JPH11189647A - Polyol resin and electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyol resin excellent in low-temp. fixability by reacting a bisphenol, a bisphenol epoxy resin, at least one compd. selected from among polyhydric alcohols and reaction products of polyhydric alcohols with acid anhydrides, and an active hydrogen compd. SOLUTION: This polyol resin, having a number average mol.wt. of 1,000-10,000, a ratio of wt. average mol.wt. to number average mol.wt. of 5-50, a softening point of 85-150 deg.C, and a glass transition temp. of 50-90 deg.C, is obtd. by the polyaddition of a bisphenol of formula I (e.g. bisphenol A), at least one bisphenol epoxy resin of formula II, at least one compd. selected from among polyhydric alcohols (e.g. an arom. diol of formula II) and reaction products of polyhydric alcohols with acid anhydrides, and an active hydrogen compd. in a specified ratio at 120-180 deg.C in the presence of a catalyst. In the formulas, R<1> to R<4> are each H, methyl, or the like; R<5> and R<6> are each ethylene or propylene; (n) is 0 or higher; and (p) and (q) are each 1 or higher provided p+q is 2-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyol resin and a toner for electrophotography, and more particularly to a polyol useful as a toner for dry development for developing an electrostatic image or a magnetic latent image in electrophotography of a copying machine, a facsimile, a printer and the like. The present invention relates to a resin and an electrophotographic toner containing the polyol resin as a main component.

[0002]

2. Description of the Related Art In electrophotography of a copying machine, a facsimile, a printer, and the like, there are a wet developing method and a dry developing method as a method for developing an electrostatic image, and a dry developing method is often used. In the dry development method, a triboelectric developer is used in which a carrier such as iron powder or glass beads is mixed with fine toner powder containing a colorant such as carbon black and other additives in a toner resin serving as a binder. Can be In order to obtain a copy, usually, an electrostatic latent image is formed on a photoreceptor, a triboelectric toner is electrically attached to the electrostatic latent image and developed, and the obtained toner image is printed on paper. And then fixed with a hot-press roller having releasability to the toner or with a flash light source to form a permanent visible image. In the case of a magnetic latent image, the latent image on the magnetic drum is developed with toner containing a magnetic material, and then subjected to fixing as described above.

[0003] This type of toner is required to have excellent fixability (the toner is firmly attached to the paper) and excellent blocking resistance (the toner particles do not agglomerate). Further, in the heat roll fixing, anti-offset property (the toner is not adhered to the fixing roller and the paper is not stained) is required. In recent years, as copiers, fax machines or printers have become more prevalent in the home, it is required to reduce power consumption and improve the speed of visible image formation when using these devices, and use binder resins with low fixing temperatures. Is required. In order to lower the fixing temperature, a method such as lowering the softening point of the binder resin or narrowing the molecular weight distribution is generally adopted. However, these methods decrease the offset resistance and the blocking resistance. For this reason, low-temperature fixing of the toner is not yet sufficient.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problems of conventional toners, to provide excellent low-temperature fixability, and excellent offset resistance and blocking resistance. Polyol resin,
And an electrophotographic toner containing the polyol resin as a main component.

[0005]

Means for Solving the Problems To solve the above problems, the present invention provides the following general formula (a):

Embedded image (R ¹ and R ² may be the same or different and are a hydrogen atom, a methyl group, an ethyl group or a phenyl group), and a bisphenol (A) represented by the following general formula (b):

Embedded image (R ³ and R ⁴ may be the same or different and each is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, and n is an integer of 0 or more). Compound (E) having at least one selected from a polyhydric alcohol (C) and a reactant (D) of the polyhydric alcohol and an acid anhydride, and at least one active hydrogen group in the molecule that reacts with an epoxy group And a polyol resin obtained by reacting

The present invention also provides an electrophotographic toner containing the above polyol resin as a main component, as a toner having excellent low-temperature fixability, offset resistance and blocking resistance.

Hereinafter, the polyol resin of the present invention (hereinafter, referred to as the polyol resin)
The “resin of the present invention”) and the toner for electrophotography will be described in detail.

The resin of the present invention comprises a bisphenol (A) represented by the general formula (a), a bisphenol epoxy resin (B) represented by the general formula (b), and a polyhydric alcohol (C). ) And a compound (E) having at least one active hydrogen group capable of reacting with an epoxy group in the molecule, and at least one selected from a reaction product (D) of the polyhydric alcohol and an acid anhydride. It is obtained by using the crosslinking agent (E) as a main raw material and reacting these main raw materials accordingly.

The bisphenols used as the main raw material (A) of the resin of the present invention are those represented by the general formula (a). In the general formula (a), R ¹ and R
² may be the same or different and is a hydrogen atom, a methyl group, an ethyl group or a phenyl group. Specific examples of the bisphenols (A) include 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] and bis (4-hydroxyphenyl) methane [commonly referred to as
Bisphenol F], 1,1-bis (4-hydroxyphenyl) ethane [commonly known as bisphenol AD], 1-phenyl-1,1-bis (4-hydroxyphenyl) methane, 1-phenyl-1,1-bis ( 4-hydroxyphenyl) ethane and the like. In the present invention, these bisphenols may be used alone or may be used alone.
A combination of more than one species may be used.

