JP2013054378A - Toner for image formation, image forming apparatus, image forming method, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for image formation that has excellent thermal characteristics, heat-resistant storage stability, and transparency; an image forming apparatus; an image forming method; and a process cartridge.SOLUTION: Toner for image formation contains at least as a binder resin, a linear polyester-based resin (b1) obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol other than (b11)(b12) with an extender.

Description

  The present invention relates to a toner used for forming an electrophotographic image such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and an image forming apparatus, an image forming method, and a process cartridge using the toner.

  Conventionally, in an electrophotographic image forming apparatus or the like, a latent image formed electrically or magnetically has been visualized with an image forming toner (hereinafter also simply referred to as “toner”). For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed on the transfer material such as paper. In the process of fixing a toner image onto a transfer paper, a heat fixing method such as a heating roller fixing method or a heating belt fixing method is widely used because of its energy efficiency.

In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and transparency and that can provide high-quality images. However, in order to achieve the low-temperature fixability of the toner, it is necessary to lower the softening point of the binder resin. If the softening point of the binder resin is low, a part of the toner image adheres to the surface of the fixing member at the time of fixing, and a so-called offset (hereinafter also referred to as hot offset) occurs on the copy sheet. Further, the heat resistance of the toner is lowered, and so-called blocking occurs in which toner particles are fused with each other particularly in a high temperature environment. In addition, in the developing device, there are problems that the toner is fused and contaminated inside the developing device and the carrier, and that the toner is liable to film on the surface of the photoreceptor.
One of the measures taken to address these problems is to improve toner physical properties by improving the binder resin. Toners using polylactic acid-containing polyester resins are storage-stable, low-temperature fixability, offset resistance, and environmental stability. It has been proposed as an excellent material and environmental conservation. Compared to polyester resins that have been used in conventional toner applications, the thermal properties of polyester resins containing polylactic acid are not sufficiently controlled, so there are many restrictions on the amount of resin formulated and the manufacturing method, and sufficient storage stability. Low temperature fixability and offset resistance have not been achieved. (See Patent Documents 1 and 2).
JP 2006-208455 A JP 2006-091278 A

  The present invention has been made in view of the above circumstances in the prior art. That is, the present invention provides an image forming toner, an image forming apparatus, an image forming method, and a process cartridge that are excellent in thermal characteristics, heat-resistant storage stability, and transparency.

As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is, the present invention has the following configuration.
(1) A linear polyester system obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11) together with an extender as at least a binder resin The toner for image formation containing the resin (b1), and the monomer for forming the polyhydroxycarboxylic acid skeleton of (b11) is an optically active monomer, and the optical purity X (%) = | X (L isomer) -X (D isomer) | [where X (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) is the D isomer ratio in terms of optically active monomer. (Representing (mol%)) is 80% or less, or the content Y (mass%) of the resin (b1) in the total binder resin and the optical purity X (mol%) in terms of monomer components = X (L isomer) -X (D isomer) | [where X (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) is the D isomer ratio in terms of optically active monomer. (Representing (mol%)) satisfying Y ≦ −1.5X + 220 (80 <X ≦ 100).

(2) In the polyester-based resin (b1), the mass ratio of the polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) is 31:69 to 90:10. The toner for image formation as described in (1) above.
(3) The polyhydroxycarboxylic acid skeleton of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton is a skeleton obtained by polymerizing a hydroxycarboxylic acid having 2 to 6 carbon atoms. The toner for image formation as described in 2).
(4) Any of (1) to (3) above, wherein the polyhydroxycarboxylic acid skeleton of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton is obtained by direct dehydration condensation of hydroxycarboxylic acid. The image forming toner according to claim 1.

(5) The binder resin other than the polyester-based resin (b1) contains at least one resin selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins (1) The toner for image formation according to any one of to (4).
(6) The image forming toner further comprises a wax (c) and a modified wax (d) in which a vinyl polymer chain is grafted to (c). The image forming toner according to claim 1.
(7) The image forming toner comprises particles obtained by pulverizing after melt-kneading a toner component containing at least a binder resin containing a resin (b1) and a colorant. The image forming toner according to any one of (1) to (6).

(8) an electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image. Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit, wherein the toner is the image forming toner according to any one of (1) to (7).
(9) A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image with toner. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium The image forming method, wherein the toner is the image forming toner according to any one of (1) to (7).
(10) At least an electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forming an image A process cartridge that is detachable from an apparatus main body, wherein the toner is the image forming toner according to any one of (1) to (7).

  According to the present invention, it is possible to provide an image forming toner, an image forming apparatus, an image forming method, and a process cartridge that are excellent in thermal characteristics, heat-resistant storage stability, and transparency.

In the linear polyester-based resin (b1) obtained by reacting a polyester diol (b12) other than (b11) and a polyester diol (b12) containing a polyhydroxycarboxylic acid skeleton of the present invention with an extender, In order to obtain a linear polyester, each of (b11), (b12) and the extender needs to be bifunctional. If any of them is trifunctional or more, a crosslinking reaction proceeds and a linear polyester cannot be obtained.
Linear polyester has a simple structure, and it is easy to control the molecular weight and physical properties (thermal characteristics, compatibility with other resins, etc.) generated thereby. The linear polyester resin in the present invention is composed of the units (b11) and (b12), and the physical properties of (b1) can be controlled by the polyester type, molecular weight, and structure used in the unit (b12). This is a merit and is characterized in that a physical property control means is clearly provided for a conventional composition containing lactic acid.

