JP2675830B2 - Polyester resin for toner, manufacturing method thereof, and toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a polyester resin for toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc., and a method for producing the same. And a color toner.

(Background technology)

Conventionally, as the electrophotographic method, a large number of methods are known, as described in U.S. Pat.No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, but generally, A photoconductive substance is used to form an electrical latent image on the photoconductor by various means, and then the latent image is developed with toner, and the toner image is transferred to a transfer material such as paper as necessary. After that, it is fixed by heating, pressure or solvent vapor to obtain a copy.

Various methods and apparatuses have been developed for the final step of fixing the toner image to a sheet such as paper. Currently, the most common method is a pressure heating method using a heating roller.

The pressure-bonding heating method using a heating roller performs fixing by allowing the toner image surface of the sheet to be fixed to pass under pressure while contacting the surface of the heating roller whose surface is formed of a material having releasability for toner. . In this method, since the surface of the heating roller and the toner image on the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and the fixing can be performed quickly. Very effective in high speed electrophotographic copying machines. However, in the above method, since the surface of the heating roller and the toner image are in contact with each other in a molten state under pressure, a part of the toner image adheres to and transfers to the surface of the fixing roller and retransfers to the next sheet to be fixed. A so-called offset phenomenon may occur and the sheet to be fixed may be soiled. Preventing toner from adhering to the surface of the heat fixing roller is one of the essential conditions of the heat roller fixing method.

In other words, under the present circumstances, it is desired to develop a binder resin for toner having a wide fixing temperature range and high offset resistance.

Further, studies and practical use of two-color color copying machines and full-color copying machines have been made. For example, "Journal of the Electrophotographic Society" Vol22, No1 (1983) and "Journal of the Electrophotographic Society" Vol25, No
There are also reports of color reproducibility and gradation reproducibility as described in 1, P52 (1986).

However, it is not immediately compared to the real thing like TV, photographs and color prints, and for those who can see the color image that is more beautifully processed than the real thing, the full-color electrophotographic image currently in practical use is not always necessary. It is not satisfactory.

In full-color electrophotography, multiple developments are performed, and several types of toner layers of different colors are required to be superimposed on the same support. Includes the following items.

(1) In order that the fixed toner does not diffusely reflect light and hinder color reproduction, the toner needs to be in a state of almost complete melting such that the shape of the toner particles cannot be determined.

(2) It must be a binder resin having transparency that does not interfere with the toner layers of different colors under the toner layer.

Thus, for toners for mono-color copiers, development of a binder resin for toners with a wide fixing temperature range and high offset resistance is expected, and not only for the full-color copiers, the fixing temperature range is wide, but also the transparency of the resin. It is required that the fixing surface becomes flat when fixed.

Conventionally, for the purpose of expanding the fixing temperature range of a polyester resin, an offset preventing agent is used in JP-A-57-208559, JP-A-58-11954, and JP-A-59-228661. For use as a toner, the transparency of the toner tends to be insufficient, and Japanese Patent Publication No. 59-11902 and Japanese Unexamined Patent Publication No.
JP-A 0-214368 describes a polyester resin using a polycarboxylic acid, but when these resins are used, the smoothness of the fixing surface of the toner is likely to be lost. That is, it is not easy to expand the fixing temperature range of the toner and simultaneously satisfy the transparency of the toner and the smoothness of the fixing surface after fixing.

[Object of the invention]

An object of the present invention is to provide a novel resin for an electrostatic charge image developing toner which solves these problems and a method for producing the same.

An object of the present invention is to provide a resin for toner which is used in a heat roller fixing method having good fixability and particularly good offset resistance, and a method for producing the same.

It is an object of the present invention to provide a resin for producing a heat roller fixing toner which has excellent fluidity, does not cause aggregation, and has excellent impact resistance, and a method for producing the same.

Further, an object of the present invention is to provide a resin for producing a heat roller fixing toner which has good chargeability and always shows stable chargeability during use, and which can obtain a clear and fog-free image, and a method for producing the same. To provide.

An object of the present invention is to provide a toner resin capable of forming a smooth fixing surface so that the fixed toner diffusely reflects light when used as a full-color toner resin and does not interfere with color reproduction. And to provide a manufacturing method thereof.

An object of the present invention is to provide a resin having transparency and a method for producing the same when used as a resin for a full-color toner so as not to interfere with toner layers having different color tones under the toner layer.