The bisphenol type epoxy resin used as the main raw material (B) of the resin of the present invention is represented by the general formula (b). In the above formula (b),
R ³ and R ⁴ may be the same or different and are a hydrogen atom, a methyl group, an ethyl group or a phenyl group;
Is an integer of 0 or more. Examples of the bisphenol-type epoxy resin (B) include a so-called one-step epoxy resin or a one-step epoxy resin produced from the bisphenol (A) represented by the general formula (a) and epichlorohydrin. Examples include a two-step epoxy resin which is a product of a polyaddition reaction with bisphenols [Hiroshi Kakiuchi, edited by "New Epoxy Resin", Shokodo, p. 30 (Showa 60)
Year)]. In the present invention, the bisphenol type epoxy resin may be used alone or in combination of two or more kinds or a mixture of two or more kinds having different number average molecular weights. When two or more kinds or a mixture of two or more kinds having different number average molecular weights are used, the molecular weight distribution (Mw / Mn) becomes large as compared with the case of using one kind alone, which is advantageous in improving the offset resistance. In this case, the number average molecular weight of the low molecular weight component is preferably 300 to 3000, and the number average molecular weight of the high molecular weight component is preferably 3000 to 10,000. In the production of the polyol resin of the present invention, it is generally preferable that a low molecular weight component is a main component from the viewpoint of operability of raw material supply.

[0011] The resin of the present invention comprises the above (A) and (B)
In addition, at least one selected from a polyhydric alcohol (C) and a reaction product (D) of the polyhydric alcohol and an acid anhydride is used as a main raw material. Examples of the polyhydric alcohol used as the main raw material (C) include dihydric alcohols such as aromatic diols, aliphatic diols, and alicyclic diols, and trihydric or tetrahydric alcohols. As the aromatic diol, the following general formula (c):

Embedded image The compound represented by these is mentioned. In the general formula (c), R ⁵ and R ⁶ may be the same or different,
An ethylene group or a propylene group, p and q are 1
Is an integer as described above, and p + q is 2 to 10. Specific examples of the aromatic diol include polyoxyethylene-
(2,0) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (2,0) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxypropylene- (1,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene-
(1,1) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (2,2) -polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene-
(6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3,3) -2,2-bis (4-hydroxyphenyl) propane and the like. In the present invention, the aromatic diol is P
-Xylylene glycol and m-xylylene glycol can also be used.

Examples of the aliphatic diol include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetramethylene glycol, pentamethylene glycol, neopentyl glycol and the like. Examples of the alicyclic diol include dihydroxymethylcyclohexane and hydrogenated bisphenol A.

The trihydric or tetrahydric alcohols include, for example, 1,2,3,6-hexanetetrol, 1,4-
Sorbitan, pentaerythritol, tripentaerythritol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like can be mentioned.

The reactant used as the main raw material (D) is a reactant of the polyhydric alcohol (C) and an acid anhydride. Examples of the acid anhydride used in the reaction with the polyhydric alcohol (C) include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate,
Maleic anhydride, tetrahydrophthalic anhydride, methyltentrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, Methyl hexahydrophthalic anhydride, succinic anhydride,
Examples thereof include methylcyclohexenedicarboxylic anhydride, alkylstyrene-maleic anhydride copolymer, chlorendic anhydride, and polyazelain anhydride.

The reaction between the polyhydric alcohol and the acid anhydride can be carried out usually at 80 ° C. to 150 ° C. for 1 to 8 hours in the presence of a catalyst. The reaction between the polyhydric alcohol and the acid anhydride may be carried out simultaneously with the polyaddition reaction in the production of the resin of the present invention described later, or may be carried out before the polyaddition reaction. Since the acid anhydride acts as a cross-linking agent and may cause gelation in some cases, it is preferably performed before the polyaddition reaction. Examples of the catalyst used in this reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal alcoholates such as sodium methylate, N, N-dimethylbenzylamine, triethylamine, pyridine Quaternary ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride; organic phosphorus compounds such as triphenylphosphine and triethylphosphine; alkali metal salts such as lithium chloride and lithium bromide; Examples thereof include Lewis acids such as boron chloride, aluminum chloride, tin tetrachloride, tin octylate, and zinc benzoate. Its usage is
The amount is usually 1 to 1000 ppm, preferably 5 to 500 ppm, based on the amount of the product. In this reaction, a solvent may or may not be used. When a solvent is used, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, and ketones such as methyl isobutyl ketone and methyl ethyl ketone are preferred.

The compound having at least one active hydrogen group which reacts with an epoxy group in the molecule, which is used as the main raw material (E) of the resin of the present invention, is a monovalent phenol, a secondary amine or a monovalent phenol. Carboxylic acids. Examples of the monovalent phenol include phenol, cresol, isopropylphenol, octylphenol, nonylphenol, dodecylphenol, xylenol, P-cumylphenol, α-naphthol, β-naphthol, and the like. Examples of the secondary amines include aliphatic amines such as diethylamine, dipropylamine, dibutylamine, dipentylamine, didodecylamine, distearylamine, diethanolamine, diallylamine, N-methylaniline, N-methyltoluidine, N-
Aromatic ring-containing secondary amines such as methylnitroaniline, diphenylamine, ditolylamine, and benzyldimethylamine are exemplified. Examples of the monovalent carboxylic acids include, for example, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, aliphatic carboxylic acids such as stearic acid, benzoic acid, toluic acid, α-naphthoic acid, β-naphthoic acid,
An aromatic ring-containing monocarboxylic acid such as phenylacetic acid can be used.

