind represented by the following general formulas (1) to (6).

（式中ｎは１または２を、Ｒ₁はメチレン基、エチレン基、またはプロピレン基を、Ｒ₉はアルキレンもしくは複脂環を１つ以上含む脂肪族炭化水素基を、Ｒ₁₀は炭素数１〜４のアルキル基を、Ｒ₁₁およびＲ₁₂はそれぞれ独立で水素原子もしくはメチル基を、Ｘ^-は酸陰イオンを表す。ｍは重量平均分子量が２，０００〜１５０，０００になる数である。）

(Wherein n is 1 or 2, R ₁ is a methylene group, ethylene group or propylene group, R ₉ is an aliphatic hydrocarbon group containing one or more alkylene or double alicyclic rings, and R ₁₀ is carbon number 1) ˜4, R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a methyl group, X ⁻ represents an acid anion, and m is a number with a weight average molecular weight of 2,000 to 150,000. .)

（式中ｎは１または２を、Ｒ₂およびＲ₃はそれぞれ独立で水素原子、水酸基またはアルキル基を、Ｒ₂およびＲ₃は同一であっても異なっていてもよい。尚、Ｒ₉〜₁₂およびＸ^-およびｍは一般式（１）と同義である。）

(A wherein n is 1 or 2, R ₂ and R ₃ are independently a hydrogen atom, a hydroxyl group or an alkyl group, R ₂ and R ₃ may be be the same or different. In addition, R ₉ ~ ₁₂ and X ^- and m have the same meaning as in general formula (1).)

（式中ｎは０または１を表す。Ｒ₉〜₁₂およびＸ^-およびｍは一般式（１）と同義である。）

(In the formula, n represents 0 or 1. R ₉ to ₁₂ and X ⁻ and m have the same meaning as in the general formula (1).)

（式中ｎは１または２を、Ｒ₄は硫黄原子または酸素原子を、Ｒ₅は硫黄原子または−ＳＯ₂ −を、Ｒ₄およびＲ₅は同一ではなく、それぞれ異なる基で構成される。尚、Ｒ₉〜₁₂およびＸ^-およびｍは一般式（１）と同義である。）

(In the formula, n is 1 or 2, R ₄ is a sulfur atom or an oxygen atom, R ₅ is a sulfur atom or —SO ₂ — , and R ₄ and R ₅ are not the same, but are composed of different groups. R ₉ to ₁₂ and X ⁻ and m have the same meanings as those in the general formula (1).)

（式中Ｒ₆およびＲ₇はそれぞれ独立で水素原子またはアルキル基を表し、Ｒ₆およびＲ₇は同一であっても異なっていてもよい。尚、Ｒ₉〜₁₂およびＸ^-およびｍは一般式（１）と同義である。）

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group, and R ₆ and R ₇ may be the same or different. R ₉ to ₁₂ and X ⁻ and m are (It is synonymous with Formula (1).)

（式中Ｒ₈は水酸基またはアルキル基を表す。尚、Ｒ₉〜₁₂およびＸ^-およびｍは一般式（１）と同義である。）

(In the formula, R ₈ represents a hydroxyl group or an alkyl group. R ₉ to ₁₂ and X ⁻ and m have the same meanings as those in the general formula (1).)

  Further, the present invention is a recording medium in which at least one ink receiving layer is provided on at least one surface of a support, wherein at least the ink receiving layer contains the antioxidant of the present invention. A recording medium is provided.

  The present invention also provides a polymer compound represented by the general formulas (1) to (6).

  The recording medium in which the antioxidant of the present invention is applied to at least the ink receiving layer effectively prevented the image from being discolored by acid gas or light in the atmosphere and bleeding of the image under high temperature and high humidity. This is a recording medium suitable for long-term storage of images.

Next, the present invention will be described in more detail with reference to preferred embodiments.
Although it does not specifically limit as the compound A used for the synthesis | combination of the antioxidant of this invention, The compound which has at least 1 sulfide group in a molecule | numerator is preferable, Specifically, following General formula (7)-(12) Mention may be made of the compounds represented. In particular, the compound represented by the general formula (8) or the general formula (12) has a high effect of suppressing discoloration of an image due to acidic gas or light in the atmosphere, and can be preferably used. In addition, the following compound A can be used alone or in combination of two or more to synthesize the antioxidant of the present invention.

（式中ｎは１または２を表す。また、Ｒ₁はメチレン基、エチレン基、またはプロピレン基を表す。）

(In the formula, n represents 1 or 2. R ₁ represents a methylene group, an ethylene group, or a propylene group.)

（式中ｎは１または２を表す。また、Ｒ₂およびＲ₃はそれぞれ独立で水素原子、水酸基またはアルキル基を表し、Ｒ₂およびＲ₃は同一であっても異なっていてもよい。）

(In the formula, n represents 1 or 2. R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group or an alkyl group, and R ₂ and R ₃ may be the same or different.)

（式中ｎは０または１を表す。）

(Wherein n represents 0 or 1)

（式中ｎは１または２を表す。また、Ｒ₄は硫黄原子または酸素原子を表し、Ｒ₅は硫黄原子または−ＳＯ₂ −を表し、Ｒ₄およびＲ₅は同一ではなく、それぞれ異なる基で構成される。）

(In the formula, n represents 1 or 2, R ₄ represents a sulfur atom or an oxygen atom, R ₅ represents a sulfur atom or —SO ₂ — , and R ₄ and R ₅ are not the same and are different groups. Composed of)

（式中Ｒ₆およびＲ₇はそれぞれ独立で水素原子またはアルキル基を表し、Ｒ₆およびＲ₇は同一であっても異なっていてもよい。）

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group, and R ₆ and R ₇ may be the same or different.)

（式中Ｒ₈は水酸基またはアルキル基を表す。）

(Wherein R ₈ represents a hydroxyl group or an alkyl group.)

  Examples of the compound B used for the synthesis of the antioxidant of the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane. Diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1, 5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, etc. Although it is mentioned, it is not limited to these. Moreover, it is possible to synthesize the antioxidant of the present invention by using these polyisocyanate compounds alone or in combination of two or more thereof.

（式中Ｒ₁、Ｒ₂、Ｒ₃はいずれか一つが炭素数１〜６のアルキル基、アルカノール基、またはアミノアルキル基であり、それ以外は同一若しくは異なっていてもよく、アルカノール基、アミノアルキル基、またはアルカンチオール基を表す。） As the compound C used for the synthesis of the antioxidant of the present invention, for example, a tertiary amine represented by the following general formula (13) is preferable.

(In the formula, any one of R ₁ , R ₂ and R ₃ is an alkyl group having 1 to 6 carbon atoms, an alkanol group, or an aminoalkyl group, and the others may be the same or different. Represents an alkyl group or an alkanethiol group.)

  Specific examples of the compound C represented by the general formula (13) include, for example, diol compounds such as N-methyl-N, N-diethanolamine, N-ethyl-N, N-diethanolamine, N-isobutyl-N, N-diethanolamine. Nt-butyl-N, N-diethanolamine, Nt-butyl-N, N-diisopropanolamine and the like, and the triol compound includes triethanolamine and the like. Examples of the diamine compound include methyliminobispropylamine and butyliminobispropylamine, and examples of the triamine compound include tri (2-aminoethyl) amine. These amine compounds can be used alone or in combination of two or more to synthesize the antioxidant of the present invention.

  The antioxidant of the present invention reacts compound A, compound B and compound C as described above, and compound A unit, compound B unit and compound C unit (the tertiary amine in the unit is cationized). Is obtained as a polymer containing in the molecule. In order for the polymer to be effective as an antioxidant, the content of compound C in the polymer is preferably 5.5 to 18.5% in terms of molar ratio. If the content of Compound C is lower than 5.5% in terms of molar ratio, the content of hydrophilic groups will decrease, which may be inconvenient when preparing an aqueous dispersion of an antioxidant, or use an antioxidant. In some cases, therefore, it is difficult to formulate the ink-receiving layer in the aqueous coating solution. On the other hand, when the content of Compound C is higher than 18.5% in terms of molar ratio, there may be a problem that glossiness and print density are lowered in a recording medium containing the antioxidant.