[Summary of the Invention]

Specifically, the present invention is a polyester resin produced from a polyhydric alcohol component and a polycarboxylic acid component, the value of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyester is 20 or less. And the glass transition temperature (Tg) of the polyester resin and the weight average molecular weight (Mw) satisfy the following relationship: 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻⁴ × Mw + 47 Glass transition temperature (Tg)
And the softening temperature (Sp) measured by the flow tester have the following relationship The present invention relates to a polyester resin for toner and a toner containing the resin.

Furthermore, the present invention is a polycondensation of an unsaturated polycarboxylic acid component having an unsaturated double bond group, a saturated polycarboxylic acid component having no unsaturated double bond and a polyhydric alcohol component, a weight average molecular weight (Mw) is 200,000 or less (preferably 10,000 to 150,000) and the number average molecular weight (Mn) is 1,0
A polyester resin having a glass transition temperature of 45 to 75 ° C and a glass transition temperature of 00 or more (preferably 3000 to 10000) is produced, and the unsaturated double bond group contained in the produced polyester resin is reacted to form a polyester having a three-dimensional structure. The relationship between the glass transition temperature (Tg) and the weight average molecular weight (Mw) of the polyester resin having a three-dimensional structure imparted to the resin is as follows: 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻ The glass transition temperature (Tg) of a polyester resin that satisfies ⁴ × Mw + 47 and has a three-dimensional structure, and the softening temperature (Sp) measured by a flow tester have the following relationship. The present invention relates to a method for producing a polyester resin for toner, which comprises producing a polyester resin satisfying the above conditions.

[Specific description of the invention]

Its characteristic is that in a polyester resin with a relatively molecular weight distribution of Mw / Mn of 20 or less, which is synthesized from a polyhydric alcohol component and a polycarboxylic acid component, Tg
And Mw and Tg and the softening temperature Sp by the flow tester are expressed by the following equations (1) and (2) 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻⁴ × Mw + 47 (1) In the polyester resin used in the toner for dry electrophotography satisfying the above conditions, especially Tg and Mw and Tg and the softening temperature by the flow tester are the following formulas (3) and (4) 9 × 10 ⁻⁴ × Mw + 36 ≦ Tg ≦ 9 × 10 ^-4 × Mw ＋ 43.5 …… (3) Those satisfying the above are preferable in terms of powder characteristics, fixing characteristics and image characteristics.

A further feature of the present invention is that a polycarboxylic acid having an unsaturated double bond and a polycarboxylic acid having no unsaturated double bond and a polyhydric alcohol are subjected to copolycondensation to obtain a weight average molecular weight. (Mw) 200,000 or less, number average molecular weight (Mn) 1,000 or more, glass transition temperature 45 ~ 75 ℃ to produce a polyester resin, the unsaturated double bond portion of the polymer by a peroxide or radical polymerization initiator. Cross-link or
Alternatively, by using a peroxide or a radical polymerization initiator and a radically polymerizable monomer to crosslink them to have a three-dimensional structure, the glass transition temperature (T
g), weight average molecular weight (Mw) and softening temperature (Sp) measured by a flow tester are 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻⁴ × Mw + 47 And a method for producing a polyester resin for an electrophotographic toner, which satisfies the above condition.

Conventionally, Mw / Mn used as a resin for dry electrophotographic toner has a relatively sharp molecular weight distribution of 20 or less, and Tg and Mw, and Tg and the softening temperature Sp by a flow tester are respectively 9 x 10 ^-4 x Mw + 47 <Tg <9 x 10 ^-4 x Mw + 55 (5) There is a relationship shown by the equations (5) and (6).

As a result of diligent research, the present inventors have found that it is possible to crosslink the unsaturated portion of the unsaturated polyester resin with a peroxide or a radical polymerization initiator, and to use a radical polymerization initiator and a radical polymerizable monomer. It is possible to crosslink the unsaturated part of the unsaturated polyester resin by using, and further, by crosslinking in this way to give a three-dimensional structure, the above formulas (1) and (2) It is possible to produce a polyester resin satisfying the range shown.

Further, the electrophotographic toner prepared using the resin is
Compared with conventional electrophotographic toners, it is superior in fixing characteristics and image characteristics.

In the polyester resin used in the present invention, preferably 45 to 55 mol% of the polyester resin component is an acid component and 55 to 45 mol is an alcohol component. As the polyhydric alcohol component as the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1 , 5-Pentanediol, 1,6-hexanediol, neopentyl glycol, pentaerythritol diallyl ether, trimethylene glycol, 2-
Ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivative represented by the following formula, (Wherein R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2
~ 10. ) And other diols, and polyhydric alcohols such as glycerin, sorbit, and sorbitan.