Further, in the production of the resin of the present invention, it is necessary to react (A) and (B) with at least one selected from (C) and (D) and (E). Accordingly, a crosslinking agent (F) may be used. Examples of the crosslinking agent (F) include polyamines such as aromatic polyamines and aliphatic polyamines, acid anhydrides, trivalent or higher phenol compounds, and trivalent or higher epoxy resins. Examples of the polyamines include diethylenetriamine, triethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, trimethylhexamethylenediamine, diethylaminopropylamine, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like. Is mentioned.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Acid, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic acid Anhydrous,
Examples thereof include an alkylstyrene-maleic anhydride copolymer, chlorendic anhydride, and polyazelain anhydride.
Examples of the trivalent or higher phenol compound include phenol novolak resin, orthocresol novolak resin, 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,3-tris (2-methyl-4-hydroxy -5-tert-butylphenyl) propane, 1,
1,3-tris (2-methyl-4-hydroxy-5-t
tert-butylphenyl) butane, 1- [α-methyl-
α- (4-hydroxyphenyl) ethyl] -3- [α,
α-bis (4-hydroxyphenyl) ethyl] benzene and 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene be able to.

The trivalent or higher epoxy resin is a glycidyl compound obtained by reacting a trivalent or higher phenol compound or a trivalent or higher alcohol compound with epihalohydrin. Examples of the trivalent or higher phenol compound include phenol novolak resin, orthocresol novolak resin, 1,1,1-tris (4-hydroxyphenylmethane, 1,1,3-tris (2-methyl-4-hydroxy- 5-tert-butylphenyl) propane, 1,
1,3-tris (2-methyl-4-hydroxy-5-t
tert-butylphenyl) butane, 1- [α-methyl-
α- (4-hydroxyphenyl) ethyl] -3- [α,
α-bis (4-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene and the like No. Examples of the trihydric or higher alcohol include 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, glycerol,
2-methylpropanetriol, 2-methyl-1,2,2
4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, and the like.

In the production of the resin of the present invention, the main raw material (A)
And (B), and at least one selected from raw materials (C) and (D), and a compound (E) having at least one active hydrogen group in the molecule that reacts with an epoxy group;
Further, if necessary, the reaction can be carried out by a polyaddition reaction with a crosslinking agent (F). In this reaction, it is preferable that the usage ratio of each raw material satisfies the following formulas (1) to (8). A: Weight of bisphenol N _5A : Active hydrogen equivalent of bisphenol B ₁ : Weight of low molecular weight bisphenol type epoxy resin N _B1 : Epoxy equivalent of low molecular weight bisphenol type epoxy resin B ₂ : Weight of high molecular weight bisphenol type epoxy resin N _B2 : Epoxy equivalent of high molecular weight bisphenol-type epoxy resin C: Weight of polyhydric alcohol N _C : Active hydrogen equivalent of polyhydric alcohol D: Amount of acid anhydride used for reaction with polyhydric alcohol N _D : Molecular weight of acid anhydride E: Amount of compound having one active hydrogen in the molecule that reacts with the epoxy group _NE : Molecular weight of compound having one active hydrogen in the molecule that reacts with the epoxy group F: Weight of crosslinking agent _NF : Activity of crosslinking agent Hydrogen equivalent, epoxy equivalent (molecular weight for acid anhydride)

[0021]

(Equation 2) Here, elongation of the molecular chain means being incorporated into the main chain of the polyol resin, and molecular chain blocking means being incorporated into the terminal of the main chain. The low-molecular-weight bisphenol-type epoxy resin has an average molecular weight of 300 to
3000 epoxy resin, and high molecular weight bisphenol type epoxy resin means an average molecular weight of 3,000 to 100.
00 means an epoxy resin. The epoxy equivalent of the epoxy resin is about half of the average molecular weight of the epoxy resin.

In the production of the resin of the present invention, this polyaddition reaction is usually carried out using a catalyst. Examples of the catalyst used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal alcoholates such as sodium methylate, N, N
Tertiary amines such as dimethylbenzylamine, triethylamine and pyridine, and quaternary amines such as tetramethylammonium chloride and benzyltriethylammonium chloride;
Examples thereof include organic ammonium compounds such as quaternary ammonium salts, triphenylphosphine and triethylphosphine; alkali metal salts such as lithium chloride and lithium bromide; and Lewis acids such as boron trifluoride, aluminum chloride and tin tetrachloride. . When a catalyst is used in the production of the resin of the present invention, the amount used is usually 1 to the amount of the product.
To 1000 ppm, preferably 5 to 500 ppm.