  In the antioxidant of the present invention, if the molar ratio of compound C is within the above range, the compound C unit can occupy 3 to 80% by mass in the antioxidant. Exceeding this range may cause a reduction in the function of the antioxidant as described above.

  In the antioxidant of the present invention, if the content of compound C is in the above-mentioned range, the mass of the incorporated compound A unit preferably occupies 10 to 65% by mass in the polymer. More preferably, it is the ratio which occupies 30-65 mass%. When the proportion of the compound A unit is less than 10% by mass, the effect as an antioxidant may be insufficient. On the other hand, when the proportion of the compound A unit exceeds 65% by mass, the content of the hydrophilic group is relatively lowered, which may be inconvenient when adjusting the aqueous dispersion of the polymer compound.

  Compound B has a function of linking compound A and compound C, and the amount of compound B used is not particularly limited. However, if the content of compound C is in the above range, the mass of compound B unit is obtained. It is preferable to occupy 10 to 80% by mass in the polymer. More preferably, it is the ratio which occupies 30-60 mass%. When the proportion of the compound B unit is within this range, an amount sufficient to sufficiently exert the functions of the unit of compound A and compound C can be combined.

  Moreover, the manufacturing method of the antioxidant using the said compounds AC may be a so-called one-shot method in which the above-mentioned compounds A to C are reacted at once to form a random polymer, or the compound A (or the compound C) and A so-called prepolymer method may be used in which a prepolymer having a terminal isocyanate group is produced by reacting compound B with a ratio rich in isocyanate groups, and the prepolymer and compound C (or compound A) are reacted. . In any method, a chain extender such as a low molecular weight polyol or a low molecular weight diamine may be used in combination. In addition, the molecular weight of the obtained antioxidant can be adjusted by changing the amount of compounds A to C used or adding a reaction terminator such as monoalcohol or monoamine to the reaction system at an appropriate timing.

  The weight average molecular weight of the antioxidant thus obtained depends on the reaction conditions, but is preferably in the range of 2,000 to 150,000, and more preferably in the range of 2,000 to 50,000. If the weight average molecular weight of the antioxidant is less than 2,000, the glossiness or the print density may be lowered. If it exceeds 150,000, the reaction time becomes longer and the production cost increases, which is not preferable.

  In the production of the antioxidant of the present invention, a compound having two or more active hydrogen groups other than the compound A and the compound C (hereinafter referred to as “compound D”) may be copolymerized as necessary. Good. As such compound D, it is also possible to synthesize the antioxidant used in the present invention by using the following polyester polyol, polyether polyol, or polycarbonate polyol alone or in combination of two or more. .

  Examples of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane. Diol, neopentyl glycol diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 300 to 1000, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanedimethanol, bisphenol A , Glycol components such as bisphenol S, hydrogenated bisphenol A, hydroquinone, alkylene oxide adduct, malonic acid, succinic acid, glutaric acid, adipic acid Pimelic acid, suberic acid, azelaic acid, sebacic acid, hedecane dicarboxylic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bisphenoxyethane-p, p'-dicarboxylic acid, dicarboxylic acid Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, including polyesters obtained by dehydration condensation reaction from acid components such as anhydrides or ester-forming derivatives, or the like Examples of copolyesters It is done.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Diol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, sorbitol, sucrose, bisphenol A, bisphenol S, hydrogenated bisphenol A, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanol Compound having at least two active hydrogens such as amine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol The product obtained by subjecting a product to addition polymerization by a conventional method using one or more monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene as an initiator. It is done. In addition, as a polyol, an ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc., using a compound having at least two primary amino groups such as ethylenediamine and propylenediamine as an initiator. It is also possible to use those obtained by addition polymerization of one or more of these monomers by a conventional method. Particularly preferred is polyethylene glycol.

  Examples of the polycarbonate polyol include compounds obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol and the like with diphenyl carbonate and phosgene.

  The antioxidant of the present invention desirably uses a tin-based catalyst and / or an amine-based catalyst in the isocyanate polyaddition reaction. Examples of the tin-based catalyst include dibutyltin dilaurate and stannous octoate. Examples of the amine-based catalyst include triethylenediamine, triethylamine, tetramethylpropanediamine, tetramethylbutanediamine, and N-methylmorpholine. It is not limited to.

  The above-mentioned isocyanate polyaddition reaction can be carried out in the absence of a solvent depending on the composition, but a hydrophilic organic solvent that does not directly participate in the isocyanate polyaddition reaction system is reacted for the purpose of controlling the reaction system or controlling the base viscosity. It is common to use as a solvent. Examples of such hydrophilic organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Examples thereof include organic acid esters such as methyl propionate, ethyl propionate and butyl propionate, and amines such as N, N-dimethylformamide and N-methylpyrrolidone. Moreover, it is preferable that the used hydrophilic organic solvent is finally removed.

  The antioxidant of the present invention can be dispersed and stabilized or dissolved in water by cationizing at least a part of the compound C unit with an acid. Alternatively, when cationized with a quaternizing agent such as an alkyl halide, it cannot be stabilized or dissolved in water at a preferred particle size. The acid used here is not particularly limited, but when a polyvalent acid is used, it may cause a thickening when the antioxidant of the present invention is dispersed or dissolved in water. A monovalent acid is preferred. Examples of phosphoric acid include phosphoric acid and phosphorous acid. Examples of the monovalent acid include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, pyruvic acid, and methanesulfonic acid, and inorganic acids such as hydrochloric acid and nitric acid. In addition, when an antioxidant cationized with a hydroxy acid is applied to the formation of an ink receiving layer of a recording medium, the non-printing portion is compared with the case of using an antioxidant cationized with another acid. Since yellowing of (blank paper part) is suppressed, it can be used more preferably.

Particularly preferred among the antioxidants and polymer compounds of the present invention obtained by the method as described above are represented by the following general formulas (1) to (6). In the formula, n, R _{1 to} R ₁₂ , X ⁻ and m are as defined above.

  In addition, when the antioxidant of this invention is disperse | distributed to an aqueous medium, it is preferable that the average particle diameter of this dispersion is the range of 5 nm-500 nm from a viewpoint of storage stability. In addition, the average particle diameter in the present invention is measured by a dynamic light scattering method, and is described in “Structure of polymer (2) Scattering experiment and morphology observation Chapter 1 Light scattering” (Edited by Kyoritsu Publishing Society of Polymer Science). Chem. Phys., 70 (B), 15 Apl., 3965 (1979). The dynamic light scattering method has a distribution in the decay of the time correlation function from scattered light when fine particles having different particle sizes are mixed. By analyzing this time correlation function using the cumulant method, the average (<Γ>) and variance (μ) of the decay rate can be obtained. Since the decay rate (Γ) is expressed as a function of the particle diffusion coefficient and the scattering vector, the hydrodynamic average particle diameter can be obtained using the Stokes-Einstein equation. The average particle size defined in the present invention can be easily measured using, for example, a laser particle size analyzer PARIII (manufactured by Otsuka Electronics Co., Ltd.) or the like.

  The recording medium of the present invention is characterized in that the ink receiving layer contains the antioxidant of the present invention. The ink receiving layer is formed by applying and drying a coating solution in which a suitable binder and a suitable inorganic pigment are dispersed and dissolved in an aqueous solvent on the surface of a suitable support. In the present invention, the method of forming the ink receiving layer by dissolving or dispersing the antioxidant of the present invention in the coating solution, or forming the ink receiving layer with a coating solution containing no antioxidant, The ink receiving layer is impregnated with the antioxidant of the present invention by an appropriate method such as overcoating.