Further, it is preferable that 50 mol% or more of the divalent unsaturated carboxylic acid component is contained in all the acid components. Examples of the divalent or higher unsaturated carboxylic acid or its acid anhydride include fumaric acid, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic acid anhydride and itaconic acid anhydride.

Further, polycarboxylic acids such as phthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and trimellitic acid as divalent or higher carboxylic acids are contained in the unsaturated carboxylic acid described above and 50 mol% of all acid components. You may use it together in the range of less than.

In the present invention, a polyester resin obtained by copolycondensing a polyhydric alcohol component with an unsaturated carboxylic acid or a polyhydric alcohol with an unsaturated carboxylic acid or a polyvalent carboxylic acid is further crosslinked with a peroxide or a radical polymerization initiator, or It is produced by crosslinking an unsaturated portion by using a peroxide or a radical polymerization initiator and a radical polymerizable monomer.

Here, in the copolycondensation reaction, 0.5 to 10,000 ppm, preferably 5 to 500 p, based on the total amount of acidic components and total alcohol components.
A pm catalyst is used. Examples of the catalyst used include tin oxide, zinc oxide, titanium oxide, dibutyltin dilaurate, dibutyltin oxide and the like. Peroxide or radical polymerization initiator used for cross-linking reaction, 0.1 to 200,000 pp based on total polyester resin amount
m, preferably 10 to 50,000 ppm.

The following compounds are mentioned as a peroxide. Cetyl cyclohexyl sulfonyl peroxide, isobutyl peroxide, cumyl peroxy neodecanoate, di-
n-propyl peroxydicarbonate, t-butyl peroxy neodecanoate, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl Peroxide, succinic acid peroxide,
Acetyl peroxide, benzoyl peroxide, t-butyl peroxymaleic acid, cyclohexanone peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, n-butyl 4,4-bis-t-butyl peroxyvaleate , Methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl cumyl peroxide, citric hydroperoxide.

Examples of the radical polymerization initiator include the following compounds. Peroxodisulfates such as potassium peroxosulfate and ammonium peroxosulfate, and azo compounds such as 2,3-azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile.

The radical polymerizable monomer is 0.1 to 50% by weight, preferably 1 to 10% by weight based on the total acid component and the total alcohol content.
It is good to use weight%. Examples of the radically polymerizable monomer include the following monomers.

For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p
-N-butylstyrene, p-tert-butylstyrene, p
-N-hexylstyrene, pn-octylstyrene,
pn-nonylstyrene, pn-decylstyrene, p
-N-dodecylstyrene, p-methoxystyrene, p-
Chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene,
Styrene derivatives such as; ethylene and unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated diolefins such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride Vinyl acetates such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacryl 2-ethylhexyl acid, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and other α-methylene aliphatic monocarboxylic acid esters; acrylic Methyl, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ropyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Acrylic acid esters; maleic acid, maleic acid half esters; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl Pyrrole, N-vinylcarbazole, N-
N-vinyl compounds such as vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile;
Acrylic acid or methacrylic acid derivatives such as methacrylonitrile and chrylamide; acrolein; and the like.

In particular, a bisphenol derivative represented by the following formula (In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to
It is 10. ) Or a substitution product as an alcohol component, and an unsaturated polyester co-condensed with fumaric acid as an unsaturated carboxylic acid is used. Lauroyl peroxide or benzoyl peroxide is used as the peroxide, or azobis initiator is used as the radical polymerization initiator. Method of cross-linking by using unsaturated dioleophins such as isoprene and acrylic acid esters such as 2-ethylhexyl acrylate as azo compounds such as -2,4-dimethylvaleronitrile and radical-polymerizable monomers to give a three-dimensional structure Are preferable in terms of powder characteristics, fixing characteristics and image characteristics of the electrophotographic toner. In the present invention, the copolycondensation reaction is 30 ~ 300 ℃, preferably 80
It is better to carry out at -250 ° C, and the crosslinking reaction should be carried out at 20-180 ° C, preferably 40-120 ° C.

When the toner using the toner resin of the present invention is mixed with a carrier and used as a two-component developer, examples of the carrier include surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, and chromium. , Metals such as rare earths and their alloys or oxides and ferrites can be used. It is preferable that the carrier surface is coated with resin.