In the polyaddition reaction in the production of the resin of the present invention, a solvent can be used in combination. Suitable solvents include aromatic compounds such as xylene and toluene;
-Butane, methyl isobutyl ketone, ketones such as cyclohexanone, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethers such as anisole,
Aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, 1-methyl-2-pyrrolidinone and the like can be exemplified. These solvents can be used alone or in combination of two or more. When a solvent is used, the amount used is usually 1 to 100% by weight, preferably 5 to 50% by weight, based on the weight of the raw materials.

The reaction temperature in this polyaddition reaction is usually in the range of 120 to 180 ° C., although it depends on the amount of the catalyst.
In addition, the reaction can be generally followed by measuring the epoxy equivalent, the phenolic hydroxyl group content, the softening point, and the number average molecular weight by GPC, but in the present invention, the epoxy group is substantially eliminated. The time when the reaction was completed, that is, the time when the epoxy equivalent became 20,000 (g / equivalent) or more was defined as the reaction end point.

The resin of the present invention thus obtained is
Usually, the number average molecular weight (Mn) is preferably in the range of 1,000 to 10,000, particularly preferably 2500 to 50.
00 range. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mw / Mn) is preferably from 5 to 50, and particularly preferably from 10 to 35. The softening point is preferably from 85 to 150 ° C, particularly preferably from 100 to 135 ° C. Furthermore, Tg
Is preferably 50 ° C to 90 ° C, particularly 55 to 70 ° C
Are preferred in terms of ensuring low-temperature fixability, offset resistance and blocking resistance. Further, the resin of the present invention generally has a hydroxyl value of 100 to 200 KOHmg / g, preferably 120 to 200 KOHmg / g.

The present invention also provides an electrophotographic toner containing the polyol resin as a main component (hereinafter, referred to as “toner of the present invention”). The toner of the present invention contains the polyol resin as a main component, if necessary,
The toner contains various components such as a colorant, a magnetic powder, and a binder resin, which are blended in this type of electrophotographic toner.

The colorant compounded in the toner of the present invention may be a colorant commonly used in this type of electrophotographic toner, and is appropriately selected according to a desired color, compatibility with a binder resin, and the like.
There is no particular limitation. For example, in the case of preparing a black electrophotographic toner, a conventionally known black colorant can be used. Specific examples of the black colorant include pigments such as carbon black and grafted carbon black whose surface is chemically treated. When preparing electrophotographic toners other than black, for example, electrophotographic toners of three primary colors, yellow, magenta and cyan, conventionally known colorants can be used, and there is no particular limitation. For example, as a colorant used when preparing a yellow electrophotographic developer toner, chrome yellow, quinoline yellow and the like can be mentioned. Further, as a colorant used for preparing a magenta electrophotographic toner, for example, Dupont Oil Red, Rose Bengal and the like can be mentioned. Further, as a colorant used when preparing a cyan electrophotographic developer toner, for example, aniline blue, methylene blue chloride, and phthalocyanine blue can be mentioned.

The amount of the colorant in the toner of the present invention is usually about 0.01 to 20% by weight, preferably about 1 to 10% by weight, based on the total amount of the toner. When the toner of the present invention is used as a magnetic toner as a one-component developer, a magnetic powder is blended. Examples of the magnetic powder to be used include those composed of metals such as iron oxide such as ferrite and magnetite, iron, cobalt and nickel, and these may be used alone or in combination of two or more. The magnetic powder is preferably a fine powder having a particle size of 1 μm or less. When the toner of the present invention is a magnetic toner containing magnetic powder, the compounding ratio is usually 30 parts by weight to 100 parts by weight of the binder resin.
The amount is about 300 to 300 parts by weight, preferably 50 to 200 parts by weight.

Further, in the toner of the present invention, various compounding agents commonly used in conventional electrophotographic toners may be added, if necessary, in addition to the binder resin, the colorant, or the magnetic powder. it can. For example, a styrene acrylic resin, a polyester resin, an epoxy resin, or the like, which is commonly used as a binder resin, can be blended. If necessary, a charge controlling agent, a plasticizer, a low-molecular-weight polypropylene, a low-molecular-weight polyethylene, a paraffin wax, an amide wax, a release agent such as silicone oil, a fluidity improver such as silica, and the like can be blended. .

The toner of the present invention generally has an average particle size of 3 to 2
It is provided for use in the form of particles of 0 μm, preferably 5 to 15 μm. When the toner of the present invention is used as a binder resin, a pigment or a dye as a colorant, and a magnetic toner as a one-component developer, a magnetic powder and, if necessary, a charge adjusting agent and other additives. After thoroughly mixing the ingredients and the like with a mixer such as a Henschel mixer and a ball mill,
Melt mixing is performed using a heating mixer such as a heating roll, a kneader, an extruder or the like. Next, after cooling and solidifying, it can be manufactured by pulverization and classification using a jet mill or the like.

[0031]

EXAMPLES Hereinafter, Examples and Comparative Examples of the present invention will be described.
The present invention will be described more specifically, but the present invention is not limited by these examples. The epoxy equivalent, the number average molecular weight (Mn) and the weight average molecular weight (Mw) by GPC, the glass transition point, the softening point, the fixing property and the blocking resistance in Examples and Comparative Examples are as follows:
It was measured or evaluated according to the following method.