The polyhydroxycarboxylic acid skeleton constituting (b11) has a skeleton obtained by polymerizing hydroxycarboxylic acid, and can be formed by a method of directly dehydrating and condensing hydroxycarboxylic acid or a method of ring-opening polymerization of a corresponding cyclic ester. From the viewpoint that the degree of freedom in composition design is high, a method of directly dehydrating and condensing hydroxycarboxylic acid is preferable. Examples of the hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), aromatic hydroxycarboxylic acids (such as salicylic acid, creosote acid, mandelic acid, burric acid, and syringic acid), or a mixture thereof. Corresponding cyclic esters include glycolide, lactide, γ-butyrolactone, 6-valerolactone and the like. Among these, from the viewpoints of transparency and thermal properties, the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid and a cyclic ester, more preferably a hydroxycarboxylic acid having 2 to 6 carbon atoms ( Corresponding cyclic esters are also included), particularly preferably glycolic acid, lactic acid, glycolide, and lactide, and most preferably glycolic acid and lactic acid.
When the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, the optical purity X (%) = | X (L isomer) −X (D isomer) | [where X (L Is a L-form ratio (%) in terms of optically active monomer, and X (D-form is a D-form ratio (%) in terms of optically active monomer)] is preferably 80% or less, more preferably 60% or less. Within this range, the crystallinity of the polyester resin (b1) is lowered, and it is possible to prevent poor dispersion with other toner components derived from crystallization.

  When the polyhydroxycarboxylic acid skeleton is formed, a polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton is obtained by adding a diol (11) described later and copolymerizing. Preferred as diols are alkylene oxides of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (Alkylene oxide is hereinafter abbreviated as AO. Specific examples include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) 2-30), and combinations thereof, more preferably 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and AO adducts of bisphenol A, particularly preferably With 1,3-propylene glycol That.

  The polyester diol (b12) other than (b11) can be the same as the reaction product of the diol (11) and the dicarboxylic acid (13) among the polyester resins described later, and charged with the diol and the dicarboxylic acid during the polymerization. It is obtained by adjusting the ratio to make the hydroxyl group excessive. Preferred as (b12) is 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.). One or more diols selected from AO (EO, PO, BO, etc.) adducts (addition moles 2 to 30) and combinations thereof, terephthalic acid, isophthalic acid, adipic acid, succinic acid, and combinations thereof A reaction product with one or more dicarboxylic acids selected from

The hydroxyl value of (b11) and (b12) is preferably 3 to 224, more preferably 5 to 112, and most preferably 10 to 56, from the viewpoint of adjusting the physical properties of (b1).
The number average molecular weight of the resin (b) (measured by gel permeation chromatography, details of the measurement method will be described later, abbreviated as Mn), melting point (measured by DSC), and glass transition temperature (Tg) are preferably ranges depending on the application. It may be adjusted as appropriate.
Tg in the present invention is a value obtained from DSC measurement or flow tester measurement (when it cannot be measured by DSC).
In the case of measurement by DSC, it is measured by a method (DSC method) prescribed in ASTM D3418-82 using DSC20, SSC / 580 manufactured by Seiko Denshi Kogyo Co., Ltd.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The flow tester measurement conditions are as follows. All measurements are performed under these conditions.
(Flow tester measurement conditions)
Load 30 kg / cm ²
Heating rate 3.0 ° C / min
Die diameter 0.50mm
Die length 10.0mm
The number average molecular weight (hereinafter abbreviated as Mn) of (b11) and (b12) is preferably from 500 to 30,000, more preferably from 1000 to 20,000, most preferably from 2000, from the viewpoint of adjusting the physical properties of (b1). 5000.
The Mn of the resin (b1) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of the resin (b1) is preferably 20 ° C to 200 ° C, more preferably 80 ° C to 180 ° C. The Tg of the resin (b1) is preferably 20 ° C to 100 ° C, more preferably 40 ° C to 800 ° C.

The extender used for the extension of (b11) and (b12) is not particularly limited as long as it has two functional groups capable of reacting with the hydroxyl groups contained in (b11) and (b12). However, among dicarboxylic acids (13) and their anhydrides, polyisocyanates (15) and polyepoxides (19) described later, bifunctional ones can be mentioned. Of these, from the viewpoint of compatibility with (b11) and (b12), preferred are diisocyanate compounds and dicarboxylic acid compounds, and more preferred are diisocyanate compounds. Specifically, succinic acid, adipic acid, maleic acid and its anhydride, fumaric acid and its anhydride, phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2 , 4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane 4,4 ' -Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, etc. Among these, succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and its anhydride) are preferred. Product), fumaric acid (and its anhydride) , HDI, a IPDI, most preferably maleic acid (and its anhydride), fumaric acid (and its anhydride), and IPDI.
The content of the extender in (b1) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, from the viewpoints of transparency and thermal characteristics.

The content of the linear polyester resin (b1) contained in the total binder resin may be appropriately adjusted within a preferable range depending on the use, but from the viewpoint of dispersibility, it is preferably 40% with respect to the total binder resin. It is -100 mass%, More preferably, it is 60-100 mass%. Even when the hydroxycarboxylic acid contained in the resin (b1) is an optically active monomer such as lactic acid, the above content is preferable if the optical purity is 80% or less in terms of monomer components. When the optical purity in terms of monomer component exceeds 80%, from the viewpoint of dispersibility, the content of (b1) with respect to the total binder resin is the content Y (%) of the resin (b1) in the total binder resin. And X preferably satisfy Y ≦ −1.5X + 220.
The mass ratio of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) constituting the linear polyester is preferably 31:69 to 90:10, From the viewpoint of the transparency and thermal characteristics of the resin particles (C), it is more preferably 40:60 to 80:20.

The toner of the present invention contains at least the above-described linear polyester (b1) as a binder resin, and other resins can be used in combination with the linear polyester (b1). As the binder resin used in combination with the linear polyester (b1), any known resin may be used in combination. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, Examples thereof include phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. Of these, vinyl resins, polyester resins, polyurethane resins, epoxy resins, and combinations thereof are preferred, polyurethane resins and polyester resins are more preferred, and 1,2-propylene glycol is particularly preferred. Is a polyester resin and a polyurethane resin.
In addition, as a resin other than (B1), a non-linear polyester resin obtained by extending a polyester diol (b11) containing a poly α-hydroxycarboxylic acid skeleton and a later-described tri- or octavalent or higher polyol (12) with an extender. Can also be used.

  Hereinafter, vinyl resins, polyester resins, polyurethane resins, and epoxy resins that are preferable resins will be described in detail. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene, Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitution products such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene , Isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (C1-24) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxylic group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereafter.

(3) Sulfone group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) sulfuric acid of mono (meth) acrylate Esters [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfates or sulfones represented by the following general formulas (1-1) to (1-3) Acid group-containing monomers; and salts thereof.

