JP2017026684A - Resin composition, toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that has suppressed a reduction in infrared absorption performance.SOLUTION: There is provided a resin composition comprising: a polyester resin having a structural unit derived from bisphenol A in an amount of 1 mass% or less based on the total amount of the polyester resin; and a compound represented by the following general formula (I). In the general formula (I), Rrepresents a group represented by the general formula (I-R), and R, R, and Reach independently represent an alkyl group. In the general formula (I-R), Rrepresents hydrogen or a methyl group, and e represents an integer of 0 or more and 3 or less.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, an electrostatic charge image developing toner, an electrostatic latent image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  Patent Document 1 discloses a magenta toner for light fixing containing a binder resin, at least one selected from a diimonium compound and an aminium compound having a specific structure as an infrared absorber, and monomethylquinacridone as a magenta pigment. It is disclosed.

  Patent Document 2 discloses an infrared light absorber containing a perimidine-based squarylium dye having a specific structure.

JP 2012-008279 A JP 2011-068706 A

  An object of the present invention is to use a polyester resin in which a structural unit derived from bisphenol A is 1% by mass or less based on the whole polyester resin, and a compound represented by the general formula (I) as an infrared absorber. It is providing the resin composition by which the fall of infrared absorption performance was suppressed compared with the case where it replaces and using only an infrared absorber (A4).

The above problem is solved by the following means. That is,
The invention according to claim 1
The resin composition containing the polyester resin whose structural unit derived from bisphenol A is 1 mass% or less with respect to the whole polyester resin, and the compound represented by the following general formula (I).

(In General Formula (I), R ^a represents a group represented by General Formula (IR), and R ^b , R ^c, and R ^d each independently represents an alkyl group.
In General Formula (IR), R ^e represents hydrogen or a methyl group, and e represents an integer of 0 or more and 3 or less. )

The invention according to claim 2
The resin composition containing the acrylic resin which has OH group in a side chain, and the compound represented by the said general formula (I).

The invention according to claim 3
3. The resin composition according to claim 1, wherein at least one of R ^b , R ^c, and R ^{d in} the general formula (I) is a group represented by the general formula (IR).

The invention according to claim 4
The resin composition according to claim 1 or 2, wherein all of R ^b , R ^c, and R ^{d in} the general formula (I) are groups represented by the general formula (IR).

The invention according to claim 5
Formula (I-R) in the R ^e is methyl claim 1 resin composition according to any one of claims 4.

The invention according to claim 6
E in the said general formula (IR) is 0, The resin composition as described in any one of Claims 1-5.

The invention according to claim 7 provides:
An electrostatic charge image developing toner comprising the resin composition according to any one of claims 1 to 6.

The invention according to claim 8 provides:
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 7.

The invention according to claim 9 is:
Containing the electrostatic image developing toner according to claim 7;
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 10 is:
A developing means for accommodating the electrostatic charge image developer according to claim 8 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 11 is:
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 8 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising:

The invention according to claim 12
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer according to claim 8;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising:

  According to the first aspect of the present invention, a polyester resin in which the structural unit derived from bisphenol A is 1% by mass or less based on the whole polyester resin is used as the resin, and the general formula (I) is used as an infrared absorber. In comparison with the case where only the infrared absorbent (A4) is used in place of the compound represented, a resin composition in which a decrease in infrared absorption performance is suppressed is provided.

  According to the invention which concerns on Claim 2, it replaces with the compound represented by the said general formula (I) as an infrared absorber as an infrared absorber (A4) instead of using the acrylic resin which has OH group in a side chain as resin. The resin composition in which the decrease in the infrared absorption performance is suppressed as compared with the case of using only the resin is provided.

  According to the invention which concerns on Claim 3, 4, 5 or 6, it replaces with the infrared rays absorber compared with the case where only an infrared absorber (A4) is used instead of the compound represented by the said general formula (I). Provided is a resin composition in which a decrease in absorption performance is suppressed.

  According to the invention which concerns on Claim 7, it replaces with the compound represented by the said general formula (I) as an infrared absorber, and compared with the case where only the resin composition using only an infrared absorber (A4) is included, infrared absorption There is provided a toner for developing an electrostatic charge image in which a decrease in performance is suppressed.

  According to the invention concerning Claim 8, 9, 10, 11, or 12, it replaces with the compound represented by the said general formula (I) as an infrared absorber, and uses the infrared absorber (A4) only. An electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, or an image forming method in which a decrease in fixability of a toner image is suppressed as compared with a case where a toner for developing an electrostatic charge image containing only toner is used. .

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment.

  Hereinafter, the present embodiment which is an example of the present invention will be described.

<Resin composition>
The resin composition according to the first aspect of the present embodiment is a polyester resin in which the structural unit derived from bisphenol A is 1% by mass or less with respect to the entire polyester resin (hereinafter may be referred to as “specific polyester resin”). And a compound represented by the following general formula (I) (hereinafter sometimes referred to as “specific infrared absorber”).

(In General Formula (I), R ^a represents a group represented by General Formula (IR), and R ^b , R ^c, and R ^d each independently represents an alkyl group.
In General Formula (IR), R ^e represents hydrogen or a methyl group, and e represents an integer of 0 or more and 3 or less. )

  Since the resin composition according to the first aspect is configured as described above, the specific polyester resin is used, and instead of the specific infrared absorber, the following infrared absorber (A4) (hereinafter referred to as “comparative infrared absorber”). In comparison with a resin composition using (which may be the case), a decrease in infrared absorption performance is suppressed.

  Conventionally, by using a polyester resin in which the structural unit derived from bisphenol A exceeds 1% by mass with respect to the entire polyester resin as a resin (hereinafter sometimes referred to as “conventional polyester resin”) and an infrared absorber, infrared absorption is achieved. A large amount of the resin composition was obtained. However, when a specific polyester resin is used, the infrared absorption amount of the resin composition may be smaller than when a conventional polyester resin is used even when the infrared absorber having the same concentration is used. That is, the infrared absorbing ability of the infrared absorbent may be reduced by mixing the infrared absorbent with the specific polyester resin.

  As one of the causes that the infrared absorbing ability of the infrared absorbent is reduced by mixing with the specific polyester resin, for example, the solubility of the infrared absorbent in the specific polyester resin is low. Specifically, when the conventional polyester resin is used, the solubility of the infrared absorber in the resin is enhanced by the bisphenol A skeleton in the conventional polyester resin, whereas the specific polyester resin has a structure derived from bisphenol A. Since a unit is 1 mass% or less, it is thought that the solubility of an infrared absorber is low. And it is estimated that it is difficult to disperse | distribute an infrared absorber in specific polyester resin by low solubility, and it becomes difficult to exhibit infrared absorption ability because an infrared absorber is unevenly distributed.

On the other hand, when a specific infrared absorber is used as the infrared absorber, even if the resin is a specific polyester resin, a resin composition in which a decrease in infrared absorption performance is suppressed can be obtained. The reason for this is not clear, but the specific infrared absorber has an alkyl group branched at the end of the molecule, so that the solubility of the specific infrared ray absorbent becomes high with respect to a specific polyester resin having a small bisphenol A skeleton. It is presumed that the infrared absorption amount of the object increases.
As described above, the specific infrared absorber imparts high infrared absorption performance to a wide range of resins including the specific polyester resin.

  Further, the resin composition according to the second aspect of the present embodiment is represented by an acrylic resin having an OH group in the side chain (hereinafter sometimes referred to as “specific acrylic resin”) and the following general formula (I). And a compound (specific infrared absorber).

(In General Formula (I), R ^a represents a group represented by General Formula (IR), and R ^b , R ^c, and R ^d each independently represents an alkyl group.
In General Formula (IR), R ^e represents hydrogen or a methyl group, and e represents an integer of 0 or more and 3 or less. )

  Since the resin composition according to the second aspect has the above-described configuration, the infrared ray absorbing performance is higher than that of the resin composition using the specific acrylic resin and using the comparative infrared absorber instead of the specific infrared absorber. Reduction is suppressed.

  When an acrylic resin having no OH group in the side chain is used as the resin (hereinafter sometimes referred to as “conventional acrylic resin”), a resin composition having a large infrared absorption amount can be obtained even if a comparative infrared absorber is used. . However, when the specific acrylic resin is used, the infrared absorption performance of the resin composition is lowered as compared with the case where the conventional acrylic resin is used even if the comparative infrared absorbent having the same concentration is used. The reason is not clear, but it is presumed that the specific acrylic resin has an OH group in the side chain, so that the polarity is high and the solubility of the comparative infrared absorbent in the specific acrylic resin is low.

On the other hand, when a specific infrared absorber is used, even when a specific acrylic resin is used, a resin composition in which a decrease in infrared absorption performance is suppressed as compared with the case where a comparative infrared absorber is used is obtained. The reason is not clear, but the specific infrared absorber has a branched alkyl group at the end of the molecule, so that the solubility of the specific infrared absorber becomes high even for a specific acrylic resin having a high polarity. It is presumed that the amount of infrared absorption increases.
As described above, the specific infrared absorber imparts high infrared absorption performance to a wide range of resins including the specific acrylic resin.

(resin)
-Specific polyester resin-
The resin composition according to the first aspect includes at least a specific polyester resin as a resin, and may include a resin other than the polyester resin as necessary. However, 10 mass% or more is preferable, as for the ratio of specific polyester resin with respect to the whole resin contained in the resin composition which concerns on a 1st aspect, 40 mass% or more is more preferable, and 100 mass% is the most preferable. The specific polyester resin is preferably contained in the resin composition as a binder resin.