1) Epoxy equivalent 0.2 to 5 g of a resin sample is precisely weighed and placed in a 200 ml Erlenmeyer flask, and 25 ml of dioxane is added and dissolved. 25 ml of 1 / 5N hydrochloric acid solution (dioxane solvent)
, And tightly stoppered. After thoroughly mixing, the mixture is allowed to stand for 30 minutes. Next, a toluene-ethanol mixed solution (1: 1 volume ratio) 5
After adding 0 ml, use cresol red as an indicator and add 1 ml.
Titrate with a / 10 N aqueous sodium hydroxide solution. Epoxy equivalent (g / equivalent) according to the following formula based on the titration result
Is calculated. Epoxy equivalent (g / equivalent) = 1000 × W / [(B−
S) × N × F] W: Sampling amount (g) B: Amount of sodium hydroxide aqueous solution (m
l) S: Amount of normal sodium hydroxide aqueous solution required for test of sample (ml) N: Normality of sodium hydroxide aqueous solution F: Potency of sodium hydroxide aqueous solution

2) Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) by GPC A resin solution was prepared by dissolving 80 mg of a resin sample in 10 ml of THF, and 100 μl of the sample solution was injected into a column. The retention time is measured with. The retention time was measured using polystyrene having a known average molecular weight as a standard substance, and the number average molecular weight of the resin sample was determined in terms of polystyrene from a calibration curve prepared in advance. -Column: Guard column + GLR400M + GLR400M + GLR400 (all manufactured by Hitachi, Ltd.)-Column temperature: 40 ° C-Mobile phase (flow rate): THF (1 ml / min)-Peak detection method: UV (254 nm)

3) Glass transition temperature (Tg): measured using the following differential scanning calorimeter under the following conditions.・ Differential scanning calorimeter: SEIKO1 DSC100 SEIKO1SSC5040 (Disk Station) ・ Measurement conditions: Temperature range: 25 to 150 ° C. Heating rate: 10 ° C./min Sampling time: 0.5 sec Sample amount: 10 mg

4) Softening point: The softening point of the sample was measured at a heating rate of 1 ° C./min using a softening point measuring device (FP90, manufactured by METTLER CORPORATION). 5) Measurement of hydroxyl value (a) 1.5 to 2.0 g of the resin was precisely weighed and placed in a 25 ml volumetric flask, and purified chloroform from which ethanol and water had been removed with a molecular sieve 4A was added and dissolved. After completely dissolving the resin, purified chloroform was added, and the volume was adjusted to the mark of 25 ml to prepare a sample solution. (B) The sample solution was transferred to a KBr liquid cell (thickness: 0.2 mm)
And purified chloroform at 4000 cm ^-1 as a control.
The absorption spectrum in the wave number region of の 3000 cm ⁻¹ was measured.

(C) Absorbance T of two appearing absorption peaks
₁ and T ₂ were determined absorbance as a base as a reference (zero). Next, from the value of T ₁ + T ₂ , the hydroxyl group concentration (eq / l) was determined from a previously prepared calibration curve, and the hydroxyl value was converted according to the following equation. Hydroxyl value (KOHmg / g) = (hydroxyl concentration / 4) x 56.1 x F /
[Sample weight (g)] × 100 F: Thickness correction of KBr cell F = L ₁ / L ₂ L ₁ : Thickness (mm) of cell when preparing calibration curve L ₂ : Thickness of cell used in measurement (Mm)

Preparation of calibration curve (a) Molecular sieve 4 was placed in six 25 ml flasks.
0.1 g of purified diethylene glycol dehydrated in A
After collecting 0.2, 0.3, 0.4, 0.5 and 0.6 g, respectively, 6 standard solutions were prepared by making up to the marked line with purified chloroform. These standard solutions were 0.075, 0.151, 0.226, and 0.30, respectively.
Standard solutions with hydroxyl equivalents of 1, 0.376 and 0.452 eq / l. (B) The KBr liquid cell (thickness:
0.2 mm) to measure an absorption spectrum in a wave number region of 4000 to 3000 cm ^-1 . Appear two absorbance T ₁ and T ₂ of the absorption peaks calculated absorbance as a base as a reference (zero), by plotting the relationship between the value and the hydroxyl equivalent of T ₁ + T _2, the calibration curve. 6) Fixing test The surface temperature of the fixing heat roller was adjusted to 100 to 200 by using a copying test machine modified so that the surface temperature of the fixing heat roller of an electrophotographic copying machine (Fuji Xerox 3500) manufactured by Fuji Xerox Co., Ltd. could be changed. Copying was performed with the above-mentioned developer while changing the temperature in the range of ° C. The density change of the copy image when the obtained copy image was rubbed with the eraser was visually observed. The surface temperature of the heat roller for fixing was raised from 110 ° C. in steps of 5 ° C., and the temperature when the fixing rate exceeded 85% was defined as the minimum fixing temperature. The temperature was further increased to perform a test, and the temperature at which the toner began to adhere to the heat roller was defined as the offset start temperature.