（式中、Ｒは炭素数１〜１５のアルキル基、Ａは炭素数２〜４のアルキレン基を示し、ｎが複数の場合同一でも異なっていてもよく、異なる場合はランダムでもブロックでもよい。Ａｒはベンゼン環を示し、ｎは１〜５０の整数を示し、Ｒ’はフッ素原子で置換されていてもよい炭素数１〜１５のアルキル基を示す。）

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate phenyl-2-acryloyloxyethyl phosphate (meth) acryloyloxyalkyl (C1-24) phosphonic acids For example, 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (2) to (4) include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K. Alkali metal salts and amine salts are preferred, and sodium wax and tertiary monoamine salts having 3 to 20 carbon atoms are more preferred.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, ( (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthio (6-2) Amido groups such as pyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and their salts Vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene (6-4) quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethyl Aminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride chlorostyrene VI bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meta ) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms. Rudialkyl maleate (dialkyl maleate) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [ Vinyl monomers having a polyalkylene glycol chain, such as diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc. [polyethylene glycol (molecular weight 300) mono (Meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate Methyl alcohol EO 10 mol adduct (meth) acrylate lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.], etc. (9-2) Vinyl (thio) ether, for example vinyl methyl Ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-12-pyran, 2-butoxy-2, -vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketones such as Vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  Examples of the vinyl resin include polymers obtained by copolymerizing any of the above monomers (1) to (10) in two or more and in any proportion. For example, styrene- (meth) acrylic acid Ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meth) acrylic acid monoacrylic acid ester copolymer, styrene-acrylonitrile- (meth) acrylic acid monodivinylbenzene copolymer Examples thereof include polymers, styrene-styrenesulfonic acid mono (meth) acrylic acid ester copolymers, and salts of these copolymers. Among these, preferred is a copolymer containing 20 to 80% of an acrylate ester as a structural unit.

Examples of the polyester resin include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol having 3 to 8 or more valences (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and 3 to 6 or more valences. The above polycarboxylic acid (14) and these acid anhydrides or lower alkyl esters are mentioned.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1 to the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/4, particularly preferably 1 / 1.3 to 1/3.
In order to keep the carboxyl group content within the above preferred range, the polyester having an excess of hydroxyl groups may be treated with polycarboxylic acid.

  Diol (11) includes alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol. , Decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .: C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); C4-C36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); AO [EO, PO, BO, etc.] adduct of recall or alicyclic diol (addition mole number 1 to 120): AO (AO, PO, BO, etc.) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Examples include adducts (addition mole number: 2 to 30); polylactone diols (poly ε-caprolactone diol and the like); and polybutadiene diols and the like.

As the diol, in addition to the diol having no functional group other than the hydroxyl group, a diol (11a) having another functional group may be used. Examples of (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [things of C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolhebutane. Acid, 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [NN-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (AO is EO or PO, Addition mole number of AO 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 mole adduct, etc.]: Bis (2-hydroxy Ethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, AO adducts of diol bisphenols having a carboxyl group, and combinations thereof.

  Examples of the polyol (12) having 3 to 8 or more valences include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; saccharides and derivatives thereof such as sucrose and methylglucoside); AO adducts of polyhydric aliphatic alcohols (addition mole number: 2-120) : AO adduct (addition mole number 2-30) of trisphenol (trisphenol PA, etc.); AO adduct (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxy Ethyl (meth) acrylate and others Such as copolymer of vinyl monomers]; and the like. Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acid (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acids having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid) etc.), alkenedicarboxylic acids having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.): C8-36 aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like. Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the tri- or hexavalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid (13) or polycarboxylic acid (14) having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester) Etc.) may be used.

  As the polyurethane resin, polyisocyanate (15) and active hydrogen-containing compound {water, polyol [diol (11) [including diol (11a) having a functional group other than hydroxyl group], and 3 to 8 or more valences] Polyol (12)] polycarboxylic acid [dicarboxylic acid (13) and polycarboxylic acid (14) having 3 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, carbon number 6 to 12 lactone ring-opening polymer, polyamine (16), polythiol (17), and a combination thereof, and the like, and a terminal isocyanate group prepolymer obtained by reacting (15) with an active hydrogen-containing compound, , Equal amounts of primary and / or secondary monoamines (with respect to the isocyanate groups of the prepolymer) 8) and reacting the obtained, and amino group-containing polyurethane resins.

  Examples of the diol (11), 3 to 8 or more polyol (12), dicarboxylic acid (13), and 3 to 6 or more polycarboxylic acid (14) include those described above, and are preferable. The thing is the same.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate C2-C18 aliphatic polyisocyanate C4-C15 alicyclic poly (excluding carbon in NCO group) Isocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups And the like, and mixtures of two or more thereof.