A specific polyester resin will not be specifically limited if the structural unit derived from bisphenol A is 1 mass% or less with respect to the whole polyester resin. The specific polyester preferably contains substantially no structural unit derived from bisphenol A, and more preferably contains no structural unit derived from bisphenol A.
Examples of the method for obtaining the content of the structural unit derived from bisphenol A include a method for obtaining the content by analyzing the composition of the polyester resin contained in the resin composition by NMR or the like.

In the present specification, the “structural unit derived from bisphenol A” means a structure represented by the following structural formula (R) (hereinafter sometimes referred to as “bisphenol A structure”). That is, the “structural unit derived from bisphenol A” is not only the bisphenol A structure in the polyester resin using bisphenol A itself as a monomer, but also the bisphenol A structure in the polyester resin using modified bisphenol A as a monomer. It is a concept that also includes
Here, “modified bisphenol A” in the present specification means a compound in which a hydrogen atom of the hydroxy group of bisphenol A is substituted, and specifically includes, for example, a bisphenol A alkylene oxide adduct.
Further, “content of structural unit derived from bisphenol A” in the polyester resin using modified bisphenol A as a monomer does not include the mass of the modified part, but only the bisphenol A structure represented by the following structural formula (R). The content calculated from the mass of. Specifically, for example, when a bisphenol A alkylene oxide adduct is used as the modified bisphenol A, the “content of structural unit derived from bisphenol A” means the mass of the bisphenol A structure relative to the mass of the entire polyester resin, It is calculated without including the mass of the alkylene oxide.

In addition to the structural unit derived from bisphenol A, the specific polyester more preferably contains substantially no structural unit derived from the bisphenol A derivative. That is, the total of the content of the structural unit derived from bisphenol A and the content of the bisphenol A skeleton contained in the structural unit derived from the bisphenol A derivative is 1% by mass or less based on the entire polyester resin. It is more preferable that the structural unit derived from bisphenol A and the structural unit derived from the bisphenol A derivative are not included at all.
Here, examples of the bisphenol A derivative include derivatives in which hydrogen bonded to the benzene ring of bisphenol A is substituted with a substituent.
In addition, “content of bisphenol A skeleton contained in structural unit derived from bisphenol A derivative” does not include the mass of the substituent, the structural unit derived from bisphenol A derivative is replaced with bisphenol A structure, and the substituted bisphenol is replaced. It means the content calculated from the mass of the A structure.

  As specific polyester resin, the condensation polymer of polyhydric alcohol other than polyhydric carboxylic acid and bisphenol A is mentioned, for example. In addition, as a specific polyester resin, a commercial item may be used and what was synthesize | combined may be used.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (eg, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.) Alicyclic dicarboxylic acids (for example, cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or lower (for example, having 1 or more carbon atoms) 5 or less) alkyl esters. Among these, as polyvalent carboxylic acid, aromatic dicarboxylic acid is preferable, for example.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower (for example, having 1 to 5 carbon atoms) alkyl esters.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (for example, cyclohexanediol, cyclohexanedimethanol, And hydrogenated bisphenol A) and aromatic diols other than bisphenol A (for example, hydroquinone, 4,4′-dihydroxybiphenyl, etc.). Among these, as the polyhydric alcohol, aliphatic diols and alicyclic diols are preferable, and aliphatic diols are more preferable.
As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used together with the diol. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

The glass transition temperature (Tg) of the specific polyester resin is not particularly limited; .
As a method for adjusting the glass transition temperature (Tg) of the specific polyester resin to the above range, for example, at least one aromatic diol other than the aromatic dicarboxylic acid and bisphenol A is used as compared with the case where a conventional polyester resin is synthesized. A method often used is mentioned.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically described in the method for determining the glass transition temperature in JIS K 7121-1987 “Method for Measuring Plastic Transition Temperature”. Of “extrapolated glass transition start temperature”.

Although the weight average molecular weight (Mw) of specific polyester resin is not specifically limited, For example, when using a resin composition for the toner for electrostatic image development, 5000-1 million are preferable and 7000-500000 are more preferable.
The number average molecular weight (Mn) of the specific polyester resin is not particularly limited. However, for example, when the resin composition is used for an electrostatic image developing toner, it is preferably from 2,000 to 100,000.
The molecular weight distribution Mw / Mn of the specific polyester resin is not particularly limited. For example, when the resin composition is used for the toner for developing an electrostatic image, it is preferably from 1.5 to 100, more preferably from 2 to 60.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

The specific polyester resin is obtained by a known production method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polymerized together with the main component. It is good to condense.

-Specific acrylic resin-
The resin composition which concerns on a 2nd aspect contains specific acrylic resin at least as resin, and may contain resin other than an acrylic resin as needed. However, the ratio of the specific acrylic resin to the entire resin contained in the resin composition according to the second aspect is preferably 20% by mass or more, more preferably 40% by mass or more, and most preferably 100% by mass. The specific acrylic resin is preferably contained in the resin composition as a binder resin.

In this specification, “acrylic resin” includes a structural unit derived from a monomer having at least one of an acryloyloxy group and a methacryloyloxy group (hereinafter sometimes referred to as “(meth) acryloyloxy group”). Say resin.
A monomer having an acryloyloxy group is an “acrylic monomer”, a monomer having a methacryloyloxy group is a “methacrylic monomer”, and a monomer having a (meth) acryloyloxy group is “(meth)” It may be referred to as “acrylic monomer”.
The acrylic resin only needs to contain at least a structural unit derived from a (meth) acrylic monomer, and may be referred to as a monomer other than the (meth) acrylic monomer (hereinafter referred to as “other monomer”). ) May be included. That is, in the present specification, a (meth) acrylic monomer and other monomer copolymer) also corresponds to “acrylic resin”.

A specific acrylic resin will not be specifically limited if it is an acrylic resin which has OH group in a side chain. The specific acrylic resin may be a resin containing a structural unit derived from a (meth) acrylic monomer having an OH group, or another unit having a structural unit derived from a (meth) acrylic monomer and an OH group. It may be a resin containing a structural unit derived from a monomer. Among these, the specific acrylic resin preferably includes a structural unit derived from a (meth) acrylic monomer having an OH group.
Here, “OH group” in the present specification means a group represented by “—OH”, and is a concept including “—OH” in a carboxy group in addition to a hydroxy group. Further, the “side chain” refers to a carbon chain having 2 or more carbon atoms bonded to the main chain (the longest trunk chain in the resin molecular structure).

Examples of the specific acrylic resin include a copolymer of a (meth) acrylic monomer having an OH group and a (meth) acrylic monomer not having an OH group, and a (meth) acrylic monomer having an OH group. Copolymer of (meth) acrylic monomer having no OH group and other monomer not having OH group, (meth) acrylic monomer having OH group and no OH group Copolymer of (meth) acrylic monomer and other monomer having OH group and other monomer not having OH group, (meth) acrylic monomer having no OH group and OH A copolymer of another monomer having a group and another monomer having no OH group, a (meth) acrylic monomer having no OH group, and another monomer having an OH group; And the like.
In addition, the specific acrylic resin may use a commercial item, and may use what was synthesize | combined.

Examples of the acrylic monomer having an OH group include an acrylate ester having an OH group. Specific examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate. Monofunctional acrylic acid hydroxyalkyl esters such as 1,4-cyclohexanedimethanol monoacrylate; monofunctional acrylic acid carboxyalkyl esters such as 2-carboxyethyl acrylate; and the like. Moreover, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid etc. are mentioned as acrylic acid ester which has OH groups other than monofunctional acrylic acid hydroxyalkyl ester and monofunctional acrylic acid carboxyalkyl ester.
Among these, the acrylic monomer having an OH group is preferably an acrylic acid hydroxyalkyl ester, and more preferably an acrylic acid hydroxyalkyl ester having an alkyl chain having 2 to 4 carbon atoms.

Specific examples and preferred examples of the methacrylic monomer having an OH group include a methacrylic monomer corresponding to the acrylic monomer having the OH group (that is, the acryloyl group of the acrylic monomer having the OH group is methacryloyl). A compound substituted with a group).
The (meth) acrylic monomer having an OH group may be used alone or in combination of two or more.

Examples of the acrylic monomer having no OH group include acrylic acid and acrylic acid ester having no OH group.
Examples of the acrylate ester having no OH group include n-methyl acrylate, n-ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, N-heptyl acrylate, n-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-lauryl acrylate, n-tetradecyl acrylate, n-hexadecyl acrylate, n-octadecyl acrylate, etc. Monofunctional acrylic acid ester having a chain alkyl group; isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, isopentyl acrylate, neopentyl acrylate, isohexyl acrylate, isoheptyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate Branching etc. Monofunctional acrylic acid ester having an alkyl group; monofunctional acrylic acid ester having an aromatic ring such as phenyl acrylate, biphenyl acrylate, diphenylethyl acrylate, t-butylphenyl acrylate, terphenyl acrylate; cyclohexyl acrylate, Monofunctional acrylic acid ester having a cycloalkyl group such as t-butylcyclohexyl acrylate; Monofunctional acrylic acid ester having an amino group such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate; alkoxy group such as methoxyethyl acrylate Monofunctional acrylic acid ester having polyfunctional acrylic acid ester such as ethylene glycol diacrylate, nonanediol diacrylate, decanediol diacrylate, trimethylolpropane triacrylate Etc. The.