7) Blocking resistance 10 g of the toner was placed in a 70 ml glass sample bottle, and left in a constant temperature and humidity chamber at 60 ° C. and a relative humidity of 35% for 3 hours. After cooling to room temperature, the degree of aggregation was observed and evaluated according to the following criteria. A: The toner drops when the sample bottle is turned upside down. B: The toner drops when the sample bottle is turned upside down and shakes lightly. C: The sample bottle is turned upside down, and the toner drops when the tap is tapped. D: The sample bottle is turned upside down. When strong vibration is applied, toner drops E: When the sample bottle is turned upside down and strong vibration is applied, toner does not drop

(Example 1) Polyoxypropylene- (1,1) -2,2 was placed in a 500-ml separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a reflux tube.
-Bis (4-hydroxyphenyl) propane (manufactured by Mitsui Toatsu Chemicals, KB-280, OH value: 291 KOHmg /
g) 33.9 g, 26.1 g of phthalic anhydride, and 15 g of xylene were charged and stirred at an internal temperature of 80 ° C. until the system became homogeneous. Next, 30 mg of benzyldimethylamine (BDMA) was added as a catalyst, and the temperature was increased to 130 ° C.
Allowed to react for hours.

After cooling the reaction mixture to 50 ° C. or less, 41.3 g of bisphenol A, 127.6 g of bisphenol A type liquid epoxy resin (Epomic R140P, manufactured by Mitsui Petrochemical Co., epoxy equivalent 188 g / eq), bisphenol A type solid epoxy resin (Mitsubishi Petrochemical Co., Ltd., Epomic R309, epoxy equivalent 2750 g / eq) 48
g, benzoic acid 19.7 g, and stearic acid 3.5 g
Was added, and 0.12 g of a 50% aqueous solution of tetramethylammonium chloride was added at 80 ° C. After reacting at 160 ° C. for 1 hour, the reflux tube was replaced with a vacuum distillation apparatus, and xylene and water were distilled off while gradually increasing the degree of vacuum. After one hour, the degree of reduced pressure reached 1333 Pa (10 mmHg). One more
After stirring for an hour, the pressure in the reaction system was returned to normal pressure, and stirring was continued for 7 hours. At this time, the produced polyol resin was sampled, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20,000 or more, the produced polyol resin was extracted from the flask.

The softening point of the obtained polyol resin is 124
° C, glass transition temperature: 59 ° C, number average molecular weight (Mn):
3400, weight average molecular weight (Mw): 75000, ratio (Mw) between weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn) is 22, and the hydroxyl value is 158 (KOHmg / g).
Met. Hereinafter, this polyol resin is referred to as (P-1). Here, for each charged raw material, the above (1) to
When the value of equation (6) was obtained, 3200 was obtained in equation (1),
0.98 in equation (2), 0.16 in equation (3), (4)
The formula was calculated to be 0.20 and the formula (6) was calculated to be 0, and it was confirmed that each of the formulas (1) to (6) was satisfied.

Example 2 In Example 1, the raw materials used were 46.1 g of bisphenol A, 133.7 g of bisphenol A type liquid epoxy resin, and bisphenol A type solid epoxy resin (epoxy equivalent = 2640 g / eq).
Was changed to 40.5 g, benzoic acid to 19.7 g and stearic acid to 0 g, and the reaction was carried out in the same manner as in Example 1 to produce a polyol resin.

The softening point of the obtained polyol resin is 121.
° C, glass transition temperature: 60 ° C, number average molecular weight (Mn):
3350, weight average molecular weight (Mw): 54800, ratio (Mw) between weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn) is 16.4, and the hydroxyl value is 159 (KOHmg /
g). Hereinafter, this polyol resin is referred to as (P-2)
That. Here, for each charged raw material, the above (1) to
When the value of the equation (6) was obtained, it was found that the equation (3)
0.98 in equation (2), 0.135 in equation (3),
The value was calculated to be 0.20 in the expression (4) and 0 in the expression (6), and it was confirmed that the expressions (1) to (6) were satisfied.

Example 3 In Example 1, the amounts of the starting materials used were 51 g of bisphenol A, 150.5 g of bisphenol A type liquid epoxy resin, 0 g of bisphenol A type solid epoxy resin, benzoic acid and stearic acid.
-Reaction was carried out in the same manner as in Example 1 except that 6.6 g of phthalic anhydride was added instead of 31.9 g of cumylphenol, to produce a polyol resin.

The softening point of the obtained polyol resin is 123
° C, glass transition temperature: 63 ° C, number average molecular weight (Mn):
4100, weight average molecular weight (Mw): 71000, ratio (Mw) between weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn) is 17.3, and the hydroxyl value is 141 (KOHmg /
g). Hereinafter, this polyol resin is referred to as (P-3)
That. Here, for each charged raw material, the above (1) to
When the value of the equation (6) was obtained, 3600 was obtained in the equation (1), and
Equation (2) is calculated as 0.98, Equation (3) is calculated as 0, Equation (4) is calculated as 0.20, and Equation (6) is calculated as 0.022.
It was confirmed that each of the expressions (1) to (6) was satisfied.