  The content of the antioxidant of the present invention in the ink receiving layer is preferably 0.05% by mass to 20% by mass in terms of solid content with respect to the ink receiving layer. If the content is in this range, it is possible to effectively prevent discoloration or discoloration of the image due to gas and light in the atmosphere and image bleeding under high temperature and high humidity. If the content with respect to the ink receiving layer is less than 0.05% by mass, it is not possible to sufficiently prevent discoloration or discoloration of the image due to gas or light, which is the object of the present invention, and if the content exceeds 20% by mass, the ink There is a possibility of causing deterioration of absorbability and lowering of print density.

  The support for the recording medium in the present invention is not particularly limited, but paper such as fine paper, medium paper, coated paper, art paper, cast coated paper, synthetic paper, white plastic film, transparent A plastic film, a translucent plastic film, a resin-coated paper or the like can be used.

  In order to effectively develop the gloss of the image, a base material having a high barrier property with respect to the ink receiving layer forming coating liquid is preferable, and a pigment such as titanium oxide or barium sulfate is blended or made porous. There are so-called resin-coated paper in which polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyimide, polyacetate, polyethylene, polypropylene, polystyrene, and other white plastic films made opaque, and thermoplastic paper such as polyethylene and polypropylene are laminated to the base paper. Is preferred. In order to effectively develop semi-glossy paper, a matte or embossed resin-coated paper is preferably used when laminating the thermoplastic resin.

  Further, in the case where the recording medium is provided with the same image quality and texture as a high-gloss silver salt photograph, the base paper that is most preferably used as a support is at least one surface provided with an ink receiving layer is coated with a polyolefin resin. Examples include polyolefin resin-coated paper, and more preferable examples include polyolefin resin-coated paper coated on both sides. As a preferred form of the polyolefin resin-coated paper, the 10-point average roughness according to JIS-B0601 is 0.5 μm or less, and the 60-degree specular gloss according to JIS-Z-8741 is 25 to 75%.

Moreover, there is no restriction | limiting in particular in the thickness of resin-coated paper, However, It is preferable that it is 25 micrometers-500 micrometers. If the thickness is less than 25 μm, the rigidity of the ink jet recording sheet is low, which causes inconveniences such as a decrease in touch, texture, or opacity when it is held. On the other hand, if it is thicker than 500 μm, it becomes rigid and difficult to handle, which may cause troubles during feeding with a printer. A more preferable range is 50 μm to 300 μm. No particular limitation on the weight of the resin-coated paper, is preferably in the range of ^{25g / m 2 ~500g / m 2} .

  Further, when using paper such as high-quality paper as a support, it is preferable to use a paper having a Steecht sizing degree of 15 seconds or more, more preferably 25 seconds or more in order to obtain good color developability and resolution. In addition, a sheet made of glass or metal may be used. Further, in order to improve the adhesive strength between the support and the ink receiving layer, the support surface can be subjected to corona discharge treatment or various undercoat treatments.

  The inorganic pigment that can be used in the present invention is preferably fine particles that have high ink absorbability, excellent color developability, and can form high-quality images. Examples of such inorganic pigments include synthetic amorphous silica, colloidal silica, calcium carbonate, magnesium carbonate, kaolin, clay, talc, hydrotalcite, aluminum silicate, calcium silicate, magnesium silicate, synthetic amorphous silica, Colloidal silica, diatomaceous earth, alumina, alumina hydrate, colloidal alumina, aluminum hydroxide, boehmite structure alumina hydrate, pseudoboehmite structure alumina hydrate, lithopone, zeolite, etc. Species can be used together.

  As the form of the inorganic pigment, in order to obtain a highly glossy and highly transparent ink-receiving layer, the average particle size is preferably in the range of 50 nm to 500 nm, more preferably in the range of 100 nm to 300 nm. When the average particle size of the inorganic pigment is smaller than 50 nm, the ink absorbability of the ink receiving layer is remarkably reduced, and ink bleed or beading (granular density without being able to absorb ink) when printing with a printer with a large discharge amount Uneven phenomenon) occurs. On the other hand, when the average particle size is larger than 500 nm, the transparency of the ink receiving layer is lowered, and the print density and gloss of the image may be lowered. In addition, the average particle diameter as used in the field of this invention is measured by the dynamic light-scattering method, "A structure of a polymer (2) Scattering experiment and form observation Chapter 1 light scattering" (Kyoritsu Publishing Society of Polymer Science), Chem. Phys., 70 (B), 15 Apl., 3965 (1979).

  Among the inorganic pigments, alumina hydrate having a boehmite structure or a pseudoboehmite structure is particularly preferably used. These inorganic pigments have particularly high ink absorbability, excellent color developability, and high-quality images. It can be formed.

In particular, alumina, boehmite structure or pseudoboehmite structure alumina hydrate having a BET specific surface area of 50 m ² / g or more is preferable, more preferably 50 to 500 m ² / g, and still more preferably 50 to 250 m ^2. / G. When the BET specific surface area of the alumina hydrate is in the range of 50 to 250 m ² / g, the ink absorbing property, beading and smoothness of the ink receiving layer are excellent. On the other hand, when the BET specific surface area is less than 50 m ² / g, the transparency of the ink receiving layer and the print density are lowered, and the printed matter tends to be white and dull, and the BET specific surface area is low. If it exceeds 500 m ² / g, the ink absorptivity decreases, and a large amount of acid is required as a peptizer to stably disperse the alumina hydrate, which is not preferable.

The alumina hydrate having a boehmite structure or pseudoboehmite structure preferably used in the present invention is represented by the following general formula (14).
Al ₂ O _3-n (OH) _2n · mH ₂ O General formula (14)
In the formula, n represents any one of integers of 0, 1, 2, or 3, and m represents a value of 0 to 10, preferably 0 to 5. Since mH ₂ O often represents a detachable aqueous phase that does not participate in the formation of a crystal lattice, m can take a non-integer value. Also, when this type of alumina hydrate is calcined, m may reach a value of zero.

  In general, an alumina hydrate crystal having a boehmite structure is a layered compound having a (020) plane forming a giant plane, and exhibits a diffraction peak peculiar to an X-ray diffraction pattern. As the boehmite structure, in addition to perfect boehmite, a structure called excess boehmite and containing excess water between layers of the (020) plane can be taken. The pseudo-boehmite X-ray diffraction pattern shows a broader diffraction peak than the complete boehmite. Since complete boehmite and pseudoboehmite are not clearly distinguishable, unless otherwise specified, they are both referred to as alumina hydrate showing a boehmite structure.

  Although it does not specifically limit as a manufacturing method of the said alumina hydrate, For example, any methods, such as a buyer method and a light van pyrolysis method, are employable. A particularly preferable method is a method in which an acid is added to a long-chain aluminum alkoxide for hydrolysis. In addition, the obtained alumina hydrate can be controlled to a specific range of the particle shape of the alumina hydrate by adjusting the conditions of the aging process for growing the particles through the hydrothermal synthesis process. When the time is set appropriately, primary particles of alumina hydrate having a relatively uniform particle diameter grow. The sol obtained here can be used as a dispersion by adding an acid as a peptizer, but in order to further improve the dispersibility of alumina hydrate in water, the sol is spray-dried, etc. After pulverizing by this method, an acid can be added to form a dispersion. Moreover, conventionally known acids can be used as the acid for peptizing alumina hydrate, such as formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, pyruvic acid, methanesulfonic acid and other organic acids, and hydrochloric acid. Inorganic acids such as nitric acid can be used, and one or more of them can be freely selected and used.