Among these, the acrylic monomer having no OH group is preferably acrylic acid or a monofunctional acrylic ester, more preferably acrylic acid or a monofunctional acrylic ester having an alkyl group.
Specific examples and preferred examples of the methacrylic monomer having no OH group include a methacrylic monomer corresponding to the acrylic monomer having no OH group (that is, an acrylic monomer having no OH group). Compound in which the acryloyl group of the body is substituted with a methacryloyl group).
The (meth) acrylic monomer having no OH group may be used alone or in combination of two or more.

Examples of other monomers include monomers having a vinyl group. Specifically, for example, styrenes, vinyl nitriles, vinyl ethers, vinyl ketones, acids having a vinyl group, and vinyl groups. And bases having a vinyl group, and esters having a vinyl group.
Examples of styrenes include styrene and alkyl-substituted styrene (for example, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, etc. ), Halogen-substituted styrene (for example, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, etc.), vinylnaphthalene (2-vinylnaphthalene, etc.), hydroxystyrene (4-ethenylphenol, etc.), and the like.

Examples of vinyl nitriles include acrylonitrile and methacrylonitrile.
Examples of vinyl ethers include vinyl methyl ether, vinyl isobutyl ether, hydroxyalkyl vinyl ether (2-hydroxyethyl vinyl ether, etc.) and the like.
Examples of vinyl ketones include vinyl alkyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone.
Examples of the acids having a vinyl group include maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid and the like.
Examples of bases having a vinyl group include vinylpyridine and vinylamine.
Examples of the ester having a vinyl group include vinyl acetate.

Among these, as other monomers, styrenes are preferable, styrene, alkyl-substituted styrene, and hydroxystyrene are more preferable, and styrene and alkyl-substituted styrene are more preferable.
Other monomers may be used alone or in combination of two or more.

As content of OH group in a specific acrylic resin, 10 mgKOH / g or more and 200 mgKOH / g or less are mentioned, for example, 20 mgKOH / g or more and 150 mgKOH / g or less are preferable, and 30 mgKOH / g or more and 120 mgKOH / g are more preferable.

Although the glass transition temperature (Tg) of the specific acrylic resin is not particularly limited, for example, when the resin composition is used for toner for developing an electrostatic image, it is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower. .

The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically described in the method for determining the glass transition temperature in JIS K 7121-1987 “Method for Measuring Plastic Transition Temperature”. Of “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the specific acrylic resin is not particularly limited. For example, when the resin composition is used for a toner for developing an electrostatic image, it is preferably from 5,000 to 1,000,000, and more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the specific acrylic resin is not particularly limited.
The molecular weight distribution Mw / Mn of the specific acrylic resin is not particularly limited. For example, when the resin composition is used for the toner for developing an electrostatic charge image, it is preferably from 1.5 to 100, and more preferably from 2 to 60.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

  The specific acrylic resin is obtained by a well-known manufacturing method. Specifically, for example, a (meth) acrylic monomer and other monomers as required are mixed into an emulsion polymerization method, a soap-free emulsion polymerization method, a suspension polymerization method, a miniemulsion polymerization method, a microemulsion polymerization method. It can be obtained by polymerizing by a radical polymerization method such as a combination method.

(Specific infrared absorber)
The resin composition contains at least a compound represented by the general formula (I) as an infrared absorber.

In general formula (I), R ^a represents a group represented by general formula (IR).
The total number of carbon atoms of the group represented by the general formula (IR) is preferably 6 or less, more preferably 5 or less, further preferably 4 or less, and further preferably 3. The lower limit of the total carbon number is 3.

In the general formula (I-R), R ^e represents hydrogen or a methyl group, preferably a methyl group. When R ^e in the general formula (I-R) is a methyl group, the terminal is a trifurcated structure (tertiary), and the infrared absorption performance is further prevented from lowering than when R ^e is hydrogen. The This is considered to be because the solubility in the specific polyester resin and the specific acrylic resin is higher when ^Re is a methyl group than when ^Re is hydrogen.

  In general formula (IR), e represents an integer of 0 or more and 3 or less, e is preferably 0 or more and 2 or less, e is preferably 0 or more and 1 or less, and more preferably 0. The smaller the value of e in the general formula (IR), the more the decrease in infrared absorption performance is suppressed. This is because, as the value of e is smaller, the distance between the branched structure portion in the group represented by the general formula (IR) and the squarylium structure in the compound represented by the general formula (I) is closer. It is considered that the solubility in the polyester resin and the specific acrylic resin is increased.

  Specific examples of the group represented by the general formula (IR) include i-propyl group, t-butyl group, i-butyl group (2-methylpropan-1-yl group), i-pentyl group (3 -Methylbutan-1-yl group), t-pentyl group (2,2-dimethylpropan-1-yl group), i-hexyl group (4-methylpentan-1-yl group), t-hexyl group (3, 3-dimethylbutan-1-yl group) and t-heptyl group (4,4-dimethylpentan-1-yl group). Among these, i-propyl group, t-butyl group, and i-butyl group (2-methylpropan-1-yl group) are more preferable, and t-butyl group is still more preferable.

In general formula (I), R ^b , R ^c and R ^d each independently represents an alkyl group. It is preferable that at least one of R ^b , R ^c, and R ^d is a group represented by the general formula (IR), and all of R ^b , R ^c, and R ^d are the general formula (IR). It is more preferable that it is group represented by these. As the number of groups represented by the general formula (IR) in the general formula (I) increases, the decrease in the infrared absorption performance is further suppressed. This is presumably because the more groups represented by the general formula (IR), the higher the solubility in the specific polyester resin and the specific acrylic resin.
When one of R ^b , R ^c and R ^d is a group represented by the general formula (IR), that is, the compound represented by the general formula (I) is represented by the general formula (IR). R ^a and R ^b may be a group represented by the general formula (IR), and R ^a and R ^c or R ^d may be represented by the general formula (I-R). It may be a group represented by R).
In addition, when two or more of R ^{a to} R ^d are groups represented by the general formula (IR), the structures of the groups represented by a plurality of general formulas (IR) are the same. It may or may not be. A preferable structure in the case where at least one of R ^b , R ^c and R ^d is a group represented by the general formula (IR) is the same as that described above.

In general formula (I), when at least one of R ^b , R ^c and R ^d is other than the group represented by general formula (IR), the alkyl group is linear, branched, and cyclic Any structure may be used. In this case, the alkyl group preferably has a larger number of branches and more preferably has a shorter carbon chain. The number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less, and still more preferably 1 or more and 6 or less.
Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, s-butyl group (2-butyl group), and 2-methylbutan-2-yl group. 3-methylbutan-2-yl group, 3,3-dimethylbutan-2-yl group, 3-pentyl group, 2-methylpentan-3-yl group, 3-methylpentan-3-yl group, cyclopentyl group, A cyclohexyl group etc. are mentioned. When at least one of R ^b , R ^c and R ^d is other than the group represented by the general formula (IR), among the above specific examples, a 2-methylbutan-2-yl group, 3-methylpentane- A 3-yl group is preferred.

Specific examples (exemplary compounds) of the compounds represented by formula (I) are shown below. In addition, the compound shown by general formula (I) is not limited at all by these.
First, specific examples having four groups represented by the general formula (IR) are shown.

  Next, specific examples having two groups represented by formula (IR) are shown.

  Among the specific examples of the compounds represented by the general formula (I) listed above, exemplary compounds (Ia-1) to (Ia-7), (Ib-1) to (Ib) -6) and (Ic-1) to (Ic-6) are preferable. Furthermore, (Ia-1), (Ib-3), and (Ic-3) are more preferable, and exemplary compound (Ia-1) is most preferable.

  An example of a method for synthesizing the compound represented by the general formula (I) will be described.

In the case where R ^{a to} R ^d are all compounds having the same structure, the compound represented by the general formula (I) is synthesized according to the following scheme 1, for example. However, in Scheme 1, the synthesis route of Compound (I) -A in which R ^{a to} R ^d in General Formula (I) are all groups represented by General Formula (IR) and are groups having the same structure Show.

  First, the starting material 1 is allowed to act dropwise on an organic solvent (for example, tetrahydrofuran) solution of an organic magnesium halide (for example, Grignard reagent, for example, ethylmagnesium chloride) under cooling in an inert atmosphere. Thereafter, the temperature may be returned to room temperature (for example, 23 ° C. to 25 ° C.) or higher in order to complete the reaction. Next, under cooling, a formic acid derivative (for example, ethyl formate) is allowed to act dropwise. Thereafter, the temperature may be returned to room temperature (for example, 23 ° C. to 25 ° C.) or higher in order to complete the reaction. An organic substance is extracted from the mixture after the reaction, and intermediate A is obtained from the separated organic layer.

  Next, the intermediate A and an oxidizing reagent (for example, manganese oxide) are added to a solvent (for example, cyclohexane), and the mixture is reacted by heating under reflux. Water generated during the reaction may be removed. Intermediate B is obtained from the organic layer of the reaction mixture. In addition, when obtaining the intermediate body B, you may refine | purify.