  Specific examples of the aromatic polyisocyanate include 1,3- and / or 14-phenylene diisocyanate 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or Or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20%) of 3 Mixtures with functional or higher polyamines]: Polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenyl Sulfonyl isocyanate Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate tetramethylene diisocyanate hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate 1,6,11-undecane triisocyanate 2,2'4-trimethylhexamethylene diisocyanate lysine. Aliphatics such as diisocyanate 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4′-diisocyanate. Nate (hydrogenated MDI), cyclohexylene diisocyanate methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2, Specific examples of the aromatic aliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α, α, -tetramethylxylylene diisocyanate ( Examples of the modified polyisocyanates include urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, and the like. Mentioned That. Specifically, a modified product of polyisocyanate such as modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified 'MDI, etc.), urethane modified' TDI, etc., and a mixture of two or more of these [for example, modified MDI And urethane-modified TDI (isocyanate-containing prepolymer)]. Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI and HDI. , Hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines (C2 to Cl8): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. ), Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1 C4) or hydroxyalkyl (C2-C4) substituted [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa [3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4-C15) such as diaminocyclohexaneisophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylbiperazine, 1,4 -Aromatic poly, such as diaminoethylbiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Mines (C6-C20): [1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4- and 4,4-diphenylmethanediamine, crude diphenylmethanediamine ( Polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenol) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 " -Triamines, naphthylenediamines and the like; [2] Aromatic polyamines having a nucleus-substituted alkyl group [C1-C4 alkyl groups such as methyl, ethyl, n- and i-propylbutyl], for example 2.4 and 2,6 -Tolylenediamine, Crudetolylenediamine, Diethyltolylenediamine 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (O-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 1, 3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2, 3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3,5,5-tetramethylbenzidine, 3,3,5,5-tetramethyl-4,4 '-Diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4-diamino-3,3-dimethyldiphenylmethane, 3,3,5,5-tetraethyl-4,4-diaminobenzophenone, 3,3,5,5-tetraethyl-4,4′-diaminodiphenyl ether, 3, 3,5,5-tetraisopropyl-4,4′-diaminodiphenylsulfone, etc.), and mixtures of these isomers in various proportions: [3] nuclear substituted electron withdrawing groups (Cl, Br, 1, F, etc. Aromatic polyamines having halogens; alkoxy groups such as methoxy and ethoxy: nitro groups, etc. [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino -4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, -Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3-dichlorobenzidine, 3 , 3-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3- Methoxyphenyl) decane, bis (4-aminophenyl) sulfide bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4-methylenebis (2 -Iodoaniline), 4,4-methylenebis (2-bromoaniline), 4,4-methylenebi (4-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [in the above-mentioned [1] to [3] aromatic polyamines —NH ₂ Partially or entirely replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4-di (methylamino) diphenylmethane, 1-methyl-2 -Methylamino-4-aminobenzene, etc.], polyamide polyamine: by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamine (such as alkylenediamine, polyalkylenepolyamine, etc.) Low molecular weight polyamide polyamines such as polyether polyamine: polyether polyol (polyalkylene glycol, etc.) Examples thereof include hydrides of anoethylated products.

  Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (ethylamine, -butylamine, isobutylamine, etc.) and the like.

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and an active hydrogen group-containing compound {water, polyol [the diol (11) and a polyol having 3 to 8 or more valences (12)], The dicarboxylic acid (13), the trivalent to hexavalent or higher polycarboxylic acid (14), the polyamine (16), the polythiol (17), etc.}, or the polyepoxide (19) and the dicarboxylic acid (13) or a cured product of an acid anhydride of a polycarboxylic acid (14) having a valence of 3 to 6 or more, and the like.

  The polyepoxide (19) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. A thing preferable as a polyepoxide (19) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (19) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65. is there.

  Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. The glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol, and A diglycidyl tetrachlorobisphenol. A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl Diglycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Glycidyl ethers of enol or cresol novolac resins, glycidyl ethers of limonene phenol novolak resins, diglycidyl ethers obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation of phenol and glyoxal glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ether of polyphenol obtained by the reaction, polyglycidyl ether of polyphenol obtained by the condensation reaction of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and the like. Examples of the glycidyl aromatic polyamine include NN-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine: Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, and bis (2,3-epoxycyclopentyl) ether. , Ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6, -methylcyclohexanecarboxylate bis (3,4-epoxy-6-methylcyclohexylmethyl) Examples include adipate and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate diglycidyl malate diglycidyl succinate diglycidyl glutarate, diglycidyl adipate diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) of resins other than polyurethane resins such as polyester resins are gel permeation chromatography for tetrahydrofuran (THF) soluble components. (GPC) is used under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
: TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

Tg in the present invention is a value obtained from DSC measurement or flow tester measurement (when measurement cannot be performed by DSC).
In the case of measurement by DSC, it is measured by the method (DSC method) defined in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Electronics Industry. For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions. (Flow tester measurement conditions) Load: 30 kg / cm ² , heating rate: 3.0 ° C./min, die diameter: 0.50 mm, tie length: 10.0 mm

  Examples of the wax (c) include polyolefin wax, paraffin wax, carbonyl group-containing wax, and mixtures thereof. Among these, paraffin wax is particularly preferable, and the melting point is 50 to 90 ° C. and the carbon number is 20 to 36. And petroleum-based waxes mainly composed of the above linear saturated hydrocarbons. Further, from the viewpoint of template properties, Mn in (c) is preferably 400 to 5000, more preferably 1000 to 3000, and particularly 1500 to 2000. In the above and below, Mn of the wax is measured using GPC (solvent: orthodichlorobenzene, reference material: polystyrene).

  The wax (c) is dispersed in the binder resin after being melt-kneaded in the absence of a solvent and / or heat-dissolved and mixed in the presence of the organic solvent (u) with the modified wax (d) grafted with the vinyl polymer chain. It is preferable. By this method, the wax base portion of the modified wax (d) is efficiently adsorbed on the surface (c) or partially entangled with the matrix structure of the wax, whereby the surface of the wax (c) and the polyester resin (b1) (C) can be more uniformly encapsulated in (b1), and the dispersion state can be easily controlled.

  The modified wax (d) is obtained by grafting a vinyl polymer chain onto the wax. Examples of the wax used in (d) include the same waxes as the wax (c), and preferred ones are also the same. Examples of the vinyl monomer constituting the vinyl polymer chain of (d) include those similar to the monomers (1) to (10) constituting the vinyl resin. Among these, (1), ( 2) and (6). The vinyl polymer chain may be a homopolymer of a vinyl monomer or a copolymer.

  The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5%, more preferably 1 to 80%, particularly preferably 5 to 50%, and most preferably 10. ~ 30%. The Tg of (d) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, from the viewpoint of heat resistant storage stability of the resin particles (C). Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000. When Mn is in the range of 1500 to 10,000, the resulting toner has good mechanical strength.

  The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in an organic solvent (for example, toluene or xylene) and heating to 100 to 200 ° C., and then converting the vinyl monomer into a peroxide-based initiator (benzoyl peroxide, diter It can be obtained by dripping together with sharry butyl peroxide, tertiary butyl peroxide benzoate, etc.) and distilling off the solvent after polymerization. The amount of the peroxide-based initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10%, more preferably 0.5 to 5%, based on the total mass of the raw material (d).

  As the peroxide polymerization initiator, an oil-soluble peroxide polymerization initiator and a water-soluble peroxide polymerization initiator are used. Specific examples of these initiators include those described above.