Example 4 In Example 1, the amounts of the raw materials used were 17.0 g of polyoxypropylene (1,1) -2,2-bis (4-hydroxyphenyl) propane, 13 g of phthalic anhydride, 48.8 g of bisphenol A,
150.8 g of bisphenol A type liquid epoxy resin,
29.9 g of benzoic acid, 0 g of stearic acid, bisphenol A type solid epoxy resin (epoxy equivalent = 2640)
g / eq) to 30 g, and further add phthalic anhydride to 10.5 g.
Except for adding g, the reaction was carried out in the same manner as in Example 1 to produce a polyol resin.

The softening point of the obtained polyol resin is 125
° C, glass transition temperature: 60 ° C, number average molecular weight (Mn):
2500, weight average molecular weight (Mw): 59300, ratio (Mw) between weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn) is 20.6 and the hydroxyl value is 156 (KOHmg /
g). Hereinafter, this polyol resin is referred to as (P-4)
That. Here, for each charged raw material, the above (1) to
When the value of equation (6) was obtained, 2300 was obtained from equation (1).
0.98 in equation (2), 0.10 in equation (3), (4)
The formula was calculated to be 0.10, and the formula (6) was calculated to be 0.035, which confirmed that the equations (1) to (6) were satisfied.

Example 5 A 500-ml separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a distillation condenser, and a receiver was charged with a bisphenol A liquid epoxy resin (Epomic, manufactured by Mitsui Petrochemical Co., Ltd.). R140P, epoxy equivalent: 188 (g / eq)) 139.0 g, bisphenol A type solid epoxy resin (manufactured by Mitsui Petrochemical Co., Ltd.)
Epomic R309, epoxy equivalent: 2640 (g / e
q)) 30.0 g, bisphenol A 39.6 g, polyoxypropylene (1,1) -2,2-bis (4-hydroxyphenyl) propane (manufactured by Mitsui Toatsu Chemicals, KB-
280, OH number: 291 KOHmg / g)) 15.0
g, 67.4 g of P-cumylphenol, 9.0 g of phthalic anhydride and 30 g of xylene were charged, and the temperature was raised under a nitrogen atmosphere, and the mixture was uniformly dissolved at an internal temperature of 80 ° C. Next, a 10% aqueous solution of sodium hydroxide was used as a reaction catalyst.
0 g was added. When the internal temperature reached 180 ° C., the xylene was concentrated under reduced pressure to about 0.5
The pressure was reduced to 1333 Pa over time. After stirring for 1 hour under reduced pressure, the pressure of the reaction system was returned to normal pressure, and the reaction was continued for 7 hours while maintaining the reaction temperature at 180 ° C. At this time, when the residual amount of the epoxy group was measured, the epoxy equivalent was 20,000 (g / equivalent) or more. Since it was confirmed that the epoxy group had substantially disappeared, the produced polyol resin in a molten state was extracted from the flask.

The softening point of the obtained polyol resin is 116
° C, glass transition temperature: 59 ° C, number average molecular weight (Mn):
2600, weight average molecular weight (Mw): 45800, ratio (Mw) between weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn) is 17.6, and the hydroxyl value is 146 (KOHmg /
g). Hereinafter, this polyol resin is referred to as (P-5)
That. Here, for each charged raw material, the above (1) to
When the value of Expression (6) was obtained, 1800 was obtained in Expression (1), and
Equation (2) is calculated as 0.98, Equation (3) is calculated as 0.1, Equation (4) is calculated as 0.05, and Equation (6) is calculated as 0.03. It was confirmed that they were satisfied.

Comparative Example 1 450.1 g of dimethyl terephthalate was placed in a 1-liter separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a distillation condenser and a receiver.
13.9 g of dimethyl phthalate, 400 g of propylene glycol, and 0.18 g of tin oxalate were charged.
The temperature was raised to 0 ° C. After the distillation of methanol was started, the temperature was gradually raised, and 160 g of methanol was distilled off at 200 ° C.
Transesterification was completed. Next, while maintaining the temperature in the reaction system at 210 ° C. and the pressure at 1333 Pa, while distilling off propylene glycol, the polymerization reaction was continued for 5 hours. Furthermore, after adding 17.2 g of phthalic anhydride, the reaction was further performed for 3 hours, and the formed resin was taken out of the flask. The softening point of the obtained polyester resin is 121 ° C,
Glass transition temperature: 68 ° C, number average molecular weight (Mn): 33
00, weight average molecular weight (Mw): 7800, Mw / M
n: 2.4.

Example 6 In Example 1, 45.2 g of polyoxypropylene- (1,1) -2,2-bis (4-hydroxyphenyl) propane was used,
34.8 g of phthalic anhydride and 15 of bisphenol A
5.3 g, 34 parts of biphenol A type liquid epoxy resin
2.8 g, 12 parts of bisphenol A type solid epoxy resin
0 g, benzoic acid to 69.9 g, stearic acid was not used, and trifunctional epoxy resin (Mitsui Chemicals Co., Ltd.)
Manufactured by Techmore VG-3101, epoxy equivalent: 210 g
(Eq) was added, and a polyol resin was produced in the same manner as in Example 1 except that 32.0 g was added. The obtained polyester resin has a softening point of 120 ° C, a glass transition temperature of 64 ° C,
Number average molecular weight (Mn): 2860, weight average molecular weight (M
w): 46600, Mw / Mn: 16.3, hydroxyl value:
167 (KOHmg / g). Here, the values of the above formulas (3) to (8) were determined for each of the charged raw materials, and were found to be 0.15 in the formula (3), 0.10 in the formula (4),
It is calculated as 0.04 in the equation (6), 2600 in the equation (7), and 0.98 in the equation (8), and it is confirmed that the equations (3) to (8) are satisfied. Was.