  Next, the cycloaddition reaction is performed on intermediate B. For example, sodium hydrogensulfide n hydrate is added to a solvent (for example, ethanol), and the intermediate B is added dropwise under cooling. Thereafter, the reaction is carried out at room temperature (for example, 23 ° C. to 25 ° C.), and after removing the solvent from the reaction solution, sodium chloride is added until saturation, followed by liquid separation to recover the organic phase to obtain Intermediate C from the organic phase. In addition, when obtaining the intermediate C, you may refine | purify.

  Next, a solvent (eg, anhydrous tetrahydrofuran) and intermediate C are mixed in an inert atmosphere, and a Grignard reagent (eg, methylmagnesium bromide) is added dropwise. After completion of the dropwise addition, the reaction solution is heated to reflux, and then ammonium bromide is added dropwise under cooling. The separated organic layer is dried and concentrated to give intermediate D.

  Next, in an inert atmosphere, intermediate D and squaric acid are dispersed in a solvent (such as a mixed solvent of cyclohexane and isobutanol), a basic compound (such as pyridine) is added, and the mixture is heated to reflux to obtain compound (I). -A is obtained. Water generated during the reaction may be removed. Further, purification, isolation, concentration and the like may be performed.

In the case where R ^a and R ^d have the same structure and R ^b and R ^c have the same structure Next, R ^a and R ^d in the general formula (I) are groups having the same structure, and R ^b and R ^c A synthetic route of a compound in which ^c is a group having the same structure and different from R ^a and R ^d will be described.
This compound is synthesized by changing the synthesis of intermediate A in compound (I) -A to the method shown in Scheme 2 below.

In Scheme 2, first, the starting material 2 and the additive material 2 are added and reacted in a Grignard reagent (an organic solution (for example, a THF solution or the like) to which (for example, ethylmagnesium bromide) has been added). A strong acid (such as hydrochloric acid) is added to the solution after the reaction under cooling, and then ether is added at room temperature (such as 23 ° C. to 25 ° C.) to obtain intermediate A ′ from the organic layer. In addition, you may refine | purify when obtaining intermediate body A '.
Thereafter, synthesis is performed in the same manner except that the intermediate A shown in the above-mentioned scheme 1 is changed to the intermediate A ′.

In the case where R ^a and R ^b are the same structure and R ^c and R ^d are the same structure, R ^a and R ^b in the general formula (I) are groups having the same structure, and R ^c and R ^{d Are} compounds having the same structure and different from R ^a and R ^b , two types of intermediates D in the compound (I) -A having different structures of R ₁ are prepared, Synthesis is performed in the same manner as in Scheme 1 using these two kinds of intermediates D, and the obtained compound is purified.

In addition, the compounds having the same structure in three of R ^{a to} R ^d , the compounds having the same two structures in which two of them are different, and the compounds having different structures in the other two are also shown in Scheme 1 and Scheme 2 above. It can be synthesized according to the production method.

  The maximum absorption wavelength in the tetrahydrofuran (THF) solution of the compound represented by the general formula (I) is preferably in the range of 760 nm to 1200 nm, preferably in the range of 780 nm to 1100 nm, and preferably in the range of 800 nm to 1000 nm. Range is more desirable.

The molar extinction coefficient at the maximum absorption wavelength in the THF solution of the compound represented by the general formula (I) is preferably 100,000 Lmol ⁻¹ cm ⁻¹ or more and 600,000 Lmol ⁻¹ cm ⁻¹ or less, and 200,000 Lmol ^−1. cm ^-1 than 600,000 ^{L mol} -1 ^{cm -1} or less is preferable, 250,000 ^{L mol} -1 ^{cm -1} or more 600,000 ^{L mol} -1 ^{cm -1} or less is more preferable.

The compound represented by the general formula (I) is preferably present in a solid dispersion state in the resin composition. When the compound represented by the general formula (I) is present in the resin composition in a solid dispersion state, the mass average particle diameter is preferably 10 nm to 1000 nm, preferably 10 nm to 500 nm, more preferably 20 nm to 300 nm. desirable.
In addition, the compound represented by general formula (I) may exist in a resin composition in the molecular dispersion state disperse | distributed on a molecular level.

In addition to the compound represented by the general formula (I), the resin composition according to this embodiment may further include a known infrared light absorber. For example, when the resin composition is used for an electrostatic charge image developing toner, a known infrared light absorber may be used in combination as long as the fixing property is not affected.
Known infrared absorbers include, for example, cyanine compounds, merocyanine compounds, benzenethiol metal complexes, mercaptophenol metal complexes, aromatic diamine metal complexes, diimonium compounds, aminium compounds, nickel complex compounds, phthalocyanine compounds, anthraquinones. Compounds, naphthalocyanine compounds, croconium compounds and the like can be used.
Specific examples of known infrared light absorbers include nickel metal complex infrared light absorbers (manufactured by Mitsui Chemicals, Inc .: SIR-130, SIR-132), bis (dithiobenzyl) nickel (manufactured by Midori Chemical Co., Ltd .: MIR). -101), bis [1,2-bis (p-methoxyphenyl) -1,2-ethylenedithiolate] nickel (manufactured by Midori Chemical Co., Ltd .: MIR-102), tetra-n-butylammonium bis (cis-1, 2-diphenyl-1,2-ethylenedithiolate) nickel (manufactured by Midori Chemical Co., Ltd .: MIR-1011), tetra-n-butylammonium bis [1,2-bis (p-methoxyphenyl) -1,2-ethylenedithio Rate] Nickel (Midori Chemical Co., Ltd .: MIR-1021), bis (4-tert-1,2-butyl-1,2-dithiophenolate) nickel-teto -N-butylammonium (manufactured by Sumitomo Seika Chemicals Co., Ltd .: BBDT-NI), cyanine infrared absorber (Fuji Film (registered trademark): IRF-106, IRF-107), cyanine infrared absorber (Yamamoto Kasei Co., Ltd., YKR2900), aminium, diimonium-based infrared absorber (Nagase Chemtech Co., Ltd .: NIR-AM1, IM1), imonium compound (Nippon Carlit Co., Ltd .: CIR-1080, CIR-1081), aminium compound (Nippon Carlit Co., Ltd .: CIR-960, CIR-961), anthraquinone compounds (Nippon Kayaku Co., Ltd .: IR-750), aminium compounds (Nippon Kayaku Co., Ltd .: IRG-002, IRG-003, IRG- 003K), polymethine compounds (Nippon Kayaku Co., Ltd .: IR-820B), diimonium compounds (Nippon Kayaku Co., Ltd .: IR) G-022, IRG-023), dian compound (Nippon Kayaku Co., Ltd .: CY-2, CY-4, CY-9), soluble phthalocyanine (Nippon Shokubai Co., Ltd .: TX-305A), naphthalocyanine (Yamamoto Kasei Co., Ltd.) Manufactured by YKR5010, manufactured by Sanyo Dye Co., Ltd .: Sample 1), inorganic material system (manufactured by Shin-Etsu Chemical Co., Ltd .: ytterbium UU-HP, manufactured by Sumitomo Metals Co., Ltd .: indium tin oxide), and the like.
Among these, a diimonium compound or a croconium compound is preferable.

(Other ingredients)
The resin composition may contain other components depending on the purpose. Examples of other components include various known additives such as plasticizers, dispersants, viscosity modifiers, pH adjusters, antioxidants, preservatives, antifungal agents, organic solvents, and pigments. It is done.

(Production method of resin composition)
The method for producing the resin composition according to this embodiment is not particularly limited.
For example, a method of dissolving or dispersing a specific infrared absorber, a resin, and other components as required in a solvent; dispersing the resin in a solution in a particulate form, and a specific infrared absorber and other if necessary A method of polymerizing the monomers of the resin raw material in a solution in which the specific infrared absorber and other materials coexist if necessary; if the resin is a thermoplastic resin, And a method of melting and kneading together a specific infrared absorber, a resin, and other materials as required, and molding or pulverizing.

(Use of resin composition)
The use of the resin composition is not particularly limited. Specifically, for example, in addition to an image forming material such as a toner described later, a paint for a heating element that generates heat by absorbing infrared light, or visible light is transmitted. Examples include a filter film forming composition for an infrared filter that blocks infrared light.

<Toner for electrostatic image development>
Next, the electrostatic image developing toner according to the exemplary embodiment will be described.
The electrostatic image developing toner according to this embodiment (hereinafter also simply referred to as “toner”) includes the resin composition according to the above-described embodiment. The toner according to the exemplary embodiment includes toner particles and, if necessary, an external additive, and the resin composition according to the exemplary embodiment is preferably contained in the toner particles.
That is, when the toner particles contain the resin composition according to the first aspect, the toner particles include, for example, a specific polyester resin as a binder resin, and a specific infrared absorber (the general formula (I )).
When the toner particles contain the resin composition according to the second aspect, the toner particles include, for example, a specific acrylic resin as a binder resin, and a specific infrared absorber (the general formula (I )).

  In the toner particles, the content of the compound represented by the general formula (I) is desirably 0.01% by mass or more and 5% by mass or less, and 0.01% by mass with respect to the total mass of the toner particles. It is more preferably 1% by mass or less and more preferably 0.01% by mass or more and 0.5% by mass or less.

  In the toner particles, the content of the binder resin is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more with respect to the entire toner particles. 85 mass% or less is more preferable.

(Toner particles)
The toner particles may include, for example, a colorant, a release agent, and other additives in addition to the resin composition according to the present embodiment.