Further, as a method for coating the surface of the above-mentioned carrier with a resin or the like, a method of dissolving or suspending a coating agent such as a resin in a solvent and applying it to adhere to the carrier, a method of simply mixing with a powder, etc. are conventionally known. Either method can be applied.

The coating resin or fixing substance on the carrier surface varies depending on the toner material, but for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, vinylidene fluoride, silicone resin, polyester resin, metal complex of tert-butyl salicylic acid, styrene. Resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin,
It is suitable to use basic dyes and their lakes, silica fine powders, alumina fine powders, etc. alone or in combination, but the invention is not necessarily limited thereto.

The treatment amount of the above-mentioned material may be appropriately determined so that the carrier satisfies the above conditions, but generally, the total amount is preferably 0.1 to 30% by weight (preferably 0.5 to 20% by weight) with respect to the carrier of the present invention.

The average particle size of these carriers is 20-100μ, preferably 2
It is preferable to have 0 to 70 μ, and more preferably 30 to 65 μ.

In a particularly preferred embodiment, Cu-Zn-Fe ternary ferrite is used, and in that direction, a combination of a fluorine resin and a resin such as a styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin; A mixture of tetrafluoroethylene and styrene-methyl methacrylate resin, fluorine-based copolymer and styrene-based copolymer, etc. in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70 And 0.01 to 5% by weight, preferably 0.1 to 1
Weight% coated, 250 mesh (Taylor) pass, 3
One example is a coated ferrite carrier having the above-mentioned average particle size of 50% by weight of carrier particles of 70% by weight or more. As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:
10) is exemplified, and as the ethylene-based copolymer, styrene-2-ethylhexyl acrylate (20: 80-80: 20), styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60: 5-30: 10 to 50) are exemplified.

The above-mentioned coated ferrite carrier has a sharp particle size distribution, and has a preferable triboelectrification property with respect to the toner using the polyester resin of the present invention, and further has an effect of improving electrophotographic characteristics.

When a two-component developer is prepared by mixing with the color toner according to the present invention, the mixing ratio is 5.0 wt% to 15 wt%, preferably 6 wt% to 13 wt% as the toner concentration in the developer.
Good results are usually obtained with a percentage by weight. If the toner density is 5.0% or less, the image density will be too low to be practical and 15%.
In the above, the fog and the scattering in the machine are increased, and the useful life of the developer is shortened.

As the flow improver used in the present invention, any one can be used as long as it can be added to the colorant-containing resin particles to increase the flowability before and after the addition.

For example, fluorine-based resin powder, that is, fine powder of vinylidene fluoride, fine powder of polytetrafluoroethylene, or the like; or fatty acid metal salt, that is, zinc stearate, calcium stearate, lead stearate, or the like; or metal oxide,
That is, zinc oxide powder and the like: or finely powdered silica, that is, wet-processed silica, dry-processed silica, and silica that has been surface-treated with a silane coupling agent, a titanium coupling agent, silicone oil, and the like.

The preferred flow improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is so-called dry process silica or fumed silica,
It is manufactured by a conventionally known technique. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame is utilized, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl Also, in this manufacturing process, by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide, a composite fine powder of silica and another metal oxide is obtained. Is also possible and encompasses them.

The average particle diameter is preferably in the range of 0.001 to 2 μm, particularly preferably 0.002 to 0.2 μm.
It is preferable to use silica fine powder in the range of μ.

Commercially available fine silica powder produced by vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT CO.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 (WACKER-CHEMIE GMB) ) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil) Further, treated silica fine powder obtained by hydrophobizing silica fine powder produced by vapor phase oxidation of the silicon halogen compound is used. Is more preferable. Among the treated silica fine powders, those obtained by treating the silica fine powders so that the degree of hydrophobization measured by a methanol titration test is in the range of 30 to 80 are particularly preferable.

As a method for making water repellent, it is applied by reacting with fine silica powder or chemically treating it with an organic silicon compound that physically adsorbs.

As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane,
Trimethylethoxysilane, dimethyldichlorosilane,
Methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α
-Chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane,
Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyl dimethylacetoxysilane, dimethylethoxysilane,
Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule having terminal groups Is a dimethylpolysiloxane containing a hydroxyl group bonded to one Si each. These are used alone or as a mixture of two or more.