As a method of mixing the wax (c) and the modified wax (d), [1] a method of melt-kneading at a temperature equal to or higher than the melting point of each, [2] (c) and (d) in the organic solvent (u) A method of dissolving or suspending, then precipitating in a liquid by cooling crystallization, solvent crystallization, or the like, or precipitating in a gas by spray drying or the like, [3] (c) and (d) as an organic solvent (u) Examples of the method include a method of dissolving or suspending in the inside and then performing mechanical wet pulverization with a disperser. As a method of dispersing the wax (c) and the modified wax (d) in the polyester-based resin (b1), (c), (d), and (b1) are melt-kneaded, or a solvent solution or dispersion, respectively. And a method of mixing them together.
When the resin particle (B) contains the resin (b), the wax (c), and the modified wax (d) having a vinyl polymer chain grafted on the resin particle (B), the heat-resistant storage stability is further improved. It is preferable. The content of (c) with respect to the total binder resin is preferably 20% by mass or less, more preferably 1 to 15% by mass. The content of (d) is preferably 10% by mass or less, more preferably 0.5 to 8% by mass. The total content of (c) and (d) is preferably 25% by mass or less, more preferably 1 to 20% by mass.

(Coloring agent)
The colorant used in the present invention is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow ( 10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mercury Red Antimon Zhu, Permanent Red 4R, La Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Irred, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, reed Green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the master batch, various resins that can be used for the binder resin of the toner of the present invention described above can be used.
The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, for example, a high shearing dispersion device such as a two-roll mill or a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

  The resin for the master batch has an acid value of 30 mgKOH / g or less, and is preferably used by dispersing a colorant, and more preferably 20 mgKOH / g or less. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070.

Further, a pigment dispersant may be used together with the masterbatch resin and the colorant, but it is preferable that the compatibility with the binder resin is high in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by BYK Chemie), “EFKA-4010” (manufactured by EFKA), and the like. It is done.
The pigment dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

(Magnetic material)
In the present invention, a magnetic substance can be contained together with the binder resin and the colorant.
Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of
Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.
The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.

As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable.
The magnetic material can also be used as a colorant.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine) Modified quaternary ammonium salts), alkylamides, simple substances or compounds of phosphorus, simple substances or compounds of tungsten, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge NEG VP2036 of quaternary ammonium salt, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone, Zone-based pigment, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the like, and is not uniquely limited. It is used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded together with the masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent. Further, after the toner base particles are prepared, they may be fixed on the surface thereof.

(External additive)
The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, And aluminum oxide stearate); metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

In order to obtain the hydrophobized silica fine particles, the hydrophobized titania fine particles, and the hydrophobized alumina fine particles, the hydrophilic fine particles are made of silane cups such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with a ring agent.
Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

In addition, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, and more preferably 5 to 70 nm. More preferably, the primary particles subjected to the hydrophobization treatment include at least two types of inorganic fine particles having an average particle diameter of 20 nm or less and at least one type of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by the BET method of the said inorganic fine particle is 20-500 m < ² > / g.
The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; condensation polymerization system such as silicone, benzoguanamine, nylon; polymer particles by thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

(Toner production method)
As the method for producing the toner, conventionally known kneading and pulverization methods, polymerization methods, dissolution suspension methods, spray granulation methods, and the like can be used. From the viewpoint of dispersibility and productivity of release agents and colorants. In addition, a kneading / pulverizing method is used as a suitable means because of its high material selectivity.
The kneading and pulverizing method is a method of producing the toner base particles by, for example, pulverizing and classifying a melt-kneaded toner material.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, a Kneader manufactured by Buss, etc. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.
In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.
Next, the external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

(Developer)
The developer contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

(Career)
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (weight average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, for example, 90 to 98 mass. % Is preferable, and 93 to 97% by mass is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

(Image forming apparatus and image forming method)
An image forming apparatus according to the present invention includes an electrostatic latent image carrier, a charging unit that charges the surface of the electrostatic latent image carrier, and an electrostatic latent image formed by exposing the charged electrostatic latent image carrier surface. An exposure unit for forming, a developing unit for developing the electrostatic latent image with toner to form a visible image, a transfer unit for transferring the visible image to a recording medium, and the image transferred to the recording medium A fixing unit for fixing the transferred image, and a cleaning unit, and other units appropriately selected as necessary, for example, a discharging unit, a recycling unit, a control unit, and the like. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit. The toner used for the developing means is the image forming toner of the present invention.
The image forming method of the present invention comprises a charging step of charging the surface of the electrostatic latent image carrier, an exposure step of exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic A developing process for developing a latent image with toner to form a visible image, a transfer process for transferring the visible image to a recording medium, and a fixing process for fixing the transferred image transferred to the recording medium. It includes at least a cleaning process, and other processes appropriately selected as necessary, for example, a static elimination process, a recycling process, a control process, and the like. The charging process and the exposure process may be collectively referred to as an electrostatic latent image forming process. The toner used in the developing step is the image forming toner of the present invention.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, the fixing step can be performed by the fixing unit, and the cleaning step can be performed by the cleaning unit. The other steps can be performed by the other means.

The toner for image formation of the present invention can be used by being housed in a process cartridge having at least the electrostatic latent image carrier and a developing unit and detachable from the main body of the image forming apparatus.
FIG. 1 shows a schematic configuration of an image forming apparatus provided with a process cartridge having the image forming toner of the present invention.
In the figure, reference numeral 1 denotes the entire process cartridge, 2 denotes a photosensitive member, 3 denotes charging means, 4 denotes developing means, and 5 denotes cleaning means.
In the present invention, a plurality of components such as the photosensitive member 2, the charging unit 3, the developing unit 4, and the cleaning unit 5 described above are integrally coupled as a process cartridge, and this process is performed. The cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

The operation of the image forming apparatus provided with the process cartridge having the image forming toner of the present invention will be described as follows.
The photoreceptor 2 is driven to rotate at a predetermined peripheral speed. In the rotating process, the photosensitive member 2 is uniformly charged with a positive or negative predetermined potential on the peripheral surface thereof by the charging unit 3, and then an image from the image exposure unit such as slit exposure or laser beam scanning exposure. In response to the exposure light, an electrostatic latent image is sequentially formed on the circumferential surface of the photoreceptor, and the formed electrostatic latent image is then toner developed by the developing means 4, and the developed toner image is fed. The transfer unit sequentially transfers the image to the transfer material fed in synchronization with the rotation of the photoconductor between the photoconductor and the transfer unit. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by a cleaning means, and after being further neutralized, it is repeatedly used for image formation.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by mass.