  In the present invention, the ink receiving layer can be formed using a water-soluble resin and / or a water-dispersible resin together with the inorganic pigment. Examples of the water-soluble resin or water-dispersible resin used in the present invention include gelatin, casein and modified products thereof, cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, fully or partially saponified polyvinyl alcohol or the like. Modified products (cation modification, anion modification, silanol modification, etc.), urea resins, melamine resins, epoxy resins, epichlorohydrin resins, polyurethane resins, polyethyleneimine resins, polyamide resins, polyvinylpyrrolidone resins, polyvinyl butyral Resin, poly (meth) acrylic acid or copolymer thereof, acrylamide resin, maleic anhydride copolymer, polyester resin, SBR latex, NBR latex, methyl methacrylate A cationic group or an anionic group is added to an acrylic polymer latex such as a butadiene copolymer latex or an acrylic ester copolymer, a vinyl polymer latex such as an ethylene-vinyl acetate copolymer, and these various polymer latexes. Examples thereof include functional group-modified polymer latexes. Preference is given to polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate and having an average degree of polymerization of 300 to 5,000. The saponification degree is preferably 70 to less than 100%, particularly preferably 80 to 99.5%. In addition, these water-soluble or water-dispersible resins can be used alone or in combination.

  The mixing mass ratio of the inorganic pigment (A) to the water-soluble resin and the water-dispersible resin (B) is preferably A: B = 1: 1 to 30: 1, more preferably A: B = 1.5. : In the range of 1-20: 1. If the amount of the water-soluble resin and / or the water-dispersible resin is within these ranges, the formed ink receiving layer will not easily crack or fall off, and the ink absorption will be good.

  In the recording medium of the present invention, in order to improve the film forming property, water resistance and film strength of the film formed of the inorganic fine particles and the water-soluble or water-dispersible resin, a hardener is provided in the ink receiving layer. May be added. Generally, various hardeners are selected depending on the type of reactive group possessed by the polymer used. For example, in the case of a polyvinyl alcohol resin, an epoxy hardener, a boron compound such as boric acid, Inorganic hardeners such as basic aluminum salts.

  The amount of the boron compound used varies depending on the amount of the water-soluble resin and / or water-dispersible resin used as the binder, but is generally from 0.1 to 30% by mass relative to the water-soluble resin and / or water-dispersible resin. Should be added. If the content of the boron compound is less than 0.1% by mass with respect to the water-soluble resin and / or the water-dispersible resin, the film-forming property is lowered and sufficient water resistance cannot be obtained. On the other hand, when it exceeds 30% by mass, the change with time in the viscosity of the coating solution becomes large, and the coating stability may be lowered.

  The recording medium of the present invention has a configuration in which one or more ink receiving layers containing at least one antioxidant of the present invention are provided on a support, and a coating containing the antioxidant. A structure in which a coating solution is overcoated on the ink receiving layer, or a coating solution containing at least one antioxidant of the present invention is applied to the support surface in a small amount to form an ink receiving layer. You can choose. In the present invention, these configurations are also included as “an ink receiving layer formed on the surface of the support”.

  The solid content concentration in the coating liquid for forming the ink receiving layer is not particularly limited as long as the viscosity is such that the ink receiving layer can be formed on the substrate, but it is 5 to 5 based on the total mass of the coating liquid. 50 mass% is preferable. When the solid content concentration is less than 5% by mass, it is necessary to increase the coating amount in order to increase the thickness of the ink receiving layer, which requires a lot of time and energy for drying, which is uneconomical. There is a case. On the other hand, if it exceeds 50% by mass, the viscosity of the coating solution may increase and the coating property may deteriorate.

  Moreover, various additives can be mix | blended with the said coating liquid in the range which does not prevent the effect of this invention. Examples of such additives include surfactants, pigment dispersants, thickeners, crosslinking agents, antifoaming agents, ink fixing agents, dot adjusting agents, coloring agents, fluorescent whitening agents, preservatives, pH adjusting agents, Examples thereof include an antistatic agent and a conductive agent.

  As a method of applying the prepared coating liquid on the substrate, any known coating method can be applied, for example, blade coating method, air knife coating method, curtain die coating method, slot die coating method, bar coating. The ink receiving layer can be formed by drying using a drying device such as a hot air dryer, thermal drum, or far-infrared dryer. can do. The ink receiving layer may be formed by changing the composition ratio of the alumina hydrate, the resin, and other additives, or may be formed on one side or both sides of the substrate. Further, for the purpose of improving the resolution and transportability of the image, smoothing processing may be performed using an apparatus such as a calendar or a cast.

A preferred range for the coating amount of the coating liquid on the substrate is 0.5 to 60 g / m ² in terms of solid content, and a more preferred range is 5 to 55 g / m ² . When the coating amount is less than 0.5 g / m ² , the formed ink receiving layer may not sufficiently absorb the moisture of the ink, and the ink may flow or the image may bleed. 60 g / m ² If it exceeds 1, curling may occur at the time of drying, or a remarkable effect may not appear as expected for printing performance.

  The reason why the recording medium to which the antioxidant of the present invention is applied as described above prevents the fading and discoloration of the image by gas and light is not clear, but the antioxidant is not free of radicals or excess in the ink receiving layer. It is presumed that this is the result of suppressing the generation of oxides, and the reason why image bleeding under high temperature and high humidity was prevented is that the hydroxyl groups of compound A and compound C constituting the antioxidant are polymers. It is presumed that this is due to the fact that the properties of moisture absorption that were originally possessed have been reduced.

  The ink used for recording on the recording medium of the present invention is not particularly limited, but a dye or pigment is used as a color material, and a mixture of water and a water-soluble organic solvent is used as the medium. It is preferable to use a general water-based ink for inkjet recording in which a dye or pigment is dissolved or dispersed.

  As a method for forming an image by applying the ink to the recording medium, an ink jet recording method is particularly preferable. As the ink jet recording method, the ink is effectively separated from the nozzle and the ink is applied to the recording medium. Any method may be used as long as it can provide the above. In particular, an ink jet system in which ink subjected to the action of thermal energy undergoes a rapid volume change by a method described in Japanese Patent Application Laid-Open No. 54-59936 and the like, and ink is ejected from a nozzle by the action force due to this state change Can be used effectively.

Hereinafter, the present invention will be described specifically by way of examples. In the following examples, “parts” and “%” are based on mass unless otherwise specified.
<Production of alumina hydrate>
Aluminum dodexide was prepared by the method described in US Pat. No. 4,242,271. Next, the aluminum dodexide was hydrolyzed by the method described in US Pat. No. 4,202,870 to produce an alumina slurry. Water was added to the alumina slurry until the solid content of alumina hydrate having a boehmite structure was 7.7%. The pH of the alumina slurry was 9.4. The pH was adjusted by adding a 3.9% nitric acid solution.

  Next, using an autoclave, aging was performed at pH before aging: 6.0, aging temperature: 150 ° C., and aging time: 6 hours to obtain a colloidal sol. The colloidal sol was spray-dried at an inlet temperature of 87 ° C. to obtain an alumina hydrate powder. The obtained powder was an alumina hydrate having a flat plate shape and a boehmite crystal structure. Further, 20% of the alumina hydrate having the boehmite structure was mixed in ion-exchanged water to prepare an alumina hydrate dispersion.

  The dispersion obtained by the above method was redispersed using an ultrasonic homogenizer (UH-600S, manufactured by SMT Co., Ltd.) to prepare a 20% alumina hydrate dispersion. The average particle size of the obtained alumina hydrate dispersion was measured using a laser particle size analyzer PARIII (manufactured by Otsuka Electronics Co., Ltd.). As a result, the average particle size was 165.5 nm.

<Method for producing antioxidant 1>
Antioxidant 1 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 140 g of acetone as a reaction solvent, and 50.00 g of 3,6-dithia-1,8-octanediol and 10.46 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 79.66 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 9.14 g of 35% hydrochloric acid. Further, after adding 573 g of water, the solution was concentrated under reduced pressure to remove acetone, and the concentration was further adjusted with water, whereby an aqueous dispersion of the antioxidant of the present invention (antioxidant 1) having a solid content of 20% was obtained. Manufactured.