The treated silica fine powder preferably has a particle size in the range of 0.003 to 0.1 μm. Commercially available products include Taranox-500 (Talco), AEROSIL R-972
(Nippon Aerosil).

The amount added to the colorant-containing resin particles, the resin particles
0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight per 100 parts by weight
Parts by weight. If the amount is less than 0.01 part by weight, there is no effect on improving the fluidity.

Colorants suitable for the purpose of the present invention include the following pigments or dyes. In the present invention, light resistance is poor.
CIDisperse Y164, CISolvent Y77 and CISolvent Y
Colorants such as 93 are unrecognizable.

As the dye, for example, CI direct red 1, CI direct red 4, CI acidic red 1, CI basic red 1, CI modan red 30, CI direct blue 1, CI direct blue 2, CI acidic blue 9, CI
There are Acid Blue 15, CI Basic Blue 3, CI Basic Blue 5, CI Modern Blue 7, etc.

Pigments include Naphthol Yellow S and Hansa Yellow
G, permanent yellow NCG, permanent orange GTR,
There are pyrazolone orange, benzidine orange G, permanent thread 4R, calcium phosphate calcium salt, brilliant carmine 3B, fast biolett B, methyl biolet lake, phthalocyanine blue, fast sky blue, indanthrene blue BC and the like.

Preferably, disazo yellow, insoluble azo, copper phthalocyanine are used as pigments, and basic dyes and oil-soluble dyes are suitable as dyes.

CI Pigment Yellow 17, CI Pigment Yellow 15, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 12, CI Pigment Red 5, CI Pigment Red 3, CI Pigment Red 2, CI Pigment Red, CI Pigment Red Do 6, CI Pigment Red
7, CI Pigment Blue 15, CI Pigment Blue 16, or a copper phthalocyanine pigment having the phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups having the structural formula (I) shown below.

Examples of the dyes include CI solvent red 49, CI solvent red 52, CI solvent red 109, CI basked 12, CI basked 1, CI basked 3b and the like.

As for the content, for the yellow toner which is sensitive to the transparency of the OHP film, the binder resin 100
12 parts by weight or less based on parts by weight, preferably 0.5 to
7 parts by weight is desirable.

When it is 12 parts by weight or more, the reproducibility of green and red, which are mixed colors of yellow, and human skin color as an image is poor.

For the other magenta and cyan color toners, the amount is preferably 15 parts by weight or less, more preferably 0.1 to 9 parts by weight or less with respect to 100 parts by weight of the finalizing resin.

Especially for a black toner which is used in combination with two or more colorants, addition of 20 parts by weight or more of the total amount of colorants not only tends to cause spent to the carrier, but a large number of colorants are exposed on the toner surface. As a result, toner fusion on the drum and anxiety about fixability are also increased. Therefore, the amount of the colorant is preferably 3 to 15 parts by weight based on 100 parts by weight of the binder resin.

Preferred combinations of colorants for forming a black toner include a combination of a disazo yellow pigment, a monoazo red pigment and a copper phthalocyanine blue pigment. The mixing ratio of each pigment is preferably 1: 1.5 to 2.5: 0.5 to 1.5 in the ratio of yellow pigment, red pigment and blue pigment.

It is also preferable that the toner according to the present invention contains a charge control agent in order to stabilize the negative charge characteristics. At that time, a colorless or light-colored negative charge control agent which does not affect the color tone of the toner is preferable. Examples of the negative charge control agent include an organic metal complex such as a metal complex of an alkyl-substituted salicylic acid (for example, a chromium complex or a zinc complex of di-tert-butylsalicylic acid). When a negative charge control agent is blended in the toner, 0.1 to 100 parts by weight of the binder resin is used.
It is preferable to add 10 parts by weight, preferably 0.5 to 8 parts by weight.

 Hereinafter, each measurement method in the present invention will be described.

(1) Measurement of glass transition temperature Tg In the present invention, measurement is performed using a differential thermal analysis measurement device (DSC measurement device), DSC-7 (manufactured by Perkin Elmer Co.).

The measurement sample is precisely weighed in an amount of 5 to 20 mg, preferably 10 mg.

This is put in an aluminum pan, an empty aluminum pan is used as a reference, and the following operation is performed for the purpose of first erasing the previous history. 10 ℃ / min from room temperature to 200 ℃ under N ₂ atmosphere
The temperature is raised at and kept at 200 ° C for 10 minutes. After that, it is rapidly cooled to 10 ℃
Reduce the temperature to 10 ° C and hold for 10 minutes. Then the heating rate
The temperature is raised to 200 ° C at 10 ° C / min. During this temperature raising process, an endothermic peak of the main peak in the temperature range of 40 to 100 ° C is obtained.