Production Example 1 (Production of linear polyester resin (b1))
In an autoclave reactor equipped with a thermometer, a stirrer and a nitrogen insertion tube, 3 parts 1,3-propanediol, 450 parts L-lactic acid lactide, 50 parts D-lactic acid lactide and 2 parts tin 2-ethylhexylate The ring-opening polymerization was carried out at 160 ° C. for 3 hours at normal pressure, and further reacted at 130 ° C. at normal pressure. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2 mol adduct and terephthalic acid were dehydrated and condensed at a molar ratio of l: l. 100 parts was dissolved in methyl ethyl ketone, followed by adding 20 parts of IPDI as an extender, performing an extension reaction at 50 ° C. for 6 hours, and distilling off the solvent to obtain [polyester b1-1]. Got. [Polyester b1-1] had a Tg of 43 ° C.

Production Example 2 (Production of linear polyester resin (b1))
In an autoclave reaction vessel equipped with a thermometer, a stirrer, and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 400 parts of L-lactic acid lactide, 100 parts of D-lactic acid lactide and 2 parts of tin 2-ethylhexylate The mixture was subjected to ring-opening polymerization at 160 ° C. for 3 hours at normal pressure, and further reacted at 130 ° C. at normal pressure. The taken-out resin was cooled to room temperature, and then pulverized into a polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 60 mol%). 200 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2-mol adduct and terephthalic acid were dehydrated and condensed at a molar ratio of 1: 1. Obtained by synthesis] 300 parts are dissolved in methyl ethyl ketone, followed by adding 38 parts of IPDI as an extender, performing an extension reaction at 50 ° C. for 6 hours, and distilling off the solvent to obtain [Polyester b1-2]. Obtained. [Polyester b1-2] had a Tg of 46 ° C.

Production Example 3 (Production of linear polyester resin (b1))
In an autoclave reaction vessel equipped with a thermometer, a stirrer and a nitrogen insertion tube, 3 parts of 1,3-propanediol, 400 parts of L-lactic acid lactide, 100 parts of glycolide and 2 parts of tin 2-ethylhexylate were added. The ring-opening polymerization was performed at 160 ° C. for 3 hours at a pressure, and further reacted at 130 ° C. at a normal pressure. The taken-out resin was cooled to room temperature and then pulverized into a polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 100 mol%). 250 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2 mol adduct and terephthalic acid were dehydrated and condensed at a molar ratio of 1: 1. 250 parts of adipic acid was added as an extender, followed by reaction at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Polyester b1-3]. [Polyester b1-3] had a Tg of 49 ° C.

Production Example 4 (Production of linear polyester resin (b1))
In a reaction vessel equipped with a condenser, a stirring machine, and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 450 parts of L-lactic acid, 50 parts of D-lactic acid and 2 parts of tetrabutoxytitanate are added at normal pressure. The mixture was dehydrated and condensed at 160 ° C. for 3 hours, and further dehydrated and condensed at 160 ° C. under a reduced pressure of 10 to 15 mmHg. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2 mol adduct and terephthalic acid were dehydrated and condensed at a molar ratio of 1: 1. 100 parts obtained by synthesis] were dissolved in methyl ethyl ketone, followed by addition of 20 parts of IPDI, an extension reaction was performed at 50 ° C. for 6 hours, and the solvent was distilled off to obtain [Polyester b1-4]. [Polyester b1-4] had a Tg of 48 ° C.

Production Example 5 (Production of linear polyester resin (b1))
In a reaction vessel equipped with a cooling tube, a stirring frame, and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 450 parts of L-lactic acid, 50 parts of D-lactic acid and 2 parts of tetrabutoxy titanate were added at normal pressure. The mixture was dehydrated and condensed at 160 ° C. for 3 hours, and further dehydrated and condensed at 160 ° C. under a reduced pressure of 10 to 15 mmHg. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [synthesized by dehydration condensation of 1,2-propylene glycol and terephthalic acid at a molar ratio of 1: 1. 100 parts was dissolved in methyl ethyl ketone, followed by addition of 20 parts of IPDI, an extension reaction was performed at 50 ° C. for 6 hours, and the solvent was distilled off to obtain [Polyester b1-5]. [Polyester b1-5] had a Tg of 48 ° C.

Production Example 6 (Production of polyester resin)
9 parts of glycerin, 288 parts of L-lactic acid lactide and 2 parts of dibutyltin oxide are put into an autoclave reaction vessel equipped with a thermometer and a stirring frame, and after nitrogen substitution, ring-opening polymerization is performed at 160 ° C. for 6 hours at normal pressure. Further, after reacting for 5 hours at a reduced pressure of 10 to 15 mmHg, cooling to 110 ° C., adding 18 parts of IPDI in toluene, reacting at 110 ° C. for 5 hours, then removing the solvent, and weight average molecular weight
A [urethane-modified polyester] having an Mw of 70,000 and a free isocyanate content of 0.5% was obtained (optical purity of 100 mol%).

Production Example 7 (Production of polyester resin)
6 parts of ethylene glycol, 400 parts of L-lactic acid lactide and 2 parts of dibutyltin oxide are charged into an autoclave reaction vessel equipped with a thermometer and a stirring frame. After nitrogen substitution, ring-opening polymerization is performed at 160 ° C. for 8 hours at normal pressure. Further, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Polyester 1] (optical purity 100 mol%). [Polyester 1] had a Tg of 40 ° C.

Production Example 8 (Production of polyester resin)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 701 parts of 1,2-propylene glycol, 716 parts of dimethyl terephthalate, 180 parts of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst are placed. The reaction was carried out for 8 hours while distilling off the produced methanol under a nitrogen stream at 180 ° C. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the 1,2-propylene glycol produced and water under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg. When it reached 150 ° C., it was taken out. Into an autoclave reaction tank equipped with a thermometer and a stirring frame, 100 parts of the taken-out resin, 400 parts of L-lactic acid lactide, 100 parts of racemic lactate lactide and 1 part of titanium terephthalate were charged. Polymerization was performed for a time to obtain [Polyester 2] (optical purity 80 mol%). [Polyester 2] had a Tg of 47 ° C.