<Method for producing antioxidant 2>
Antioxidant 2 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser is charged with 98 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and 3.50 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 55.02 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.2 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 1.56 g of 85% formic acid. Further, 404 g of water was added, and then 20% of the aqueous dispersion of the antioxidant of the present invention (antioxidant 2) was produced in the same manner as in the production method of antioxidant 1.

<Method for producing antioxidant 3>
Antioxidant 3 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 109 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and 6.79 g of methyldiethanolamine were dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 62.07 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.2 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 3.09 g of 85% formic acid. Further, after adding 446 g of water, the antioxidant aqueous dispersion (antioxidant 3) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 4>
Antioxidant 4 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 128 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and 14.56 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 73.25 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.2 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.24 g of 85% formic acid. Further, after adding 523 g of water, the antioxidant aqueous dispersion (antioxidant 4) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for producing antioxidant 5>
Antioxidant 5 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 161 g of acetone as a reaction solvent, and 50.00 g of 3,6-dithia-1,8-octanediol and 17.83 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 93.29 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 3 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 8.98 g of 98% acetic acid. Further, after adding 680 g of water, the antioxidant aqueous dispersion (antioxidant 5) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for producing antioxidant 6>
Antioxidant 6 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 111 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and 8.15 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 63.64 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 7.88 g of 85% phosphoric acid. Further, after adding 470 g of water, the antioxidant aqueous dispersion (antioxidant 6) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for producing antioxidant 7>
Antioxidant 7 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 73 g of acetone as a reaction solvent, 30.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine under stirring. After dissolving 32 g, the temperature was raised to 40 ° C. and 40.52 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 2.13 g of 35% hydrochloric acid. Further, 301 g of water was added, and then the antioxidant aqueous dispersion (antioxidant 7) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

<Production Method of Antioxidant 8>
Antioxidant 8 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 81 g of acetone as a reaction solvent, 30.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine are added under stirring. After dissolving 98 g, the temperature was raised to 40 ° C. and 44.28 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 4.51 g of 35% hydrochloric acid. Further, after adding 331 g of water, the antioxidant aqueous dispersion (antioxidant 8) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Production Method of Antioxidant 9>
Antioxidant 9 was produced as follows.
Into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 99 g of acetone as a reaction solvent was added, 30.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine were added under stirring. After dissolving 52 g, the temperature was raised to 40 ° C. and 54.62 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 9.34 g of 35% hydrochloric acid. Further, 404 g of water was added, and then an antioxidant aqueous dispersion (antioxidant 9) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

<The manufacturing method of antioxidant 10>
Antioxidant 10 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 139 g of acetone as a reaction solvent, 50.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine are added under stirring. After dissolving 06 g, the temperature was raised to 40 ° C. and 76.80 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 8.62 g of 85% phosphoric acid. Further, after adding 585 g of water, the antioxidant aqueous dispersion (antioxidant 10) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<The manufacturing method of antioxidant 11>
Antioxidant 11 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 110 g of acetone as a reaction solvent, 40.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine were added under stirring. After dissolving 29 g, the temperature was raised to 40 ° C. and 60.36 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 3.20 g of 85% formic acid. Further, after adding 449 g of water, the antioxidant aqueous dispersion (antioxidant 11) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Production Method of Antioxidant 12>
Antioxidant 12 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 127 g of acetone as a reaction solvent, 50.00 g of 3,6-dithia-1,8-octanediol and t-butyldipropanolamine with stirring. After dissolving 7.85 g, the temperature was raised to 40 ° C. and 69.47 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 7 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 4.32 g of 35% hydrochloric acid. Further, after adding 515 g of water, the antioxidant aqueous dispersion (antioxidant 12) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 13>
Antioxidant 13 was produced as follows.
A reaction vessel equipped with a stirrer, thermometer and reflux condenser was charged with 105 g of acetone as a reaction solvent, 40.00 g of 3,6-dithia-1,8-octanediol and t-butyldipropanolamine under stirring. After dissolving 7.82 g, the temperature was raised to 40 ° C. and 57.38 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 7 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 2.24 g of 85% formic acid. Further, after adding 428 g of water, the antioxidant aqueous dispersion (antioxidant 13) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 14>
Antioxidant 14 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 111 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine were added under stirring. After dissolving 52 g, the temperature was raised to 40 ° C. and 61.28 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.3 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 8.98 g of 50% aqueous glycolic acid solution. Further, after adding 461 g of water, the antioxidant aqueous dispersion (antioxidant 14) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Production Method of Antioxidant 15>
Antioxidant 15 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 111 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine were added under stirring. After dissolving 65 g, the temperature was raised to 40 ° C. and 61.44 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.3 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.27 g of 98% pyruvic acid. Further, 465 g of water was added, and then the antioxidant aqueous dispersion (antioxidant 15) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

<Method for Producing Antioxidant 16>
Antioxidant 16 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 234 g of acetone as a reaction solvent, 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and methyldiethanolamine with stirring. After dissolving 6.29 g, the temperature was raised to 40 ° C. and 54.17 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.50 g of 35% hydrochloric acid. Further, 410 g of water was added, and the antioxidant aqueous dispersion (antioxidant 16) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 17>
Antioxidant 17 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 239 g of acetone as a reaction solvent, 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and methyldiethanolamine with stirring. After dissolving 3.02 g, the temperature was raised to 40 ° C. and 49.84 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 1.38 g of 85% formic acid. Further, 381 g of water was added, and the antioxidant aqueous dispersion (antioxidant 17) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

<Method for Producing Antioxidant 18>
Antioxidant 18 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 258 g of acetone as a reaction solvent, 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and methyldiethanolamine with stirring. After dissolving 6.29 g, the temperature was raised to 40 ° C. and 54.17 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 2.86 g of 85% formic acid. Further, 412 g of water was added, and the antioxidant aqueous dispersion (antioxidant 18) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 19>
Antioxidant 19 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 295 g of acetone as a reaction solvent, 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and methyldiethanolamine with stirring. After dissolving 12.24 g, the temperature was raised to 40 ° C. and 62.56 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.54 g of 85% formic acid. Further, after adding 470 g of water, the antioxidant aqueous dispersion (antioxidant 19) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 20>
Antioxidant 20 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 334 g of acetone as a reaction solvent, and 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and t- under stirring. After dissolving 8.62 g of butyldiethanolamine, the temperature was raised to 40 ° C. and 53.20 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.57 g of 35% hydrochloric acid. Further, 415 g of water was added, and the antioxidant aqueous dispersion (antioxidant 20) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<The manufacturing method of antioxidant 21>
Antioxidant 21 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 102 g of acetone as a reaction solvent, and 30.00 g of 2,2′-thiodiethanol and 6.36 g of methyldiethanolamine were dissolved with stirring until 40 ° C. The temperature was raised and 65.84 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.56 g of 35% hydrochloric acid. Further, after adding 417 g of water, the antioxidant aqueous dispersion (antioxidant 21) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<The manufacturing method of antioxidant 22>
Antioxidant 22 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 106 g of acetone as a reaction solvent, and after dissolving 30.00 g of 2,2′-thiodiethanol and 8.94 g of t-butyldiethanolamine with stirring, 40 g The temperature was raised to 0 ° C. and 67.48 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.2 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.77 g of 35% hydrochloric acid. Further, after adding 434 g of water, the antioxidant aqueous dispersion (antioxidant 22) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Production Method of Antioxidant 23>
Antioxidant 23 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser was charged with 134 g of acetone as a reaction solvent, and after dissolution, 40.00 g of 2,2′-thiodiethanol and 9.91 g of t-butyldipropanolamine were dissolved. The temperature was raised to 40 ° C. and 83.68 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 6 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.48 g of 35% hydrochloric acid. Further, after adding 544 g of water, the antioxidant aqueous dispersion (antioxidant 23) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 24>
Antioxidant 24 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 47 g of acetone as a reaction solvent, and 22.00 g of 6-oxa-3,9-dithia-1,11-undecanediol and methyldiethanolamine were stirred. After dissolving 3.60 g, the temperature was raised to 40 ° C. and 27.00 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 3.20 g of 35% hydrochloric acid. Further, 215 g of water was added, and the antioxidant aqueous dispersion (antioxidant 24) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 25>
Antioxidant 25 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser was charged with 240 g of acetone as a reaction solvent, 40.00 g of 1,2-bis (2,3-dihydroxypropylthio) ethane and methyldiethanolamine 5 under stirring. After dissolution of .76 g, the temperature was raised to 40 ° C. and 47.53 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.03 g of 35% hydrochloric acid. Further, after adding 380 g of water, the antioxidant aqueous dispersion (antioxidant 25) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 26>
Antioxidant 26 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 66 g of acetone as a reaction solvent, 30.00 g of bis (2- (2-hydroxyethylthio-ethyl)) sulfone and methyldiethanolamine 4 under stirring. After dissolution of 25 g, the temperature was raised to 40 ° C. and 32.25 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and 3.71 g of 35% hydrochloric acid was added to cationize. Further, after adding 271 g of water, the antioxidant aqueous dispersion (antioxidant 26) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 27>
Antioxidant 27 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 116 g of acetone as a reaction solvent, and 10.22 g of 1,2- (2-hydroxyethylthio) propan-2-ol, 3,6- After dissolving 30.00 g of dithia-1,8-octanediol and 9.76 g of t-butyldiethanolamine, the temperature was raised to 40 ° C. and 66.10 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 6.32 g of 35% hydrochloric acid. Further, 473 g of water was added, and then the antioxidant aqueous dispersion (antioxidant 27) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