The intersection of the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention. (See FIG. 1) (2) Measurement of molecular weight distribution In the present invention, measurement is performed by high performance liquid chromatography (JASCO TRI ROTAR-VI HPLC System manufactured by JASCO Corporation). The column is Toso TSK gel-200 manufactured by Toyo Soda Kogyo Co., Ltd.
0, -3000, -4000, -5000 are used, and the solvent is THF. D
Etector is Shodex RISE-51 manufactured by Showa Denko KK, and measurement conditions are: Flow rate 1.0 ml / min, column temperature 40 ° C, Inj vol.7.
Perform at 5μ.

The molecular weight of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples having the molecular weight distribution of the sample.

As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.15 manufactured by Pressure Chemical Co. or Toyo Soda Industry Co., Ltd.
× 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶
It is appropriate to use at least about 10 standard polystyrene samples.

Measurement of softening temperature Sp by flow tester: Flow tester CFT-500 type (manufactured by Shimadzu Corporation) is used. The sample weighs about 1.0 to 1.5 g of a 60 mesh bath product. Using a molding machine, this is pressed under a load of 100 Kg / cm ² for 1 minute.

This pressure sample is subjected to flow tester measurement under the following conditions at room temperature and normal humidity (temperature of about 20 to 30 ° C., humidity of 30 to 70% RH) to obtain a temperature-plunger position movement curve (flow tester curve).

The intersection of the flow tester curve and the line between the initial plunger position and the flanger position at the end of the measurement is defined as the softening temperature Sp in the flow tester of the present invention.
(See Fig. 2) RATE TEMP 6.0 D / M (℃ 1 minute) SET TEMP 70.0 DEG (℃) MAX TEMP 200.0 DEG INTERVAL 3.0 DEG PREHEAT 300.0 SEC (sec) LOAD 20.0 KGF (Kg) DIE (DIA) 1.0MM ( mm) DIE (LENG) 1.0 MM PLUNGER 1.0 CM ² (cm ² ) The present invention will be described in detail below with reference to examples.

 In addition, "%" and "part" show a weight% and a weight part.

Example 1 1380 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and 460 g of fumaric acid were added,
Thermometer A stainless steel stirrer, a glass nitrogen inlet tube, and a downflow condenser were placed in a 2-necked, 4-neck, round-bottomed flask. Next, the flask was placed in a mantle heater, and nitrogen gas was introduced from a glass inlet tube to keep the inside of the reactor in an inert atmosphere and heated. 0.10 g of dibutyltin oxide was added and the temperature was kept at 200 ° C. to cause a copolycondensation reaction.

The progress of the reaction is tracked by the softening point by the ring and ball method, and the softening point is
The reaction was stopped when the temperature reached 116 ° C (Mw = 20000, Mn = 5000, Tg = 62 ° C).

Next, 150 g of 2-ethylhexyl acrylate and 15 g of benzoyl peroxide (BPO) were added, the temperature was raised to 80 ° C., and the reaction was carried out for 16 hours. The resin obtained here has a Tg of 57 ° C.
The Mw was 19,000, the Mw / Mn was 10.2, and the softening temperature Sp by the flow tester was 106 ° C. The polyester resin obtained in this example is referred to as resin No. 1.

Example 2 After the copolycondensation reaction was carried out under the same conditions as in Example 1,
Softening point by ring and ball method is 114 ℃ (Mw = 18000, Mn = 4500, Tg ＝
The reaction was stopped when the temperature reached 60 ° C.

Next, 70 g of isoprene and 7 of benzoyl peroxide
g was added, and the temperature was raised to 80 ° C. and reacted for 16 hours.

The polyester resin thus obtained has a Tg of 55 ° C. and an Mw of 1
It was 7,000, Mw / Mn was 8.5, and the softening temperature Sp by the flow tester was 105 ° C. The polyester resin obtained in this example is referred to as resin No. 2.

Example 3 A copolycondensation reaction was carried out under the same conditions as in Example 1, and the softening point by the ring and ball method was 110 ° C (Mw = 16000, Mn = 4300, Tg = 58 ° C).
The reaction was stopped when. Next, 100 g of styrene
Then, 10 g of benzoyl peroxide was added, the temperature was raised to 80 ° C., and the reaction was carried out for 16 hours.