Production Example 9 (Production of polyester resin)
In a reaction vessel equipped with a cooling tube, a stirring frame and a nitrogen introduction tube, 781 parts of 1,2-propylene glycol, 794 parts of dimethyl terephthalate, 66 parts of adipic acid, 38 parts of trimellitic anhydride and terephthalate as a polymerization catalyst 1 part of titanium oxide was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the 1,2-propylene glycol and water produced under a nitrogen stream, and further the reaction is performed for 1 hour under a reduced pressure of 5 to 20 mmHg to soften. It was taken out when the point reached 160 ° C. to obtain [Polyester 3]. [Polyester 3] had a Tg of 61 ° C.

Production Example 10 (Production of modified wax)
454 parts of xylene and 150 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. sun wax LEL-400: softening point 128 ° C.) were introduced into an autoclave reaction vessel equipped with a thermometer and a stirring frame. The temperature was raised to 0 ° C. and dissolved sufficiently, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [modified wax l]. The sp value of the graft chain of [modified wax 1] was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1872, Mw was 5194, and Tg was 56.9 ° C.

Production Example 11 (Production of resin)
200 parts of [Polyester 3] and 800 parts of [Polyester b1-2] were melted and kneaded at a temperature of 100 to 130 ° C. with a biaxial kneader (manufactured by Ikegai Co., Ltd., PCM-30). Next, the obtained kneaded product was cooled to room temperature, and then coarsely pulverized to 200 to 300 μm with a hammer mill to obtain [Resin 1] (content of (b1) in resin is 80%, optical of (b1) 60% purity).

Production Example 12 (Production of resin)
[Polyester b1-1] 1000 parts were coarsely pulverized to 200 to 300 μm with a hammer mill to obtain [Resin 2] (content of (b1) in resin is 100%, optical purity of (b1) is 80%) .

Production Example 13 (Production of resin)
200 parts of [Polyester 3] and 800 parts of [Polyester b1-3] were melted, kneaded and pulverized in the same manner as in Production Example 11 to obtain [Resin 3] (content of (b1) in the resin was 80%) , (B1) optical purity 100%).

Production Example 14 (Production of resin)
200 parts of [urethane modified polyester] and 800 parts of [polyester b1-4] were melted, kneaded and pulverized in the same manner as in Production Example 11 to obtain [Resin 4] (content of (b1) in resin 80 %, Optical purity of (b1) 80%).

Production Example 15 (Production of resin)
200 parts of [urethane-modified polyester] and 800 parts of [polyester b1-5] were melted, kneaded and pulverized in the same manner as in Production Example 11 to obtain [Resin 5] (content of (b1) in resin 80 %, Optical purity of (b1) 80%).

Production Example 16 (Production of resin)
350 parts of [Polyester 3] and 650 parts of [Polyester b1-3] were melted, kneaded and pulverized in the same manner as in Production Example 11 to obtain [Resin 6] (content of (b1) in resin: 65% , (B1) optical purity 100%).

Production Example 17 (Production of resin)
200 parts of [urethane-modified polyester] and 800 parts of [polyester 1] were melted, kneaded and pulverized in the same manner as in Production Example 11 to obtain [resin 7] (content of (b1) in the resin was 0%, Optical purity of (b1) 0%).

Production Example 18 (Production of resin)
200 parts of [Urethane-modified polyester] and 800 parts of [Polyester 2] were melted, kneaded and pulverized in the same manner as in Production Example 11 to obtain [Resin 8] (content of (b1) in the resin was 0%, Optical purity of (b1) 0%).

[Method for measuring weight average particle diameter of toner]
Measuring instrument: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19
(Made by Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether
, HLB: 13.6) 5% electrolytic solution Dispersion condition: 10 mg of a measurement sample is added to 5 ml of the dispersion, and is mixed for 1 minute with an ultrasonic disperser.
And then add 25 ml of electrolyte, and further with an ultrasonic disperser
Disperse for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion into a beaker, and adjust the particle size of 30,000 particles.
Measure 30,000 particles at a concentration that can be measured in 20 seconds.
Determine the weight average particle size.

Example 1
(Toner prescription)
Resin 1 84 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Henshell mixer (Mitsui Miike Chemical Co., Ltd., FM10B) ), And then melted and kneaded at a temperature of 100 to 130 ° C. with a biaxial kneader (manufactured by Ikegai Co., Ltd., PCM-30). The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labojet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the weight average particle size becomes 6.2 ± 0.3 μm. The louver opening is adjusted so that the weight average particle size is 7.0 ± 0.2 μm and the amount of fine powder of 4 μm or less is 10% by number or less with an air classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was carried out with appropriate adjustment to obtain toner base particles. Next, 1.0 part by mass of an additive (silica: HDK-2000, manufactured by Clariant Co., Ltd.) was mixed with 100 parts by mass of the toner base particles with a Henschel mixer to produce toner 1.

(Example 2)
(Toner prescription)
Resin 2 58.8 parts Resin 4 25.2 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Except for changing to toner formulation shown above, Examples Toner 2 was produced in the same manner as in Example 1.

(Example 3)
(Toner prescription)
Resin 2 42 parts Resin 3 42 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Same as Example 1 except for changing to the toner formulation shown above Toner 3 was produced by this method.

Example 4
(Toner prescription)
Resin 3 84 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Manufactured.

(Example 5)
(Toner prescription)
Resin 4 42 parts Resin 3 42 parts Carnauba wax (melting point 80 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Toner 5 was produced by this method.

(Example 6)
(Toner prescription)
Resin 5 84 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Manufactured.

(Example 7)
(Toner prescription)
Resin 6 84 parts Carnauba wax (melting point 80 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Toner 7 in the same manner as in Example 1 except that the toner formulation was changed to the one shown above. Manufactured.