<Method for Producing Antioxidant 28>
Antioxidant 28 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser was charged with 81 g of acetone as a reaction solvent, 35.00 g of 3,6-dithia-1,8-octanediol, 6.20 g of methyldiethanolamine under stirring, After dissolving 3.00 g of polyethylene glycol monomethyl ether (molecular weight 1,500) and 0.6 g of trimethylolpropane-PO adduct (molecular weight 2,000), the temperature was raised to 40 ° C. and 55.00 g of isophorone diisocyanate was added. It was. Thereafter, the temperature was raised to 50 ° C., 0.03 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.40 g of 35% hydrochloric acid. Further, 407 g of water was added, and the antioxidant aqueous dispersion (antioxidant 28) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 29>
Antioxidant 29 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 226 g of acetone as a reaction solvent, 40.00 g of 3,6-dithia-1,8-octanediol, t-butyldiethanolamine, 9. After dissolving 1.40 g of 46 g and polyethylene glycol (molecular weight 1,000), the temperature was raised to 40 ° C. and 61.51 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 6.11 g of 35% hydrochloric acid. Further, after adding 460 g of water, the antioxidant aqueous dispersion (antioxidant 29) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<The manufacturing method of antioxidant 30>
Antioxidant 30 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 100 g of acetone as a reaction solvent, and 40.00 g of 3,6-dithia-1,8-octanediol and 2.99 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 57.08 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.2 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 1.36 g of 85% formic acid. Furthermore, after adding 410 g of water, the antioxidant aqueous dispersion (antioxidant 30) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1, but the dispersibility was poor. It settled in.

<Production Method of Antioxidant 31>
Antioxidant 31 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 94 g of acetone as a reaction solvent, and 30.00 g of 3,6-dithia-1,8-octanediol and 11.50 g of methyldiethanolamine are dissolved under stirring. Thereafter, the temperature was raised to 40 ° C. and 52.68 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.2 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was performed for 4 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 5.24 g of 85% formic acid. Further, 386 g of water was added, and the antioxidant aqueous dispersion (antioxidant 31) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1.

<Method for Producing Antioxidant 32>
Antioxidant 32 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 70 g of acetone as a reaction solvent, 30.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine are added under stirring. After dissolving 54 g, the temperature was raised to 40 ° C. and 38.00 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 1.66 g of 35% hydrochloric acid. Furthermore, after adding 288 g of water, the antioxidant aqueous dispersion (antioxidant 32) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1, but the dispersibility was poor. It settled in.

<Method for producing antioxidant 33>
Antioxidant 33 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 95 g of acetone as a reaction solvent, with stirring, 29.00 g of 3,6-dithia-1,8-octanediol and t-butyldiethanolamine 15. After dissolving 95 g, the temperature was raised to 40 ° C. and 50.08 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.4 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 5 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 10.26 g of 35% hydrochloric acid. Further, 388 g of water was added, and then the antioxidant aqueous dispersion (antioxidant 33) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

<Method for Producing Antioxidant 34>
Antioxidant 34 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 230 g of acetone as a reaction solvent, and 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and methyldiethanolamine were stirred. After dissolving 2.49 g, the temperature was raised to 40 ° C. and 47.06 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 1.13 g of 85% formic acid. Furthermore, after adding 367 g of water, the antioxidant aqueous dispersion (antioxidant 34) of the present invention having a solid content of 20% was produced in the same manner as in the production method of the antioxidant 1, but the dispersibility was poor. It settled in.

<Method for Producing Antioxidant 35>
Antioxidant 35 was produced as follows.
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser is charged with 288 g of acetone as a reaction solvent, and 40.00 g of 5-hydroxy-3,7-dithia-1,9-nonanediol and methyldiethanolamine with stirring. After dissolving 13.35 g, the temperature was raised to 40 ° C. and 58.65 g of isophorone diisocyanate was added. Thereafter, the temperature was raised to 50 ° C., 0.1 g of a tin-based catalyst was added, the temperature was further raised to 55 ° C., and the reaction was carried out for 2 hours while stirring.

  After completion of the reaction, the reaction solution was cooled to room temperature and cationized by adding 6.06 g of 85% formic acid. Further, 459 g of water was added, and the antioxidant aqueous dispersion (antioxidant 35) of the present invention having a solid content of 20% was produced in the same manner as in the production method of antioxidant 1.

Table 1 shows synthesis components and molar ratios of the antioxidants 1 to 35. Table 2 shows the weight average molecular weight and molecular weight distribution (Mw / Mn) measured by GPC (Gel Permeation Chromatography, controller: SC8010, detector: RI8012, manufactured by Tosoh Corporation). Also, FT / IR5300, C = O stretching vibration of 1730～1690Cm ^-1 which is characteristic absorption of the urethane groups by JASCO Corporation), N-H deformation vibration near 1540cm ^-1, 3450~3300cm around ^-1 Thus, it was confirmed that polymerization occurred in all the reactions and the component was polymerized.

Antioxidants 1 to 29, antioxidant 31, antioxidant 33 and antioxidant 35 are 20% aqueous dispersions.

<Example 1>
0.4 parts of boric acid (2% with respect to the alumina hydrate) and 100% aqueous dispersion of the antioxidant 1 with respect to 100 parts of the above-mentioned alumina hydrate dispersion and 2.0% in terms of solid content. Parts (10% with respect to alumina hydrate), and 5 parts aqueous solution of polyvinyl alcohol (PVA245, manufactured by Kuraray Co., Ltd.), 2 parts in terms of solid content (10% with respect to alumina hydrate) The mixture was added and stirred with a three-one motor until uniform. Thereafter, a polyethylene-coated paper (manufactured by Oji Paper Co., Ltd .; thickness: 224 μm, basis weight 234 g / m ² ; 60-degree specular gloss of 64% according to JIS-Z-8741; custom-made product) was used as the support. The above-prepared coating solution was applied with a Mayer bar so that the dry coating amount was 35 g / m ^2, and then dried at 110 ° C. for 20 minutes with a dryer to produce the recording medium of the present invention. The following evaluation 1, evaluation 2, evaluation 3, and evaluation 4 were performed. The results are shown in Table 3.