The polyester resin thus obtained has a Tg of 60 ° C and an Mw of 1
It was 9,000, Mw / Mn was 8.8, and the softening temperature Sp by the flow tester was 110 ° C. The polyester resin obtained in this example is referred to as resin No. 3.

Comparative Example 1 1380 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and 460 g of fumaric acid were equipped with a thermometer, a stirrer made of stainless steel, a nitrogen inlet pipe made of glass and a flow-down condenser. It was placed in a 2-necked 4-neck round bottom flask. Next, the flask was placed in a mantle heater, and nitrogen gas was introduced from a glass inlet tube to keep the inside of the reactor in an inert atmosphere and heated. 0.10 g of dibutyltin oxide was added and the temperature was kept at 200 ° C. to carry out a copolycondensation reaction until the softening point by the environmental method reached 118 ° C.

The Tg of the obtained polyester resin is 61.5 ° C, and the Mw is
It was 12,000, Mw / Mn was 7.4, and the softening temperature Sp by the flow tester was 108 ° C.

Example 4 Polyester resin 100 of resin No. 1 obtained in Example 1
Parts by weight, 3.5 parts by weight of CI Pigment Yellow 17 and 4.0 parts by weight of a chromium-containing organic complex (negative charge controlling agent) are premixed by a Henschel mixer, melt-kneaded at least twice with a three-roll mill, and after cooling. Coarsely crushed to about 1 to 2 mm using a hammer mill, then finely crushed to a particle size of 40 μm or less with a fine crusher using an air jet system,
The obtained finely pulverized product was classified to selectively obtain a particle size of about 2 to about 23μ. To 100 parts by weight of the obtained classified powder, 0.5 part by weight of dry silica fine powder which was hydrophobized with hexamethyldisilazane was mixed to obtain a yellow toner.

Similarly, magenta toner, cyan toner and black toner were prepared according to the formulations shown in Table 1 below.

The softening temperature (Sp) of the obtained classified powder of each color by a flow tester is 113 ° C for yellow powder, 108 ° C for magenta powder, and 112 ° C for cyan powder,
The black powder was 111 ° C. Further, the toners of each color also had substantially the same softening temperature.

About 8 to 10 parts by weight of this color toner was coated with vinylidene fluoride-tetrafluoroethylene copolymer and styrene-2-ethylhexyl acrylate-methyl methacrylate at a weight ratio of 50:50 by about 0.5% by weight, Cu
-Zn-Fe type ferrite carrier (average particle size 48 μm; 250 mesh pass, 350 mesh pass, 79 wt%; true density 4.5 g / cm
³ ) was mixed to make a total amount of 100 parts by weight to prepare a developer.
In consideration of color reproducibility and toner scattering, yellow,
The concentrations of magenta, cyan, and black color toners in the developer were 9% by weight, 8% by weight, 10% by weight, and 10% by weight, respectively. Fill the two-component developer of each color into the Canon full color copying machine (CLC-1) of the heat roller fixing system,
A durability test was performed. As a result, a clear full-color (multi-color) image without fog was obtained even after the durability of 20,000 sheets. Further, a heat and pressure soft roller system is provided which comprises a heating roller having a surface layer of silicone rubber and a pressure roller having a fluorine resin coating on the surface of the silicone rubber layer, which is printed by the copying machine to obtain an unfixed image. By the external fixing machine of
The fixing temperature range was tested for the low temperature and high temperature offsets. As a result, it was possible to obtain a clear fixed image having no offset and a flat image on the fixing surface for each color toner between 110 ° C and 220 ° C. From this, it was found that the toner of the present invention has good offset resistance to a silicone rubber heating roller. Further, in the mixed color portion, the color was beautiful and the color tone was substantially the same as that of the sample image.

Example 5 A yellow toner, a magenta toner, a cyan toner and a black toner were prepared in the same manner as in Example 4, except that the polyester resin No. 2 obtained in Example 2 was used. The softening temperature (Sp) of the obtained yellow toner is 112 ° C.
The magenta toner had a softening temperature of 107 ° C., the cyan toner had a softening temperature of 111 ° C., and the black toner had a softening temperature of 110 ° C. When a durability test was conducted in the same manner as in Example 4, a clear full-color image without fog was obtained even after the durability of 20,000 sheets. In the fixing temperature range test, in the temperature range of 105 to 210 ° C., a clear fixed image without offset was obtained for each color toner, the fixing surface was a flat image, and a full color image with beautiful color was obtained in the mixed color part. .