Comparative Example 1
(Toner prescription)
Resin 7 84 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Toner 8 in the same manner as in Example 1 except that the toner formulation was changed to the one shown above. Manufactured.

Comparative Example 2
(Toner prescription)
Resin 8 84 parts Paraffin wax (melting point 73 ° C.) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Manufactured.

  The toners obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were measured and evaluated based on the measurement methods of charging characteristics, heat storage stability, meltability and haze degree described below. The evaluation results are shown in Table 1.

[Charging characteristics] (Charge amount)
In a 50 cc glass bottle with a stopper, weigh accurately 10 g of toner and iron powder (“F-150” manufactured by Nippon Iron Powder Co., Ltd.), plug it into a stopper, and turn the shaker mixer under an atmosphere of 23 ° C. and 50% RH. (Willie a Baschofen) and stirred for 2 minutes at 90 rpm. The mixed powder O2g after stirring was loaded into a blow-off powder charge measuring device (TB-203 manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless steel mesh was set, and remained under conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa. The charge amount of the iron powder was measured, and the charge amount of the resin particles was calculated by a conventional method. For toners, the higher the negative charge amount, the better the charging characteristics. The evaluation criteria are as follows.
○: −25 μC / g or less, Δ: −25 to −20 μC / g, ×: −20 μC / g or more

[Heat resistant storage stability]
The toner was allowed to stand for 15 hours in a dryer adjusted to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

[Melting property]
The toner is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (At this time, the method of placing the powder on the paper surface is to use a printer from which the heat fixing machine is removed (the powder is uniformly placed at the above weight density). Other methods may be used as long as they can be used.) This paper is fixed to a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² . The temperature at which the cold offset was generated was measured, and the evaluation criteria are as follows.
○: 120 ° C. or lower, Δ: 120 to 140 ° C., ×: 140 ° C. or higher

[Haze degree]
An image was formed on the OHP sheet by the same operation as in the above-described meltability test, and measurement was performed using a haze meter (“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JISK7136. The haze degree is also referred to as the haze degree, and is measured as a scale indicating the transparency of the resin film. The lower the value, the higher the transparency. The evaluation criteria are as follows.
○: 20% or less, Δ: 20-30%, X: 30% or more

(Volume resistivity)
The volume specific resistance LogR of the toner was measured as follows. First, a measurement sample in which 3 g of toner was molded into a pellet of about 2 mm thickness was prepared, and this was set on an SE-70 type solid electrode (manufactured by Ando Electric Co., Ltd.), and 1 kHz between the electrodes. LogR when an alternating current was applied was measured with a measuring instrument composed of a TR-10C dielectric loss measuring instrument, a WBG-9 oscillator, and a BDA-9 equilibrium point detector (both manufactured by Ando Electric Co., Ltd.). Thus, the volume specific resistance value LogR of the toner was obtained. The higher the LogR, the easier it is to hold charges, and the smaller the environmental fluctuation of the charge amount, the better. The evaluation criteria are as follows.
O: 11.0 LogΩ · cm or more Δ: 10.0 to 11.0 LogΩ · cm
×: 10.0 LogΩ · cm or less

[Image density]
In the same manner as in the evaluation of the meltability, the toner is uniformly placed on the paper surface so as to be 0.4 mg / cm ^2. The paper is placed on a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec, a fixing pressure ( The image density of the sample passed under a pressure roller pressure of 10 kg / cm ² was evaluated by measuring the visual density using X-Rite 938 (manufactured by X-Rite). The evaluation criteria are as follows.
O: Visual density of 1.4 or more Δ: Visual density of 1.4 to 1.2
× Visual density 1.2 or less

  The toner for image formation according to the present invention is excellent in thermal characteristics, heat-resistant storage stability, and transparency, so that it can be used for image formation of electrophotographic systems such as copying machines, electrostatic printing, printers, facsimiles, and electrostatic recording. It can be suitably used as a toner.

It is the schematic which shows the structure of a process cartridge.

DESCRIPTION OF SYMBOLS 1 Process cartridge 2 Photoconductor 3 Charging means 4 Developing means 5 Cleaning means

Claims (10)

  As a binder resin, a linear polyester resin (b1) obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11) together with an extender. ) And a monomer that forms the polyhydroxycarboxylic acid skeleton of (b11) is an optically active monomer, and optical purity X (%) = | X (L ) -X (D isomer) | [where X (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) is the D isomer ratio (mol%) in terms of optically active monomer). ) Is 80% or less, or the content Y (mass%) of the resin (b1) in the total binder resin and the optical purity X (mol%) in terms of monomer components = | X ( ) -X (D isomer) | [where X (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) is the D isomer ratio (mol%) in terms of optically active monomer). ) Represents a toner satisfying the following relationship: Y ≦ −1.5X + 220 (80 <X ≦ 100).   In the polyester resin (b1), the mass ratio of the polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton to the polyester diol (b12) other than (b11) is 31:69 to 90:10. The toner for image formation according to claim 1.   3. The image forming toner according to claim 1, wherein the polyhydroxycarboxylic acid skeleton of (b11) is a skeleton obtained by (co) polymerizing a hydroxycarboxylic acid having 2 to 6 carbon atoms.   The image forming apparatus according to claim 1, wherein the polyhydroxycarboxylic acid skeleton of (b11) is a (co) polymer obtained by direct dehydration condensation of hydroxycarboxylic acid. toner.   The binder resin other than the polyester resin (b1) contains at least one resin selected from the group consisting of a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin. The image forming toner according to claim 1.   6. The image forming toner according to claim 1, wherein the image forming toner further contains a wax (c) and a modified wax (d) in which a vinyl polymer chain is grafted to (c). Image forming toner.   2. The image forming toner comprises particles obtained by pulverizing after melt-kneading a toner component containing at least a binder resin containing a resin (b1) and a colorant. The toner for image formation according to any one of -6.   An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus comprising: the image forming apparatus according to claim 1, wherein the toner is the image forming toner according to claim 1.   A charging process for charging the surface of the electrostatic latent image carrier, an exposure process for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method including at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. The image forming method according to claim 1, wherein the toner is the image forming toner according to claim 1.   The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge that is detachable, wherein the toner is the image forming toner according to claim 1.

Images