<Example 2>
A recording medium of the present invention was prepared in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 2 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 3>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 3 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 4>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 4 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 5>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 5 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 6>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 6 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 7>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 7 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 8>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 8 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 9>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 9 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 10>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 10 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 11>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 11 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 12>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 12 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 13>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 13 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 14>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 14 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 15>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 15 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 16>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 16 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 17>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 17 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 18>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 18 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 19>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 19 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 20>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 20 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 21>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 21 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 22>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 22 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 23>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 23 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 24>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 24 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 25>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 25 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 26>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 26 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 27>
In Example 1, the recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 27, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 28>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 28 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 29>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 29 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 30>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 31 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 31>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 33 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Example 32>
A recording medium of the present invention was produced in the same manner as in Example 1 except that the antioxidant 1 was changed to the antioxidant 35 in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. . The results are shown in Table 3.

<Comparative Example 1>
In Example 1, the recording medium of Comparative Example 1 was produced in the same manner as in Example 1 except that the antioxidant 1 was not added, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 2>
In Example 1, in place of antioxidant 1, 0.8 part (4% based on alumina hydrate) of 3,6-dithia-1,8-octanediol was added. Thus, the recording medium of Comparative Example 2 was produced, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 3>
Comparative Example 3 was carried out in the same manner as in Example 1 except that 0.8 part (4% based on alumina hydrate) of 2,2′-thiodiethanol was added instead of antioxidant 1 in Example 1. And the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative example 4>
In Example 1, in place of antioxidant 1, 0.8 part (4% based on alumina hydrate) of 1- (2-hydroxyethylthio) propan-2-ol was added. The recording medium of Comparative Example 4 was produced in the same manner as described above, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 5>
In Example 1, instead of the antioxidant 1, it was carried out except that 0.8 part (4% based on alumina hydrate) of 6-oxa-3,9-dithia-1,11-undecanediol was added. The recording medium of Comparative Example 5 was produced in the same manner as Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 6>
In Example 1, instead of antioxidant 1, it was carried out except that 0.8 part (4% based on alumina hydrate) of 5-hydroxy-3,7-dithia-1,9-nonanediol was added. The recording medium of Comparative Example 6 was produced in the same manner as in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 7>
In Example 1, in place of antioxidant 1, 0.8 part (4% based on alumina hydrate) of 1,2-bis (2,3-dihydroxypropylthio) ethane was added. The recording medium of Comparative Example 7 was produced in the same manner as in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 8>
In Example 1, instead of antioxidant 1, 0.8 part (4% based on alumina hydrate) of bis (2- (2-hydroxyethylthio-ethyl)) sulfone was added. The recording medium of Comparative Example 8 was produced in the same manner as in Example 1, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Comparative Example 9>
In Example 1, in place of antioxidant 1, 2.0 parts of 3,6-dithia-1,8-octanediol was added (10% with respect to alumina hydrate). Thus, a recording medium of Comparative Example 9 was produced, and the following Evaluation 1, Evaluation 2, Evaluation 3, and Evaluation 4 were performed. The results are shown in Table 4.

<Evaluation 1: Evaluation Method for Print Density>
Black (Bk) ink, cyan (C) ink, magenta (M) ink and yellow (Y) ink in a single color using the inkjet recording apparatus (BJ F870, manufactured by Canon Inc.) on the recording medium thus prepared. In addition, solid printing was performed at an ink amount of 100%, and the optical density of each color was measured using an optical reflection densitometer (RD-918, manufactured by Greta Macbeth).

<Evaluation 2: Evaluation method for fading / discoloration suppression effect by gas>
Discoloration / discoloration due to ozone exposure was printed on the black (Bk) ink and cyan (C) ink in a single color using an ink jet recording apparatus (BJ F870, manufactured by Canon Inc.) and solidly printed at 100% ink amount. The recording medium is put into an ozone exposure tester (made by Suga Test Instruments Co., Ltd., special order), exposed to ozone at a concentration of 1 ppm for 4 hours under the conditions of 40 ° C. and 55% RH, and the optical density of Bk and C is optically measured. Measurement was performed using a reflection densitometer (RD-918, manufactured by Greta Macbeth Co., Ltd.), and the remaining OD ratio was calculated and evaluated from the following formula (1).
Residual OD rate = (OD after test / OD before test) × 100% Formula (1)

<Evaluation 3: Evaluation method for fading / discoloration suppression effect by light>
Using the ink jet recording apparatus (BJ F870, manufactured by Canon Inc.), the above-mentioned recording medium in which magenta (M) ink is solidly printed with a single color and an ink amount of 100% is applied to an atlas fade meter (condition: wavelength 340 nm). Irradiation intensity of 0.39 W / m ² , temperature 45 ° C., humidity 70%), and after 100 hours, the optical density of M was measured using an optical reflection densitometer (made by Greta Macbeth, RD-918), Evaluation was performed by calculating the remaining OD ratio from the equation (1).

<Evaluation 4: Evaluation method for image bleeding under high humidity>
Using an inkjet recording apparatus (BJ F870, manufactured by Canon Inc.), solid printing with a single color of black (Bk) ink, cyan (C) ink, magenta (M) ink, and yellow (Y) ink (100% ink amount) The above-mentioned recording medium subjected to (1) was exposed to an environment of 30 ° C. and 80% RH for 1 week, and the degree of image blurring was visually evaluated. For each color, “◯” indicates that no bleeding occurs, “Δ” indicates that bleeding slightly occurs in any of the colors, and “X” indicates that bleeding greatly occurs in any of the colors.

  From the above results, the recording medium of the present invention in which the antioxidant of the present invention of Examples 1 to 32 was applied to the ink receiving layer was clearly more resistant than Comparative Example 1 in which no antioxidant was added. Gas characteristics, light resistance, and characteristics against image bleeding under high temperature and high humidity have been improved. Further, Comparative Examples 2 to 8 in which a diol having a sulfide group such as 3,6-dithia-1,8-octanediol was added in an amount substantially equal to the amount of the compound A unit contained in the antioxidant of the present invention. Compared to the recording medium, the light resistance and the characteristics against image bleeding under high temperature and high humidity were improved. On the other hand, the antioxidants used in Examples 1 to 32 (Production methods 1 to 29, 31, 33, and 35) were dispersible in water, whereas production methods 30, 32, and 34 were used. This antioxidant was poorly dispersible and immediately settled, making it impossible to produce a recording medium. From the above, it was possible to provide an antioxidant that effectively prevented discoloration and discoloration of an image due to acidic gas or light in the atmosphere and bleeding of the image under high temperature and high humidity. Also, by applying this, it was possible to obtain a recording medium suitable for long-term storage of images.

The recording medium in which the antioxidant of the present invention is applied to at least the ink-receiving layer is an image that effectively prevents color fading and bleeding of images under high temperature and high humidity due to acidic gas or light in the atmosphere. It is a recording medium suitable for long-term storage.

Claims (20)

Sulfur-containing organic compound (A) which is at least one selected from compounds having two or more active hydrogen groups represented by the following general formulas (7) to (12), a polyisocyanate compound having two or more isocyanate groups (B) and at least three compounds of amine compound (C) having two or more active hydrogen groups are reacted, and at least a part of the amino groups in the resulting product is cationized with an acid. Polymeric antioxidant characterized by

(In the formula, n represents 1 or 2. R ₁ represents a methylene group, an ethylene group, or a propylene group.)