-Colorant-
Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, and brilliant. Carmine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or acridine, xanthene, , Benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazole, and other dyes Etc.
A colorant may be used individually by 1 type and may use 2 or more types together.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Release agent-
Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. And so on. The release agent is not limited to this.

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
Note that the melting temperature is obtained from the DSC curve obtained by differential scanning calorimetry (DSC) according to “melting peak temperature” described in JIS K 7121-1987 “Method for measuring the melting temperature of plastics”. .

  The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core-shell toner particles include, for example, a core portion including a binder resin, a specific infrared absorber, and, if necessary, other additives such as a colorant and a release agent, and a binder. It is good to be comprised with the coating layer comprised including the adhesion resin.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

In addition, various average particle diameters and various particle size distribution indexes of toner particles are measured using Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and an electrolytic solution is measured using ISOTON-II (manufactured by Beckman Coulter, Inc.). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm is measured using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
For the particle size range (channel) divided based on the measured particle size distribution, the cumulative distribution is drawn from the smaller diameter side to the volume and number, respectively, and the particle size to be 16% is the volume particle size D16v, the number particle size D16p, a particle size that is 50% cumulative is defined as a volume average particle size D50v, a cumulative number average particle size D50p, and a particle size that is 84% cumulative is defined as a volume particle size D84v and a number particle size D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following formula.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

(External additive)
Examples of the external additive include inorganic particles. As the inorganic particles, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO. _{SiO 2, K 2 O · (} TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like.

The surface of the inorganic particles as an external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles, for example.

  Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, fluorine-based high molecular weight substances). Particle) and the like.

  The external addition amount of the external additive is, for example, preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less with respect to the toner particles.

(Toner production method)
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

The toner particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

Specifically, for example, when toner particles are produced by an aggregation coalescence method,
A step of preparing a resin particle dispersion in which resin particles to be a binder resin are dispersed (resin particle dispersion preparation step), and a resin particle dispersion (after mixing other particle dispersions as necessary) In the dispersion), the resin particles (other particles as necessary) are aggregated to form aggregated particles (aggregated particle formation step), and the aggregated particle dispersion in which the aggregated particles are dispersed is heated. Then, toner particles are manufactured through a process of fusing and coalescing the aggregated particles to form toner particles (fusing and coalescing process).

  In this embodiment, an infrared absorbent dispersion in which at least a specific infrared absorbent is dispersed is used as the other particle dispersion.

Details of each step will be described below.
In the following description, a method of obtaining toner particles containing a colorant and a release agent will be described. However, the colorant and the release agent are used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-Preparation step of resin particle dispersion-
First, together with a resin particle dispersion in which resin particles to be a binder resin are dispersed and an infrared absorbent dispersion in which a specific infrared absorber is dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed, a mold release A release agent particle dispersion liquid in which agent particles are dispersed is prepared.

  Here, the resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, and a dyno mill. Depending on the type of resin particles, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm to 1 μm, more preferably 0.08 μm to 0.8 μm, and further preferably 0.1 μm to 0.6 μm. preferable.
In addition, the volume average particle diameter of the resin particles is based on the particle size range (channel) divided by using the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by Horiba, Ltd.). The cumulative distribution is subtracted from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all the particles is measured as the volume average particle diameter D50v. The volume average particle size of particles in other dispersions is also measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 to 50 mass% is preferable, for example, and 10 to 40 mass% is more preferable.

  In the same manner as the resin particle dispersion, for example, an infrared absorbent dispersion, a colorant particle dispersion, and a release agent particle dispersion in which a specific infrared absorbent is dispersed are also prepared. In other words, regarding the volume average particle diameter of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the specific infrared absorber dispersed in the infrared absorber dispersion and the colorant particle dispersion are dispersed. The same applies to the colorant particles and the release agent particles dispersed in the release agent particle dispersion.

-Aggregated particle formation process-
Next, the infrared absorbent dispersion, the colorant particle dispersion, and the release agent particle dispersion are mixed together with the resin particle dispersion.
Then, in the mixed dispersion, the resin particles, the specific infrared absorber, the colorant particles, and the release agent particles are hetero-aggregated to have a diameter close to the diameter of the target toner particles, the resin particles, the specific infrared absorber, Aggregated particles including colorant particles and release agent particles are formed.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated. , Forming aggregated particles.
In the agglomerated particle forming step, for example, the aggregating agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, the pH is 2 or more and 5 or less). ), And after adding a dispersion stabilizer as necessary, the heating may be performed.

Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, an inorganic metal salt, and a divalent or higher-valent metal complex. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
As addition amount of a chelating agent, 0.01 mass part or more and 5.0 mass part or less are preferable with respect to 100 mass parts of resin particles, for example, and 0.1 mass part or more and less than 3.0 mass parts are more preferable.

-Fusion / unification process-
Next, the aggregated particle dispersion in which the aggregated particles are dispersed is heated to, for example, a glass transition temperature or higher of the resin particles (for example, a temperature of 10 to 30 ° C. higher than the glass transition temperature of the resin particles). Are fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. A process of aggregating to adhere to form second aggregated particles, and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and coalesce the second aggregated particles. The toner particles may be manufactured through a step of forming toner particles having a core / shell structure.

Here, after completion of the fusion / unification process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently carry out substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. Also, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing may be performed by, for example, a V blender, a Henschel mixer, a Laedige mixer, or the like. Furthermore, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

<Electrostatic image developer>
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin Resin impregnated type carriers; and the like.
The magnetic powder-dispersed carrier and the resin-impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and this is coated with a coating resin.

  Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer. Examples thereof include a polymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
The coating resin and matrix resin may contain other additives such as conductive particles.
Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

Here, in order to coat the surface of the core material with the coating resin, a method of coating with a coating layer forming solution obtained by dissolving the coating resin and, if necessary, various additives in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the core material, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed, a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

(Use)
The toner according to the present embodiment may be a light fixing toner or a heat fixing toner, but is particularly preferably used as a light fixing toner. In addition, the toner according to the exemplary embodiment may be a color toner containing a colorant, or may be a transparent toner (so-called invisible toner) that does not contain a colorant. Here, the invisible toner is a toner that forms an image to be decoded (read) using invisible light such as infrared rays, and is fixed as a toner image on a recording medium (for example, paper). Means a toner that is difficult to be visually recognized (ideally not recognized at all).
The invisible toner may contain a colorant as long as the addition amount is not recognized as being present (for example, 1% by mass or less).

<Image Forming Apparatus and Image Forming Method>
Next, an image forming apparatus and an image forming method according to this embodiment using the toner according to this embodiment will be described.
An image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, Developing means for containing an electrostatic charge image developer according to the present embodiment and developing the electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic image developer; and the surface of the image carrier A transfer unit that transfers the toner image formed on the surface of the recording medium, and a fixing unit that fixes the toner image transferred to the surface of the recording medium.

  The image forming apparatus according to the present embodiment includes a charging process for charging the surface of the image carrier, an electrostatic charge image forming process for forming an electrostatic image on the charged surface of the image carrier, and the present embodiment. A developing process for developing the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer, and transferring the toner image formed on the surface of the image carrier to the surface of the recording medium There is provided an image forming method comprising: a transferring step for fixing; and a fixing step for fixing the toner image transferred to the surface of the recording medium.

  Image formation in the image forming apparatus according to the present embodiment is performed, for example, as follows when an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member”) is used as an image carrier. First, the surface of the photoreceptor is charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic charge image. Next, the toner is attached to the electrostatic charge image by being brought into contact with or in proximity to a developing roll having a developer layer formed on the surface, and a toner image is formed on the photoreceptor. The formed toner image is transferred onto the surface of a recording medium such as paper using a corotron charger or the like. Further, the toner image transferred to the surface of the recording medium is fixed by a fixing device, and an image is formed on the recording medium.

As the photoreceptor, generally, an inorganic photoreceptor such as amorphous silicon or selenium, or an organic photoreceptor using polysilane, phthalocyanine or the like as a charge generation material or a charge transport material is used. In particular, from the viewpoint of abrasion resistance, the photosensitive member is an amorphous silicon photosensitive member for an inorganic photosensitive member, and a resin layer having a crosslinked structure such as a melamine resin, a phenol resin, or a silicone resin on the outermost layer for an organic photosensitive member. It is desirable that the photoreceptor has a so-called overcoat layer.
When a positively chargeable toner is used as the toner, generally, an inorganic photoreceptor represented by amorphous silicon (sometimes abbreviated as “a-Si”) is used, and when a negatively charged toner is used, In general, an organic photoconductor is used.

  In the image forming apparatus and the image forming method in the present embodiment, the toner image is preferably fixed on the recording medium by light fixing by light irradiation. Note that pressure / heat-fixing using a heating member and light-fixing by light irradiation may be used in combination.

As a fixing means for adopting a light fixing method in which a toner image is fixed by irradiating light, any means for fixing by light may be used, and a light fixing device (flash fixing device) is used.
Examples of the light source used in the light fixing device include a normal halogen lamp, a mercury lamp, a flash lamp, and an infrared laser.

As the heating member, a heating roll fixing device, an oven fixing device or the like is desirably used.
As the heating roll fixing device, a heating roll type fixing device is generally used in which a pair of fixing rolls are pressed against each other. As a pair of fixing rolls, a heating roll and a pressure roll are provided facing each other, and a nip is formed by pressure contact. The heating roll has a metal hollow core with a heater lamp inside, and a surface layer made of an oil- and heat-resistant elastic body layer (elastic layer) and a fluororesin, etc. are sequentially formed. Accordingly, an oil- and heat-resistant elastic body layer and a surface layer are sequentially formed on a metal hollow core metal core having a heater lamp inside. The toner image is fixed by passing a recording medium on which the toner image is formed through a nip region formed by the heating roll and the pressure roll.