Example 7 180 g of the polyol resin (P-1) obtained in Example 1, 12 g of carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation), polypropylene wax (Viscol 660P, manufactured by Sanyo Chemical Co., Ltd.) ) 4 g and Spiron Black TRH (manufactured by Hodogaya Chemical Co., Ltd.) 4 g
After mixing with a super mixer, the mixture was melt-kneaded with two rolls. After cooling, the obtained mixture was pulverized by a jet mill and further classified by a dry air classifier to obtain an average particle size of 10 μm.
A polyol resin powder composed of particles of the above was obtained. Next, hydrophobic silica (R972, manufactured by Nippon Aerosil Co., Ltd.) was mixed at a ratio of 0.4 wt% of the total amount, and the mixture was stirred twice in a Henschel mixer for 30 seconds to obtain an electrophotographic toner.
The blocking resistance of the electrophotographic toner was evaluated. A developer was prepared by uniformly mixing 5 g of the obtained electrophotographic toner and 95 g of an iron powder carrier (average particle size: 60 to 100 μm), and a fixing test was performed using the developer. Table 1 shows the results.

Examples 8 to 12 In each of the examples, the polyol resin (P-2) was used instead of the polyol resin (P-1).
A toner for electrophotography was produced in the same manner as in Example 7 except that the toners Nos. To 7 were used. The obtained toner was evaluated for blocking resistance and fixability. Table 1 shows the results.

Comparative Example 2 A toner was produced in the same manner as in Example 7 except that the polyester resin synthesized in Comparative Example 1 was used instead of the polyol resin (P-1). The sex was evaluated. Table 1 shows the results.

[0055]

[0056]

The polyol resin of the present invention, which is used as a main component of an electrophotographic toner, has excellent fixing properties at low temperatures, excellent anti-offset properties at high temperatures, and excellent blocking resistance. Thus, it is possible to provide a toner suitable as an electrophotographic developer that does not block even if it is blocked. Further, the electrophotographic toner of the present invention is suitable as an electrophotographic toner because it has excellent fixability at low temperatures, offset resistance at high temperatures, and blocking resistance.

Claims (7)

[Claims] (1) The following general formula (a): (Wherein R ¹ and R ² may be the same or different and are a hydrogen atom, a methyl group, an ethyl group or a phenyl group) and a bisphenol (A) represented by the following general formula (b): (R ³ and R ⁴ may be the same or different and each is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, and n is an integer of 0 or more). Compound (E) having at least one selected from a polyhydric alcohol (C) and a reactant (D) of the polyhydric alcohol and an acid anhydride, and at least one active hydrogen group in the molecule that reacts with an epoxy group And a polyol resin. 2. The polyhydric alcohol (C) has the following general formula (c): (Wherein R ⁵ and R ⁶ may be the same or different,
An ethylene group or a propylene group, p and q are 1
The polyol resin according to claim 1, wherein the polyol resin is an alkylene oxide adduct of a dihydric phenol represented by the following integer: p + q is from 2 to 10. 3. A softening point of 85 to 150 ° C. and a Tg of 50 to 9
0 ° C., number average molecular weight (Mn) of 1,000 to 10,000,
And the ratio of weight average molecular weight / number average molecular weight (Mw / Mn)
The polyol resin according to claim 1, wherein is 5 to 50. 4. The bisphenol type epoxy resin (B)
Is a mixture of two or more bisphenol type epoxy resins having different number average molecular weights. 5. The polyol resin according to claim 1, wherein the reaction is further performed using a crosslinking agent (F). 6. The bisphenols (A), the bisphenol type epoxy resin (B), the polyhydric alcohol (C),
The reactant (D), compound (E), and cross-linking agent (F) of the polyhydric alcohol and the acid anhydride were converted into the following formula: A: weight of bisphenol N _5A : active hydrogen equivalent of bisphenol B ₁ : low Weight of molecular weight bisphenol type epoxy resin N _B1 : Epoxy equivalent of low molecular weight bisphenol type epoxy resin B ₂ : Weight of high molecular weight bisphenol type epoxy resin N _B2 : Epoxy equivalent of high molecular weight bisphenol type epoxy resin C: Weight of polyhydric alcohol N _C: polyhydric alcohols active hydrogen equivalent D: the amount of a compound having one active hydrogen in a molecule that reacts with the epoxy group: multi amount valence anhydride used for the reaction with the alcohol N _D: molecular weight of the acid anhydride E N _E: molecular weight of the compound having one active hydrogen in its molecule to react with the epoxy group F: weight of crosslinking agent N _F: active hydrogen equivalent of crosslinking agent, Epoxy equivalent (molecular weight in the case of acid anhydride) Equation 1] The polyol resin according to any one of claims 1 to 5, which is reacted at a ratio satisfying the following. 7. An electrophotographic toner comprising the polyol resin according to claim 1 as a main component.