(In the formula, n represents 1 or 2. R ₂ and R ₃ each independently represent a hydrogen atom or a hydroxyl group, and R ₂ and R ₃ may be the same or different.)

(Wherein n represents 0 or 1)

(In the formula, n represents 1 or 2, R ₄ represents a sulfur atom or an oxygen atom, R ₅ represents a sulfur atom or —SO ₂ —, and R ₄ and R ₅ are not the same and are different groups. Composed of)

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, and R ₆ and R ₇ may be the same or different.)

(In the formula, R ₈ represents a hydroxyl group.)   The polymeric antioxidant according to claim 1, wherein the content of the amine compound (C) contained in the product is 5.5 to 18.5% in terms of molar ratio.   The polymeric antioxidant according to claim 1, wherein the acid is phosphoric acid and / or a monovalent acid.   The polymeric antioxidant according to claim 3, wherein the monovalent acid is a hydroxy acid.   The polymer antioxidant according to claim 1, wherein the sulfur-containing organic compound (A) contains at least one sulfide group in the molecule.   The polymeric antioxidant according to claim 1, wherein the sulfur-containing organic compound (A) has three or more active hydrogen groups, and at least one is a hydroxyl group. The mass of the sulfur-containing organic compound (A) contained in the product accounts for 10 to 65% by mass in the polymer antioxidant, and the content of the amine compound (C) is 5.5 in terms of molar ratio. The polymeric antioxidant according to claim 1, which is ˜18.5%.   The sulfur-containing organic compound (A) is 3,6-dithia-1,8-octanediol, 1,2-bis (2,3-dihydroxypropylthio) ethane, 6-oxa-3,9-dithia-1, 11-undecanediol, bis (2- (2-hydroxyethylthio-ethyl)) sulfone, 2,2-thiodiethanol, 1- (2-hydroxyethylthio) -propan-2-ol, and 5-hydroxy-3 The polymer antioxidant according to claim 1, which is at least one selected from 1,7-dithia-1,9-nonanediol. The polymer antioxidant according to claim 1, which is at least one kind represented by the following general formulas (1) to (6).

(Wherein n is 1 or 2, R ₁ is a methylene group, ethylene group or propylene group, R ₉ is an aliphatic hydrocarbon group containing one or more alkylene or double alicyclic rings, and R ₁₀ is carbon number 1) ˜4, R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a methyl group, X ⁻ represents an acid anion, and m is a number with a weight average molecular weight of 2,000 to 150,000. .)

(A wherein n is 1 or 2, R ₂ and R ₃ are independently a hydrogen atom, a hydroxyl group or an alkyl group, R ₂ and R ₃ may be be the same or different. In addition, R ₉ ~ ₁₂ and X ^- and m have the same meaning as in general formula (1).)

(In the formula, n represents 0 or 1. R ₉ to ₁₂ and X ⁻ and m have the same meaning as in the general formula (1).)

(In the formula, n is 1 or 2, R ₄ is a sulfur atom or an oxygen atom, R ₅ is a sulfur atom or —SO ₂ — , and R ₄ and R ₅ are not the same, and are composed of different groups. R ₉ to ₁₂ and X ⁻ and m have the same meanings as those in the general formula (1).)

(Wherein R ₆ and R ₇ each independently represents a hydrogen atom or an alkyl group, and R ₆ and R ₇ may be the same or different. R ₉ to ₁₂ and X ⁻ and m are (It is synonymous with Formula (1).)

(In the formula, R ₈ represents a hydroxyl group or an alkyl group. R ₉ to ₁₂ and X ⁻ and m have the same meanings as those in the general formula (1).)   An ink receiving layer comprising at least an inorganic pigment, a water-soluble and / or water-dispersible resin, a hardener, the polymer antioxidant according to any one of claims 1 to 9, and water. Coating liquid.   The recording medium in which one or more ink receiving layers are provided on at least one surface of a support, wherein at least the ink receiving layer comprises the polymer antioxidant according to any one of claims 1 to 9. A recording medium comprising at least one kind. Sulfur-containing organic compound (A) which is at least one selected from compounds having two or more active hydrogen groups represented by the following general formulas (7) to (12), a polyisocyanate compound having two or more isocyanate groups (B) and at least three compounds of amine compound (C) having two or more active hydrogen groups are reacted, and at least a part of the amino groups in the resulting product is cationized with an acid. A polymer compound characterized by

(In the formula, n represents 1 or 2. R ₁ represents a methylene group, an ethylene group, or a propylene group.)

(In the formula, n represents 1 or 2. R ₂ and R ₃ each independently represent a hydrogen atom or a hydroxyl group, and R ₂ and R ₃ may be the same or different.)

(Wherein n represents 0 or 1)

(In the formula, n represents 1 or 2, R ₄ represents a sulfur atom or an oxygen atom, R ₅ represents a sulfur atom or —SO ₂ —, and R ₄ and R ₅ are not the same and are different groups. Composed of)

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, and R ₆ and R ₇ may be the same or different.)

(In the formula, R ₈ represents a hydroxyl group.)   The polymer compound according to claim 12, wherein the content of the amine compound (C) contained in the product is 5.5 to 18.5% in terms of molar ratio.   The polymer compound according to claim 12, wherein the acid is phosphoric acid and / or a monovalent acid.   The polymer compound according to claim 14, wherein the monovalent acid is a hydroxy acid.   The polymer compound according to claim 12, wherein the sulfur-containing organic compound (A) contains at least one sulfide group in the molecule.   The polymer compound according to claim 12, wherein the sulfur-containing organic compound (A) has three or more active hydrogen groups, and at least one is a hydroxyl group. The mass of the sulfur-containing organic compound (A) contained in the product accounts for 10 to 65% by mass in the polymer compound, and the content of the amine compound (C) is 5.5 to 18 in terms of molar ratio. The polymer compound according to claim 12, which is 0.5%.   The sulfur-containing organic compound (A) is 3,6-dithia-1,8-octanediol, 1,2-bis (2,3-dihydroxypropylthio) ethane, 6-oxa-3,9-dithia-1, 11-undecanediol, bis (2- (2-hydroxyethylthio-ethyl)) sulfone, 2,2-thiodiethanol, 1- (2-hydroxyethylthio) -propan-2-ol, and 5-hydroxy-3 The polymer compound according to claim 12, which is at least one selected from 1,7-dithia-1,9-nonanediol. The polymer compound according to claim 12, which is at least one kind represented by the following general formulas (1) to (6).

(Wherein n is 1 or 2, R ₁ is a methylene group, ethylene group or propylene group, R ₉ is an aliphatic hydrocarbon group containing one or more alkylene or double alicyclic rings, and R ₁₀ is carbon number 1) ˜4, R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a methyl group, X ⁻ represents an acid anion, and m is a number with a weight average molecular weight of 2,000 to 150,000. .)

(A wherein n is 1 or 2, R ₂ and R ₃ are independently a hydrogen atom, a hydroxyl group or an alkyl group, R ₂ and R ₃ may be be the same or different. In addition, R ₉ ~ ₁₂ and X ^- and m have the same meaning as in general formula (1).)

(In the formula, n represents 0 or 1. R ₉ to ₁₂ and X ⁻ and m have the same meaning as in the general formula (1).)

(In the formula, n is 1 or 2, R ₄ is a sulfur atom or an oxygen atom, R ₅ is a sulfur atom or —SO ₂ — , and R ₄ and R ₅ are not the same, but are composed of different groups. R ₉ to ₁₂ and X ⁻ and m have the same meanings as those in the general formula (1).)

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group, and R ₆ and R ₇ may be the same or different. R ₉ to ₁₂ and X ⁻ and m are (It is synonymous with Formula (1).)

(In the formula, R ₈ represents a hydroxyl group or an alkyl group. R ₉ to ₁₂ and X ⁻ and m have the same meanings as those in the general formula (1).)