Among these, the fixing unit is preferably an apparatus that irradiates an infrared laser that irradiates a laser beam of 860 nm or more. This is because this infrared laser is excellent in energy conversion efficiency, that is, light emission efficiency, and it is easy to reduce energy required for fixing means.
In addition, the infrared absorbent represented by the general formula (I) has a maximum absorption wavelength in the wavelength region of 860 nm or more, and the absorption efficiency of the infrared laser light by the infrared absorbent is improved, so that It becomes easy to reduce the addition amount of the infrared absorber to be added.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

  FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present embodiment. The image forming apparatus shown in FIG. 1 is one that forms a toner image with toner obtained by adding black to three colors of cyan, magenta, and yellow.

  The image forming apparatus shown in FIG. 1 feeds the recording medium P wound in a roll shape by a paper feed roller 328, and on the one side of the recording medium P fed in this way, the recording medium P is fed upstream in the feeding direction. Four image forming units 312 (black (K), yellow (Y), magenta (M), cyan (C)) are provided in parallel from the side toward the downstream side. A light fixing type fixing device 326 is provided on the downstream side.

The black image forming unit 312K is a known electrophotographic image forming unit. Specifically, a charging unit 316K, an exposure unit 318K, a developing unit 320K, and a cleaner 322K are provided around the photosensitive member 314K, and a transfer unit 324K is provided via the recording medium P. The same applies to the other yellow, magenta, and cyan image forming units 312Y, 312M, and 312C.
When used for monochrome printing, only black (K) may be provided as the image forming unit 312.

  In the image forming apparatus shown in FIG. 1, toner images are sequentially transferred by a known electrophotographic method onto each recording medium P 312K, 312Y, 312M, and 312C on the recording medium P drawn from the roll state. The image is fixed by the fixing device 326 to form an image. A heating roll pair (not shown) for fixing the toner image to the recording medium P by pressurization and heating with the recording medium P interposed may be provided at a position where the fixing device 326 is installed. By providing a heating device such as a heater in the roll, the heating roll pair is heated, and when the toner image comes into contact with the heating roll pair, the toner image is melted and fixed on the recording medium P.

<Process cartridge>
The process cartridge according to the present exemplary embodiment includes a developing unit that stores an electrostatic charge image developer and develops the electrostatic charge image formed on the surface of the image holding member as a toner image with the electrostatic charge image developer. It is detachable from the forming apparatus. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

<Toner cartridge>
The toner cartridge according to the present exemplary embodiment is a toner cartridge that stores toner and is detachable from the image forming apparatus. As the toner, the electrostatic image developing toner according to this embodiment is applied.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

<Example A>
(Synthesis of specific polyester resin A1)
・ Neopentyl glycol: 114 parts ・ Ethylene glycol: 68 parts ・ Terephthalic acid: 166 parts ・ Isophthalic acid: 166 parts ・ Tetrabutoxy titanate (catalyst): 2 parts

  The above material is placed in a heat-dried three-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 200 ° C. for 7 hours, and then gradually to 1333 Pa. The specific polyester resin (resin A1) was synthesized by raising the temperature to 230 ° C. while maintaining the pressure under reduced pressure for 8 hours. The number average molecular weight (Mn) of the obtained specific polyester resin was 4,500, and the glass transition temperature was 58 ° C.

(Preparation of resin particle dispersion A1)
-Resin A1: 115 parts-Ionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts-Ion-exchanged water: 180 parts The above materials are mixed and heated to 100 ° C, IKA Corporation After sufficiently dispersing with Ultra Turrax T50 manufactured, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to prepare resin particle dispersion A1 having a volume average particle size of 170 nm and a solid content of 40%.

(Synthesis of specific polyester resin A2)
• 1,3-propanediol: 109 parts • 1,4-butanediol: 37 parts • Ethylene glycol: 13 parts • Terephthalic acid: 166 parts • Isophthalic acid: 166 parts • Tetrabutoxy titanate (catalyst): 2 parts

  The above components are placed in a heat-dried three-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 200 ° C. for 7 hours, and then gradually to 1333 Pa. The specific polyester resin (resin A2) was synthesized by raising the temperature to 230 ° C. while maintaining the pressure and holding for 8 hours. The number average molecular weight (Mn) of the obtained specific polyester resin was 4,300, and the glass transition temperature was 60 ° C.

(Preparation of resin particle dispersion A2)
-Resin A2: 115 parts-Ionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts-Ion-exchanged water: 180 parts The above materials are mixed and heated to 100 ° C, IKA Corporation After sufficiently dispersing with Ultra Turrax T50 manufactured, dispersion treatment was performed for 1 hour with a pressure discharge type gorin homogenizer to prepare resin particle dispersion A2 having a volume average particle size of 180 nm and a solid content of 40%.

(Synthesis of polyester resin A3)
Bisphenol A bis (2-hydroxyethyl) ether: 347 parts Ethylene glycol: 68 parts Terephthalic acid: 166 parts Isophthalic acid: 166 parts Tetrabutoxy titanate (catalyst): 2 parts

  The above material is placed in a heat-dried three-necked flask, and nitrogen gas is introduced into the container, and the temperature is raised while stirring in an inert atmosphere. Then, a copolycondensation reaction is performed at 210 ° C. for 7 hours, and then gradually up to 1333 Pa. The temperature was raised to 230 ° C. under reduced pressure and maintained for 8 hours to obtain Resin A3 having an acid value of 10.0 mg KOH / g, a weight average molecular weight of 13,000, and a glass transition temperature of 62 ° C. The number average molecular weight (Mn) of the obtained polyester resin was 5100.

(Preparation of resin particle dispersion A3)
Resin A3 was transferred to Cavitron CD1010 (manufactured by Eurotech) at a rate of 100 parts per minute while still in the molten state. Separately, 0.37% dilute ammonia water obtained by diluting reagent ammonia water with ion exchange water is prepared, and the resin A3 is transferred at a rate of 0.1 liter per minute while heating to 120 ° C. with a heat exchanger. It was transferred to the Cavitron. The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² to obtain a resin particle dispersion A3 in which resin particles having a volume average particle size of 160 nm and a solid content of 40% were dispersed.

(Synthesis of specific infrared absorber (A1))
A specific infrared absorber (A1): (a compound in which R ^{a to} R ^d in the general formula (I) are t-butyl groups) was synthesized according to the following scheme.
A three-necked flask was equipped with a Dean-Stark trap, a reflux condenser, a stirring seal, and a stirring rod to form a reaction vessel. 2,2,8,8-Tetramethyl-3,6-nonadiin-5-ol and cyclohexane were placed in a reaction vessel. Manganese (IV) oxide powder was added, stirred with a three-one motor, and heated to reflux. Water formed during the reaction was removed by azeotropic distillation. It was confirmed by thin layer chromatography that there was no 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol remaining. The reaction mixture was allowed to cool and then filtered under reduced pressure to obtain a yellow filtrate (F1). The solid obtained by filtration was transferred to another container, ethyl acetate was added, and the operation of ultrasonic dispersion and filtration was repeated 4 times to obtain an ethyl acetate extract (F2). The ethyl acetate extract (F2) and the filtrate (F1) were mixed and concentrated with a rotary evaporator and then with a vacuum pump to obtain a liquid colored orange. The orange-colored liquid was distilled under reduced pressure to obtain a pale yellow liquid (Intermediate 1).

  A thermometer and a dropping funnel were installed in a three-necked flask to prepare a reaction vessel. Sodium hydrogen monosulfide n hydrate was added to ethanol and stirred at room temperature (20 ° C.) until dissolved, and then cooled with ice water. When the internal temperature reached 5 ° C., a mixture of intermediate 1 and ethanol was added dropwise little by little. The liquid changed from yellow to orange by the dropwise addition. Since the internal temperature increased due to heat generation, the internal temperature was dropped within the range of 5 ° C. or higher and 7 ° C. or lower while adjusting the dropping amount. Thereafter, the ice water bath was removed, and the mixture was stirred while allowing the temperature to rise naturally at room temperature (20 ° C.). Water was added to the reaction solution, and ethanol was removed by a rotary evaporator. Thereafter, sodium chloride was added until saturation, and the mixture was separated with ethyl acetate to recover the organic phase. The organic phase was washed twice with saturated ammonium chloride and dried over magnesium sulfate. After drying, the solution was concentrated under reduced pressure to recover a brown liquid. This brown liquid was distilled under reduced pressure. A distillate starts to be produced at 200 ° C., but since the first distillate component is not included, the main distillate was selected when the amount of steam increased. A yellow liquid (Intermediate 2) was distilled.

  A stir bar and intermediate 2 were placed in a three-necked flask, and a nitrogen inlet tube and a reflux condenser were attached to replace the nitrogen. Under nitrogen atmosphere, anhydrous tetrahydrofuran was added with a syringe, and a 1M tetrahydrofuran (THF) solution of methylmagnesium bromide was added dropwise with a syringe while stirring at room temperature (20 ° C.). After completion of the dropwise addition, the reaction solution was heated and stirred and refluxed. The reaction solution was allowed to cool under a nitrogen atmosphere, and then a solution of ammonium bromide dissolved in water was added dropwise while cooling in an ice-water bath. The reaction mixture was further stirred at room temperature (20 ° C.), n-hexane was added, and the mixture was dried over sodium sulfate. After drying, the n-hexane / THF solution was taken out with a syringe and the inorganic layer was washed with ethyl acetate to obtain an extract. The n-hexane / THF solution and the extract from the inorganic layer were mixed, concentrated under reduced pressure, and then vacuum dried to obtain Intermediate 3.