Example 6 A yellow toner, a magenta toner, a cyan toner and a black toner were prepared in the same manner as in Example 4 except that the polyester resin No. 3 obtained in Example 3 was used. The obtained yellow toner had a softening temperature of 117 ° C., the magenta toner had a softening temperature of 112 ° C., the cyan toner had a softening temperature of 116 ° C., and the black toner had a softening temperature of 115 ° C. When a durability test was conducted in the same manner as in Example 4, a clear full-color image without fog was obtained even after the durability of 20,000 sheets. In the fixing temperature range test, a clear fixed image with no offset was obtained for each color in the temperature range of 115 to 230 ° C., the fixing surface was a flat image, and a full-color image with a beautiful color was obtained in the mixed color portion.

Comparative Example 2 Yellow toner, magenta toner, cyan toner and black toner were prepared in the same manner as in Example 4 except that the polyester resin obtained in Comparative Example 1 was used.
The resulting yellow toner has a softening temperature of 112 ° C, the magenta toner has a softening temperature of 106 ° C, the cyan toner has a softening temperature of 110 ° C, and the black toner has a softening temperature of 109 ° C.
° C.

When a durability test was performed in the same manner as in Example 4,
The offset phenomenon occurred at about 15,000 sheets.

In the fixing temperature range test, when the low temperature offset and high temperature offset were examined, the fixing temperature range was 130 to 1
The temperature was 70 ° C., and the fixing temperature range was narrower than that in each of the above-described examples.

Example 7 Except for using 100 parts by weight of polyester resin No. 1 with a colorant and a charge control agent in the following mixing ratios,
In the same manner as in Example 4, yellow toner, magenta toner, cyan toner and black toner were prepared. Similar to the toners of Example 4, each color toner showed good color mixture and offset resistance at the time of heat roller fixing.

[Effects of the Invention] The polyester resin of the present invention can provide a dry color toner exhibiting good mixing property, durability, fixing property and offset resistance when used as a binder resin for a full color toner. it can.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a glass transition temperature in the present invention, and FIG. 2 is a diagram for explaining a softening temperature Sp by a flow tester in the present invention.

Claims (3)

(57) [Claims] 1. A polyester resin produced from a polyhydric alcohol component and a polycarboxylic acid component, wherein the polyester has a weight average molecular weight (Mw) / number average molecular weight (Mn) value of 20 or less, The glass transition temperature (Tg) of the polyester resin and the weight average molecular weight (Mw) satisfy the following relationship: 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻⁴ × Mw + 47, and the glass transition temperature of the polyester resin (Tg) and the softening temperature (Sp) measured by the flow tester have the following relationship A polyester resin for toner, which satisfies: 2. A weight average molecular weight obtained by polycondensing an unsaturated polycarboxylic acid component having an unsaturated double bond group, a saturated polycarboxylic acid component having no unsaturated double bond and a polyhydric alcohol component. (Mw) is 200,000 or less, number average molecular weight (Mn) is 1000 or more, and glass transition temperature is 45 to 75.
The glass transition temperature of the polyester resin having a three-dimensional structure is generated by forming a polyester resin having a temperature of ℃ and by reacting the unsaturated double bond groups of the generated polyester resin to give a three-dimensional structure to the polyester resin. (Tg) and weight average molecular weight (Mw) satisfy the following relationship: 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻⁴ × Mw + 47, and the glass transition temperature of a polyester resin having a three-dimensional structure. (Tg) and softening temperature (S
p) is related to A method for producing a polyester resin for a toner, which comprises producing a polyester resin satisfying the above conditions. 3. An electrostatic charge image developing toner containing at least a binder resin and a colorant, wherein the binder resin contains a polyester resin formed from a polyhydric alcohol component and a polycarboxylic acid component, The weight average molecular weight (Mw) / number average molecular weight (Mn) value of the polyester resin is 20 or less, and the glass transition temperature (Tg) of the polyester resin and the weight average molecular weight (Mw) have the following relationship: 9 × 10 ⁻⁴ × Mw + 31.5 ≦ Tg ≦ 9 × 10 ⁻⁴ × Mw + 47 is satisfied, and the glass transition temperature (Tg) of the polyester resin and the softening temperature (Sp) measured by a flow tester have the following relationship. Toner characterized by satisfying.