  Under a nitrogen atmosphere, Intermediate 3 and squaric acid were dispersed in a mixed solvent of cyclohexane and isobutanol, and pyridine was added and heated to reflux. Then isobutanol was added and the reaction mixture was further heated to reflux. Water generated during the reaction was removed by azeotropic distillation. The reaction mixture was allowed to cool and then filtered under reduced pressure to remove hardly soluble substances. The filtrate was concentrated on a rotary evaporator. Methanol was added to the residue, heated to 40 ° C, and then cooled to -10 ° C. Crystals were obtained by filtration and vacuum-dried to obtain a specific infrared absorber (A1).

(Preparation of infrared absorber dispersion A1)
-Specific infrared absorber (A1): 10 parts-Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part-Ion-exchanged water: 89 parts Ultrasonic homogenizer (Nippon Seiki) US-150T) was used for dispersion for 30 minutes at 150 W to obtain an infrared absorbent dispersion A1 having a volume average particle size of 250 nm and a solid content of 11%.

(Synthesis of specific infrared absorber (A2))
In the synthesis of the specific infrared absorber (A1), 2,8-dimethyl-3,6-nonadiin-5-ol instead of 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol The specific infrared absorber (A2): (a compound in which R ^{a to} R ^d in the general formula (I) are i-propyl groups) was synthesized in the same procedure except that was used.
(Identification data)
¹ H-NMR spectrum (CDCl ₃ ):
9.1 (2H), 6.8 (2H), 6.1 (2H), 2.8 to 3.0 (4H), 1.2 to 1.3 (24H)
Mass spectrum (FD): m / z = 467
Molar extinction coefficient (ε) spectrum: maximum absorption wavelength (λ _max ) = 809 nm (THF), molar extinction coefficient (ε _max ) at the maximum absorption wavelength = 3.6 × 10 ⁵ M ⁻¹ cm ⁻¹

(Preparation of infrared absorber dispersion A2)
-Specific infrared absorber (A2): 10 parts-Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part-Ion-exchanged water: 89 parts Ultrasonic homogenizer (Nippon Seiki) US-150T) was used for dispersion for 30 minutes at 150 W to obtain an infrared absorbent dispersion A2 having a volume average particle diameter of 250 nm and a solid content of 11%.

(Synthesis of specific infrared absorber (A3))
In the synthesis of the specific infrared absorber (A1), 2,10-dimethyl-4,7-undecadiin-6-ol instead of 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol A specific infrared absorber (A3): (a compound in which R ^{a to} R ^d in the general formula (I) are i-butyl groups) was synthesized in the same procedure except that was used.
(Identification data)
¹ H-NMR spectrum (CDCl ₃ ):
9.1 (2H), 6.8 (2H), 6.1 (2H), 2.4 to 2.6 (8H), 1.8 to 2.0 (4H), 0.8 to 1.0 (24H)
Mass spectrum (FD): m / z = 523

(Preparation of infrared absorber dispersion A3)
・ Specific infrared absorber (A3): 10 parts ・ Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part ・ Ion-exchanged water: 89 parts Ultrasonic homogenizer (Nippon Seiki) US-150T) was used for dispersion for 30 minutes at 150 W to obtain an infrared absorbent dispersion A3 having a volume average particle diameter of 250 nm and a solid content of 11%.

(Synthesis of infrared absorber (A4))
Trideca-5,8-diin-7-ol was used instead of 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol in the synthesis of the specific infrared absorber (A1). Except that, infrared absorber (A4): (compound in which R ^{a to} R ^d in general formula (I) are n-butyl groups) was synthesized.

(Preparation of infrared absorber dispersion A4)
・ Infrared absorber (A4): 10 parts ・ Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part ・ Ion-exchanged water: 89 parts The above materials are mixed and an ultrasonic homogenizer (Nippon Seiki Co., Ltd.) US-150T) was used for dispersion treatment at 150 W for 30 minutes to obtain an infrared absorbent dispersion A4 having a volume average particle diameter of 250 nm and a solid content of 11%.

(Synthesis of infrared absorber (A5))
In the synthesis of the specific infrared absorber (A1), undeca-4,7-diin-6-ol was used instead of 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol. Except that, infrared absorber (A5): (compound in which R ^{a to} R ^d in general formula (I) are n-propyl groups) was synthesized.

(Preparation of infrared absorber dispersion A5)
・ Infrared absorber (A5): 10 parts ・ Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part ・ Ion-exchanged water: 89 parts Ultrasonic homogenizer (Nippon Seiki Co., Ltd.) US-150T) was used for dispersion for 30 minutes at 150 W to obtain an infrared absorbent dispersion A5 having a volume average particle diameter of 250 nm and a solid content of 11%.

(Synthesis of infrared absorber (A6))
Infrared absorber (A6) was synthesized as follows.
4.8 g (98%, 30 mmol) of 1,8-diaminonaphthalene, 3.9 g (98%, 30 mmol) of 2,6-dimethyl-4-heptanone, 40 mg (0.2 mmol) of p-toluenesulfonic acid monohydrate , And 45 ml of toluene was heated with stirring in a nitrogen gas atmosphere and refluxed at 110 ° C. for 7 hours. Water generated during the reaction was removed by azeotropic distillation. After completion of the reaction, toluene was distilled off, and the dark brown solid obtained was extracted with acetone, purified by recrystallization from a mixed solvent of acetone and ethanol, and dried to obtain intermediate (a). 625 g (yield 90%) was obtained.
To 7.625 g of the obtained intermediate (a), a mixed solution of 3,4-dihydroxycyclobut-3-ene-1,2-dione 1.4 g (12 mmol), n-butanol 40 ml, and toluene 60 ml was added. The mixture was heated with stirring in an atmosphere of nitrogen gas and refluxed at 105 ° C. for 3 hours. Water generated during the reaction was removed by azeotropic distillation. After completion of the reaction, the solvent was distilled off in an atmosphere of nitrogen gas, and 120 ml of n-hexane was added while stirring the obtained reaction mixture. The produced black-brown precipitate was filtered by suction, washed with n-hexane, and dried to obtain a black-brown solid. This solid was washed with ethanol to obtain 6.2 g (yield 80%) of an infrared absorber (A6).

(Preparation of infrared absorber dispersion A6)
0.25 g of the infrared absorber (A6), 2.5 mL of tetrahydrofuran (THF), and 1 g of zirconia beads having a diameter of 1 mm were placed in a 15 g ball mill container and milled for 1 hour. Water was added to the ball mill container, and the mixture was filtered through a filter to collect the finely divided infrared absorber (A6). The volume average particle size was 150 nm.
0.20 g of this micronized infrared absorber (A6), 1 ml of 12% aqueous sodium dodecylbenzenesulfonate solution and 100 ml of distilled water were mixed and ultrasonically dispersed to prepare a slurry (ultrasonic output: 4 to 4). 5W, 1/4 inch horn use, irradiation time 30 minutes). The sample concentration in the slurry was 0.20% by mass.

(Preparation of resin composition)
-Example A1-1
263 parts of the obtained resin particle dispersion A1 and 1.91 parts of the obtained infrared absorbent dispersion A1 and 0.3 part of polyaluminum chloride are placed in a round stainless steel flask, and the homogenizer (Ultra manufactured by IKA) is used. Mix and disperse with Thalax T50). Next, 0.15 part of polyaluminum chloride was added thereto, and the dispersing operation was continued with the homogenizer. The flask was heated to 47 ° C. with stirring in an oil bath for heating, and kept at this temperature for 60 minutes. Thereafter, the pH of the system was adjusted to 5.4 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal, for 2 hours. Retained.

  After completion of the reaction, the reaction mixture was cooled to room temperature, the solid was separated by filtration, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion exchanged water at 40 ° C., and washed by stirring at 300 rpm for 15 minutes. This was further repeated 5 times. When the pH of the filtrate reached 7.0, the filtrate was taken out by filtration and vacuum-dried for 12 hours to obtain resin composition particles having a volume average particle size of 5.7 μm.

-Example A1-2 and Reference Example A1-3-
Resin composition particles were obtained in the same manner as in Example A1-1 except that the resin particle dispersion A2 and the resin particle dispersion A3 were used instead of the resin particle dispersion A1, respectively.

-Example A2-1, Example A2-2, and Reference Example A2-3-
Resin composition particles in the same manner as in Example A1-1, Example A1-2, and Reference Example A1-3 except that infrared absorber dispersion A2 was used instead of infrared absorber dispersion A1. Got.

-Example A3-1, Example A3-2, and Reference Example A3-3
Resin composition particles in the same manner as in Example A1-1, Example A1-2, and Reference Example A1-3, except that infrared absorbent dispersion A3 was used instead of infrared absorbent dispersion A1. Got.

-Comparative Example A4-1, Comparative Example A4-2, and Reference Example A4-3-
Resin composition particles in the same manner as in Example A1-1, Example A1-2, and Reference Example A1-3 except that infrared absorbent dispersion A4 was used instead of infrared absorbent dispersion A1. Got.

-Comparative Example A5-1, Comparative Example A5-2, and Reference Example A5-3-
Resin composition particles in the same manner as in Example A1-1, Example A1-2, and Reference Example A1-3 except that infrared absorbent dispersion A5 was used instead of infrared absorbent dispersion A1. Got.

-Comparative Example A6-1, Comparative Example A6-2, and Reference Example A6-3-
Example A1-1, Example A1-2, and Reference Example A1-3 were used except that 105 parts of infrared absorbent dispersion A6 was used instead of 1.91 parts of infrared absorbent dispersion A1. The resin composition particles were obtained.

(Calculation of molar extinction coefficient of infrared absorber solution)
About each infrared absorber solution obtained by dissolving the specific infrared absorber A1 to the specific infrared absorber A3 and the infrared absorber A4 to the infrared absorber A6 in tetrahydrofuran, the spectrophotometer U-4100 manufactured by Hitachi, Ltd. was used. The IR transmission spectrum was measured, and the molar extinction coefficient at the absorption peak (molar extinction coefficient of the infrared absorbent solution) was calculated. The results are shown in Table 1.

(Calculation of molar extinction coefficient of resin particle solution)
The resin composition solution obtained by dissolving the obtained resin composition particles in tetrahydrofuran was measured for IR transmission spectrum with a spectrophotometer U-4100 manufactured by Hitachi, Ltd., and the molar extinction coefficient at the absorption peak. (Molar extinction coefficient of the resin composition solution) was calculated.
Further, the ratio “single ratio (%)” of the molar extinction coefficient of the resin composition solution when the molar extinction coefficient of the infrared absorbent solution was set to 100 was determined. The results are also shown in Table 1.

  The “single ratio (%)” is a value indicating how much the infrared absorbing ability of the infrared absorbing agent in the resin composition solution is exhibited as compared with the solution of the infrared absorbing agent alone. When the single ratio is close to 100%, the infrared absorption amount in the resin composition solution is equivalent to the infrared absorption amount in the infrared absorber solution, and the infrared absorber is sufficiently incorporated in the resin, It is considered that the function of the infrared absorber is exhibited in On the other hand, when the single ratio is small, by mixing the infrared absorbent with the resin, for example, the infrared absorbent is not incorporated into the resin, or the infrared absorbing ability is reduced due to aggregation or decomposition of the infrared absorbent. It is considered damaged.

  From the above results, in the resin composition solutions of Examples A1-1, A1-2, A2-1, A2-2, A3-1, and A3-2, Comparative Examples A4-1, A4-2, and A5 were used. It can be seen that the molar extinction coefficient and the single ratio at the absorption peak are larger than those of the resin composition solutions of -1, A5-2, A6-1, and A6-2. From this, the resin composition of the said Example using specific polyester resin and a specific infrared absorber is infrared absorption compared with the resin composition of the said comparative example using specific polyester resin and an infrared absorber (A4). It is considered that the decrease in performance is suppressed.

<Example B>
(Synthesis of specific acrylic resin B1, preparation of resin particle dispersion B1)
-Styrene: 238 parts-n-butyl acrylate: 80 parts-Hydroxyethyl methacrylate: 81 parts-Acrylic acid: 4 parts-Nonionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neugen EA-157): 5 Parts / anionic surfactant (Neogen SC manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 7 parts / ion-exchanged water: 550 parts

  The above materials were dispersed and emulsified in a flask, and while slowly stirring and mixing for 10 minutes, 50 parts of ion-exchanged water in which 4 parts of potassium persulfate was dissolved was added thereto, and after nitrogen substitution, While stirring the contents of the flask, the contents were heated to 50 ° C., and the monomer mixture was added over 90 minutes. After completion of the addition, emulsion polymerization was continued for 5 hours. Thus, a resin particle dispersion B1 was prepared by dispersing resin particles of the specific acrylic resin B1 having an average particle size of 160 nm, a weight average molecular weight of 90000, and a glass transition temperature of 56 ° C.

(Synthesis of acrylic resin B2 and preparation of resin particle dispersion B2)
-Styrene: 320 parts-n-Butyl acrylate: 80 parts-Acrylic acid: 10 parts-Dodecanethiol: 10 parts-Nonionic surfactant (Sanyo Chemical Industries nonipol 400): 6 parts-Anionic surfactant ( Daigen Kogyo Seiyaku Co., Ltd. Neogen R): 10 parts, ion-exchanged water: 550 parts

The above material was placed in a flask, dispersed and emulsified, and 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes. Thereafter, the inside of the flask was replaced with nitrogen, and the system was heated in an oil bath with stirring until the temperature reached 70 ° C., and the emulsion polymerization was continued for 5 hours to obtain a solid content of 43% in which the resin particles of the acrylic resin B2 were dispersed. Resin particle dispersion B2 was obtained.
The volume average particle diameter of the resin particles is 155 nm, the glass transition temperature of the acrylic resin B2 is 54 ° C., and the weight average molecular weight is 33000.

(Preparation of resin composition)
-Example B1-1
280 parts of the obtained resin particle dispersion B1, 2.19 parts of the infrared absorbent dispersion A1, 1.5 parts of a cationic surfactant (Sanisol B50 manufactured by Kao Corporation), 0.36 of polyaluminum chloride Parts and ion-exchanged water were placed in a 1000-part round stainless steel flask, mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then heated to 48 ° C. with stirring. After maintaining at 48 ° C. for 30 minutes, it was confirmed with an optical microscope that aggregated particles were formed. Thereafter, the pH of the solution was adjusted to 8.0 with an aqueous sodium hydroxide solution having a concentration of 0.5 mol / L, and then heated to 90 ° C. and further stirred for 3 hours.

  After completion of the reaction, the reaction mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. The solid content was redispersed in 1000 parts of ion-exchanged water at 30 ° C., stirred for 15 minutes at 300 rpm with a stirring blade, and subjected to solid-liquid separation by Nutsche suction filtration. This redispersion and suction filtration were repeated, and the washing was terminated when the filtrate had an electric conductivity of 10.0 μS / cmt or less. Subsequently, it was charged in a vacuum dryer and dried continuously for 12 hours to obtain particles of a resin composition having a volume average particle size of 5.8 μm.

-Reference example B1-2
Resin composition particles were obtained in the same manner as in Example B1-1 except that the resin particle dispersion B2 was used instead of the resin particle dispersion B1.

-Comparative Example B2-1 and Reference Example B2-2
Resin composition particles were obtained in the same manner as in Example B1-1 and Reference Example B1-2, except that the infrared absorbent dispersion A4 was used instead of the infrared absorbent dispersion A1.

(Calculation of molar extinction coefficient of resin particle solution)
About the resin composition solution obtained by dissolving the obtained resin composition in tetrahydrofuran, the IR transmission spectrum was measured with a spectrophotometer U-4100 manufactured by Hitachi, Ltd., and the molar extinction coefficient (resin composition) at the absorption peak was measured. The molar extinction coefficient of the product solution was calculated. The results are shown in Table 2.

  From the above results, it can be seen that the resin composition solution of Example B1-1 has a larger molar extinction coefficient and single ratio at the absorption peak than the resin composition solution of Comparative Example B2-1. From this, the resin composition of the said Example using a specific acrylic resin and a specific infrared absorber is infrared absorption compared with the resin composition of the said comparative example using a specific acrylic resin and an infrared absorber (A4). It is considered that the decrease in the amount is suppressed.

312Y, 312M, 312C, 312K Image forming units 314Y, 314M, 314C, 314K Photoconductors 316Y, 316M, 316C, 316K Chargers 318Y, 318M, 318C, 318K Exposure means 320Y, 320M, 320C, 320K Developers 322Y, 322M, 322C, 322K Cleaner 324Y, 324M, 324C, 324K Transfer device 326 Optical fixing device 328 Paper feed roller P Recording medium

Claims (12)

The resin composition containing the polyester resin whose structural unit derived from bisphenol A is 1 mass% or less with respect to the whole polyester resin, and the compound represented by the following general formula (I).

(In General Formula (I), R ^a represents a group represented by General Formula (IR), and R ^b , R ^c, and R ^d each independently represents an alkyl group.
In General Formula (IR), R ^e represents hydrogen or a methyl group, and e represents an integer of 0 or more and 3 or less. ) The resin composition containing the acrylic resin which has OH group in a side chain, and the compound represented by the following general formula (I).

(In General Formula (I), R ^a represents a group represented by General Formula (IR), and R ^b , R ^c, and R ^d each independently represents an alkyl group.
In General Formula (IR), R ^e represents hydrogen or a methyl group, and e represents an integer of 0 or more and 3 or less. ) 3. The resin composition according to claim 1, wherein at least one of R ^b , R ^c, and R ^{d in} the general formula (I) is a group represented by the general formula (IR). The resin composition according to claim 1 or 2, wherein all of R ^b , R ^c, and R ^{d in} the general formula (I) are groups represented by the general formula (IR). Formula (I-R) in the R ^e is methyl claim 1 resin composition according to any one of claims 4.   E in the said general formula (IR) is 0, The resin composition as described in any one of Claims 1-5.   An electrostatic charge image developing toner comprising the resin composition according to any one of claims 1 to 6.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 7. Containing the electrostatic image developing toner according to claim 7;
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 8 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 8 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer according to claim 8;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: