JPS62273574A - Electrostatic image developing toner for use in heat fixing roller superior in offset resistance - Google Patents

Abstract

PURPOSE:To enable low-temperature fixing by using a copolymer having one of crystalline polymer blocks chemically combined with one of amorphous polymer blocks as a binder, and specifying the content of the crystalline polymer blocks in the copolymer. CONSTITUTION:The electrostatic image developing toner contains as the binder the copolymer having at least one of the crystalline polymer blocks chemically combined with at least one of the amorphous polymer blocks. The crystalline polymer blocks have a melting point of 40-120 deg.C, and the amorphous polymer blocks are substantially incompatible with the crystalline polymer blocks, and have a glass transition point higher than the melting point of the crystalline polymer blocks by at least >=10 deg.C. The crystalline polymer blocks are contained in an amount of 10-70wt% of the copolymer, thus permitting sufficient fixing to be attained even at a temperature of 80-130 deg.C, and offset trouble to be prevented.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention is applicable to the development of electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, etc. The present invention relates to a toner for developing an electrostatic image, particularly a toner for developing a TL image for hot roller fixing, which has excellent anti-offset properties.

[Background of the invention]

For example, in electrophotography, an electrostatic latent image is usually formed by charging and exposing an electrostatic image carrier made of a photoconductive illuminant, and then this electrostatic latent image is placed in a binder made of resin with a coloring agent. The resulting toner image is transferred to a support such as transfer paper and fixed to form a visible image.

In order to obtain a visible image as described above, it is necessary to fix the toner image, and conventionally, a heat roller fixing method that has high thermal efficiency and can perform high-speed fixing has been widely used.

However, recently, there has been a strong demand from various viewpoints to perform the fixing process at a high speed while keeping the temperature of the heat roller at a lower temperature. Chino is wanted.

Furthermore, in the toner, it is possible to stably exist as a powder without agglomerating under the environmental conditions of use or storage;
In other words, it is necessary that the toner has excellent anti-printing and kinging properties.Furthermore, in the hot roller fixing method, which is preferable as a fixing method, there is an offset phenomenon, that is, a part of the toner constituting the image is transferred to the surface of the hot roller during fixing. Since this tends to transfer again to the next transferred transfer paper and stain the image, it is necessary to provide the toner with the ability to prevent the occurrence of the offset phenomenon, that is, offset resistance.

Conventionally, as a binder resin constituting a toner, a technical means (Japanese Unexamined Patent Application Publication No. 1983-1989 -87032) is known. However, although this technical means can fix toner at a relatively low temperature, it has the drawback that offset phenomenon tends to occur, and due to poor pulverization properties, it is difficult to obtain proper particles depending on the method that includes a normal pulverization process. However, there is a problem in that it is difficult to manufacture toners of this size.

[Problem that the invention seeks to solve]

On the other hand, the binder resin constituting the toner contains a crystalline block with a melting point of 45 to 90°C and an amorphous block with a glass transition point 10°C higher than the melting point of the crystalline block. A technical means has been proposed that uses a thermoplastic polymer containing 70 to 95% by weight of crystalline blocks (see JP-A-59-3446). .

However, this technical means is effective when applied to image formation using a transfer process using an intermediate transfer body, and when applied to image formation using a fixing process using a heat roller fixing method, offset There are problems that can easily cause this phenomenon. In other words, since the content of crystalline blocks in the polymer is as high as 70 to 95% by weight, the toner has low elasticity when heated and melted by a hot roller, and therefore a portion of the toner tends to transfer to the hot roller during fixing. There are drawbacks.

[Purpose of the invention]

The present invention has been made based on the above-mentioned circumstances, and an object thereof is to enable fixing at a sufficiently low temperature when applied to image formation employing a fixing process using a hot roller fixing method. Moreover, it provides sufficient offset resistance. An object of the present invention is to provide a toner for electrophotographic development.

c. Means for Solving Problems] The toner for electrostatic image development of the present invention comprises a copolymer formed by chemically bonding at least one crystalline polymer block and at least one amorphous polymer block. is contained as a binder, and the melting point of the crystalline polymer block is 4.
0 to 120°C, and the amorphous polymer block is substantially incompatible with the crystalline polymer block and has a glass transition temperature at least 10°C higher than the melting point of the crystalline polymer block. The content of the crystalline polymer block in the copolymer is 10% by weight or more and less than 70% by weight.

[Function and effect of the invention]

According to the electrostatic image developing toner of the present invention, the copolymer constituting the binder is formed by chemically bonding a specific crystalline polymer block and a specific amorphous polymer block,
Moreover, since the content of the crystalline polymer block contained in the copolymer is 10% by weight or more and less than 70% by weight,
When applied to image formation using a fixing process using a orbital roller fixing method, sufficient fixing can be achieved even at low temperatures such as 80 to 130 degrees Celsius, and when heated and melted by a PA roller, The elasticity of the toner is sufficiently high, so that part of the toner is inhibited from being transferred to the heat roller during fixing, thereby preventing the offset phenomenon from occurring, and as a result, it is possible to form a good image at high speed.

That is, in the present invention, the content ratio of the crystalline polymer block in the copolymer is lower than that of the conventional one, and the elasticity of the toner when melted is increased while maintaining the low-temperature fixability due to the crystalline polymer block. It is possible to prevent the phenomenon from occurring. In addition, the development of physical adhesion caused by the crystalline polymer block is suppressed, so toners using this copolymer as a binder have excellent blocking resistance and can exist stably as a powder without agglomerating. becomes. In addition, as a result of the amorphous polymer block content being higher than before, the amorphous polymer block improves the triboelectric charging properties of the toner, and therefore the amount of toner that adheres to the electrostatic latent image is sufficient, resulting in high image density. An image can be formed.

The present invention will be explained in detail below.

In the present invention, at least one specific crystalline polymer block, details of which will be described later, and at least one specific amorphous polymer block, details of which will be described later, are chemically bonded in a block or graft form in a specific ratio. A copolymer formed by linking with is used as a toner binder.

The crystalline polymer block has a melting point Tm of 40 to 12
0°C, preferably 50-110°C. The amorphous polymer block has a glass transition point Tg at least 10°C higher than the melting point Tm of the crystalline polymer block, that is, at least (Tm + 10°C), preferably (Tm 415°C). The temperature is above, and the crystalline block is incompatible with the crystalline block.

The content ratio of the crystalline polymer block in the copolymer is 10% or more and less than 70% by weight, preferably 10 to 50% by weight.

The above specific copolymer may be, for example, a normal block copolymer, or a graft copolymer consisting of the main chain of one block and the other block grafted thereto. may be used, but block copolymers are particularly preferred.

For example, it can be obtained by a method in which a copolymer consisting of the crystalline polymer block and the amorphous polymer block is dissolved in a common solvent and then combined by the action of a suitable coupling agent.

The crystalline polymer block has a melting point Tm of 40°C.
When it is less than 100%, the toner becomes highly sticky, and as a result, it tends to aggregate and the blocking resistance decreases. Further, when the melting point Tm exceeds 120°C, the fixability at low temperatures becomes insufficient.

When the content of the crystalline polymer block in the copolymer is less than 10% by weight, fixing properties at low temperatures will be insufficient. When the content is 70% by weight or more, the elasticity of the toner when melted is low (as a result, the offset resistance is reduced).

Further, the copolymer has a dynamic elastic modulus σ of at least 2.0 at a temperature of 80 to 130°C. OX 10'~1
．． It is preferably within the range of 0x10'dyn/cnt, and the dynamic viscosity η at a temperature of 80 to 130°C
It is preferable that at least one of the values of ゛ is 1×1 Oh-poise or less. By using a copolymer having such a dynamic elastic modulus σ and dynamic viscosity η', good anti-offset properties can be achieved during toner fixation.

Further, the copolymer has a weight average molecular in- of 5,0
00 to 300,000, and the number average molecular weight 1n is preferably 1,000 to 30,000. If these molecular weights are excessive,
The melting temperature of the toner may rise, reducing the effect of low-temperature fixing properties and reducing the pulverization efficiency. On the other hand, if it is too low, the anti-offset properties may become poor.

In the present invention, the crystalline polymer block and the amorphous polymer block are incompatible with each other. Here"
"Incompatibility" means that the chemical structures of the two are the same or that the two do not have the property of being sufficiently dispersed due to the action of Pi (or Pi), or the action of functional groups, and the solubility parameters such as S, p, Value (R,F, Fedor
s, Polym, Eng, Sci, 14. (2
)147 (1974) ) is larger than 0.5.

In the present invention, the melting point Tm of the crystalline polymer block,
The glass transition point Tg of the amorphous polymer block, the dynamic elastic modulus G' and dynamic viscosity η' of the copolymer, the weight average molecule IM- and the number average molecule IMn of the copolymer are determined as follows. This is the value measured.

Melting point Tm of the crystalline polymer block> According to differential scanning calorimetry (D SC), the crystalline polymer block tomg is melted at a constant IWl;! ! Speed CIO°
The melting peak value when added at C/mi*) is the melting Tm
shall be.

<Glass transition point Tg of amorphous polymer block> According to differential scanning calorimetry (DSC), the amorphous polymer block lomg was heated at a constant temperature increase rate (10'C/m1n), and the temperature was compared to the baseline. The glass transition point Tg is obtained from the intersection of the endothermic peak with the line.

The dynamic elastic modulus σ and dynamic viscosity η′ of the copolymer can be measured using, for example, Shimabara Rheometer RM-1j (manufactured by Shimabara Seisakusho Co., Ltd.). A sinusoidal vibration is applied to this molten sample, and the dynamic elastic modulus σ and dynamic viscosity η' are obtained from the amplitude ratio and phase difference of the torsion. Average molecular weight Mn> Gel permeation chromatography (GPC)
), the weight average molecular weight -1 and number average molecular weight i1Mn are measured under the conditions described below. At a temperature of 40°C,
The solvent (tetrahydrofuran) was flowed at a flow rate of 1.2-min/min, and 3 mg of a 0.2 g/20117 tetrahydrofuran sample solution was injected four times to perform measurements. When measuring the molecular weight of a sample, the measurement conditions are such that the molecular weight of the sample falls within the range where the logarithm of the molecular weight and the count number of the calibration curve prepared using several kinds of flower molecule TT polystyrene standard samples are in a straight line. select.

The reliability of the measurement results is determined by the N
B5706 polystyrene standard sample has a weight average molecular weight M
ga=28.8X10' number average molecule 1Mn=13.7×l
This can be confirmed by determining O'.

Moreover, any column may be used as the GPCO column as long as it satisfies the above conditions. Specifically, for example, TSK-GEL, GMH (manufactured by Toyo Soda Co., Ltd.), etc. can be used.

Examples of the crystalline polymer block that can be used in the present invention include the following polymers.

0 Polyesters: Polydecamethylene adipate, polydecamethylene azerade, polydecamethylene adipate, polydecamethylene sebacate, polydecamethylene adipate, polyethylene sebacate, polyethylene sebacate, polyethylene succinate , polyhexamethylene sebacate, polyhexamethylene herate, polyhexamethylene sebacate
, polyhexamethylene sebacate, poly-10-hydroquinocaprylic acid, poly-6-hydroxycaproic acid,
Poly-3-hydroxypropionic acid, other 0 polyolefins: poly-1-butene, poly-3-methylbutene, poly-1
-hexadecene, poly-1-octadecene, poly-1-
Pentene, poly-4-methylpentene, 0 polyvinyl esters: polyacrylic acid allyl ester, polyacrylic acid isobutyl ester, polyacrylic acid decyl ester, polyacrylic acid octadecyl ester, polyacrylic acid dodecyl ester, other 0 polydiene tn・1.2-poly-1+3-butadiene (isotactic), trans-1,4-poly-1,3-butadiene, cis-1,4-poly-2-t-butyl-1,3-butadiene, trans-chloroprene, trans-chloroprene, trans-1,4-poly-1,3-hebutadiene (isotactic), trans-1,4-poly-6-methyl-
1,3-heptadiene (isotactic), trans-1,4-poly-1,3-hexadiene (isotactic), trans-1,4-poly-5-methyl-1,3
-Hexadiene (isotactic), other 0 polyethers; polybutyl vinyl ether, polyisobutyl vinyl ether, polyisopropyl vinyl ether, polyethyl vinyl ether, poly-2-methoxyethyl vinyl ether, other 0 polyoxides; polyethylene oxide, polypropylene oxide,
Polyhexamethylene oxide, polyoctamethylene oxide, polynonamethylene oxide, polydecamethylene oxide, polychloromethylethylene oxide, other 0 polysulfides, polysulfones: polyethylene disulfide, polytetramethylene sulfide, polypentamethylene sulfide, polyethylene xamethylene sulfide, polydecamethylene sulfide, polytetramethylene sulfone, other O polysancalide neck; poly-1,4-B-D-glucose tricaprylate,
Others 0 Other than the above: Among poly-4-(4-methylthiophenoxy)-ethyleneamine, poly-6-mercaptocaproic acid, polydipropylsiloxane, and others, polyesters are particularly preferred.

Examples of the amorphous polymer block that can be used in the present invention include polyester resins, styrene resins, acrylic resins, styrene-acrylic resins, and other vinyl resins. Among these, polyester resin is particularly preferred.

This polyester resin is obtained by condensation polymerization of an alcohol component and a carboxylic acid component. Examples of the alcohol component include ethylene glycol, diethylene glycol, triethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol, 1. .4-Butanediol, neopentyl glycol, 1,4-butynediol and other diols! , 1,4-bis(hydroxymethyl)cyclohexane, and bisphenol A1 hydrogenated bisphenol A1 polyoxyethylated bisphenol A1 polyoxypropylenated bisphenol A
Examples include etherified bisphenols and other dihydric alcohol monomers.

Examples of carboxylic acid components include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid/cehatic acid, and malonic acid. , anhydrides of these acids, dimers of lower alkyl esters and lyluic acid, and other divalent organic acid monomers.

In forming such a polyester resin, in addition to the above-mentioned Ninomiya fatty monomers, trifunctional or higher polyfunctional monomers can also be used. Examples of trivalent or higher polyhydric alcohol monomers that are polyfunctional monomers include sorbitol, 1,2.3°6-hexanetetrol, l
, 4-sorbitan, pentaerythritol, dipentaerythritol, tribenerythritol, sucrose, 1,
2.4-butanetriol, 1,2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.5
~trihydroxymethylbenzene, and others.

Further, examples of trivalent or higher polyvalent carboxylic acid bodies include 1.2.4-benzenetricarboxylic acid, 1,2.5-benzenetricarboxylic acid, 1.2.4-benzenetricarboxylic acid, 2, 5.7-naphthalenetricarboxylic acid, 1.2.4-naphthalenetricarboxylic acid, 1.2.4
-butanetricarboxylic acid, 1,2.5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methylcarboxypropene, 1,3-dicarboxy-2-methyl-2-
Mention may be made of methylenecarboxypropane, tetra(methylenecarboxy)methane, 1,2.7.8-octanetetracarboxylic acid, Empol trimer acid, and acid anhydrides thereof, and others.

411 for forming a styrene resin, acrylic resin, styrene-acrylic resin, other vinyl resin, etc. that can be used as the amorphous polymer block.
For example, styrene, 0-methylstyrene,
p-methylstyrene, p-ethylstyrene, α-methylstyrene, 2,4-dimethylstyrene, p-tert-
Butylstyrene, pn-octylstyrene, pn-
Styrene compounds and their derivatives such as dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate Class; vinyl chloride; acrylic acid, methyl acrylate, ethyl acrylate, acrylic ml n
-butyl, isobutyl acrylate, ter acrylate
t-Butyl, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, dimethylaminoethyl acrylate , methacrylic acid,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 1ln-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylic acid α-methylene aliphatic monocarboxylic acids and their esters such as phenyl, dimethylamine ethyl methacrylate, and diethylaminoethyl methacrylate; Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; Vinyl methyl ether, vinyl ethyl Vinyl ethers such as ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone; N-vinyl pyrrole, N-
Examples include N-vinyl compounds such as vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; and others.

Examples of polymers or copolymers made of these monomers include polystyrene, poly p-chlorostyrene, polyvinyltoluene, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, and styrene-vinyltoluene copolymer. Polymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylate Acid methyl copolymer, styrene-
Ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene L/7-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Examples include ethyl ether copolymer and styrene-vinyl methyl ketone copolymer.

When forming a copolymer consisting of the crystalline polymer block and the amorphous polymer block, the functional groups of each of the crystalline polymer block and the amorphous polymer block are reacted to form a copolymer. Alternatively, a copolymer may be formed using an appropriate coupling agent.

Coupling agents that can be used to form such copolymers include, for example, polyfunctional isocyanates, polyfunctional amines, polyfunctional carboxylic acids, polyfunctional alcohols,
Examples include polyfunctional acid chlorides. As this coupling agent, it is preferable to select one that reacts with the crystalline polymer block and the amorphous polymer block, but does not react with each other.

Specific examples of such coupling agents include difunctional isocyanates such as hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, toridine diisocyanate, naphthylene diisocyanate, isophorone diisocyanate, quinlylene diisocyanate; for example, ethylenediamine, hexamethylene Difunctional amines such as diamines, phenylenediamines; e.g. oxalic acid, succinic acid, adipic acid,
Difunctional carboxylic acids such as sebacic acid, terephthalic acid, isophthalic acid; difunctional alcohols such as ethylene glycol, propylene glycol, hexanediol, cyclohexane dimetatool, p-xylylene glycol; e.g. terephthalic acid chloride, isophthalic acid Difunctional acid chlorides such as chloride, adipic chloride, sebacyl chloride; other difunctional coupling agents such as diisothiocyanate, bisketene, biscarbodiimide; for example triphenylmethane triisonanate, 1,3 .Tri- or higher-functional polyfunctional isocyanate such as 6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, tris(isocyanate phenyl) thiophosphate; for example, triaminobenzene, triaminotoluene, triamino Trifunctional or higher polyfunctional amines such as triphenylmethane; for example, 1°2.4-Hensentricarbon M, 1,2.5-
Benzenetricarboxylic acid, 1.2.4-cyclohexanetricarboxylic acid, 2,5.7-naphthalenetricarboxylic acid, 1.2.4-naphthalenetricarboxylic acid, 1.2.
4-butanetricarboxylic acid, 1,2.5-hexanetricarboxylic acid, l,3-dicarboxyl-2-methyl-2
- trifunctional or higher polyfunctional carphone M such as methylenecarboxylpropane, tetra(methylenecarboxyl)methane, 1,2,7.8-octanetetracarboxylic acid, Empol trimer acid, and acid anhydrides thereof; e.g. Sorbitol, 1,2,3.6-hexanetetrol,
114-Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, f$JL
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1
, 3.5-trihydroxymethylbenzene and other trifunctional or higher functional alcohols; and the like.

These coupling agents can be used alone or in combination of two or more.

The binder in the toner for electrostatic image development of the present invention may be composed only of a copolymer consisting of the above-mentioned specific crystalline polymer block and amorphous polymer block, or The copolymer may be formed by mixing other resins as necessary.

Other components constituting the toner for developing electrostatic images of the present invention include colorants, magnetic substances, and other property improving agents.

Coloring agents include carbon bra, lye, and nigrosine dye (
C,! , Kan 50415B), Aniline Blue (C, I
・m50405), Calco Oil Blue (C, 1, Th
azoicBlue 3), Chrome Yellow (
C9I, m14090), ultramarine blue (
C, R, 11 to 177103), DuPont Oil Red (C, T, Magnetic 26105), Quinoline Yellow (C
.

1, Kan 47005), methylene blue chloride (C,
1, Arashi 52015), Phthalocyanine Blue (C, 1,
Kan74160), malachite green off-salate (
C, T, fish 42000), lamp black (C, 1,
Th77266), Rose Bengal (C, 1, Th4
5435), mixtures thereof, and others. These colorants are preferably contained in such a proportion that a visible image of sufficient density can be formed.
Usually, it is preferably about 1 to 20 parts by weight per 100 parts by weight of toner.

Magnetic materials include ferrite, magnetite, iron, cobalt, nickel, and other ferromagnetic metals or alloys, or compounds containing these elements, or compounds that do not contain ferromagnetic elements but can be made stronger by applying appropriate heat treatment. Alloys that exhibit magnetism, such as manganese-copper-aluminum, manganese-i, etc.
Examples include a type of alloy called Heusler alloy containing the same, chromium dioxide, and others. These magnetic substances are preferably used in the form of fine powder with an average particle size of 0.1 to 1 μm. When obtaining a magnetic toner, the content ratio of the magnetic material is 20 to 100 parts by weight of the toner.
70 parts by weight is preferred, particularly 40 to 70 parts by weight.

Examples of other property improving agents include charge control agents, fluidity improvers, and abrasives. As the charge control agent, conventionally known ones such as nigrosine dyes, metal-containing ab dyes, and metal complexes can be used. As the fluidity improver, for example, fine particles of silica, alumina, titania, etc. can be used. As the polishing agent, for example, fine particles such as cerium oxide can be used.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.

The crystalline polymer blocks and amorphous polymer blocks used in the following Examples and Comparative Examples are as follows.

Crystalline polymer block A〉 Polytrimethylene sebacate Melting point Tm: 49°C1 Weight average molecule iMw: 1
3.100, s, p, value: 9.8 (cal/am3)
""〈Crystalline polymer block B〉 Polyethylene succinate Melting point Tm: 92°C, Weight average molecule 11Mw: 8
,900,s,p,value: 12.5 (cal/cm3)
``Crystalline polymer block C〉 Polyhexamethylene sebacate Melting point Tm: 64°C, weight average molecule 111Mw:
14. QOOls, p, value: 10.2 (cal/cm
3) Amorphous polymer block a> Propylene glycol/cyclohexanedimethanol (
Polyester glass transition point Tg: 62.5°C1 Weight average molecular weight M-: 10,000, s, p, value: 12.8 (ca
t/cm') Amorphous polymer block b> Polymethyl methacrylate glass transition point Tg: , 103°C, weight average molecule 1
1Mw: 12,500, s, p, value: 10.0 (c
amorphous polymer block C> Polystyrene glass transition point Tg: 100°C, weight average molecule 1Mw:
11,000, s, p, value: 11.3 (cal/cm
3) "" (Amorphous polymer pro, d) Polyester glass transition point Tg of polyoxypropylene (2,2)-bishydroxyphenylpropane and fumaric acid/terefucuric acid (mixed molar ratio = 50150)
: 63°C, weight average molecular weight M-; 13.300, s
, p, value: 9.8 (cat/cm') A crystalline polymer block and an amorphous polymer block having a value of 9.8 (cat/cm') or more were produced as follows.

Synthesis of crystalline polymer blocks A, B, C and amorphous polymer blocks a, d> Carboxylic acid component and alcohol component were mixed in 1 mol: 1.1
Four of them were charged into a Lough flask in a molar mixing ratio, and p-toluenesulfonic acid was added as an esterification catalyst to the mixture at a ratio of 0% to the total weight of the carboxylic acid component and alcohol component.
．． Add at a ratio of 0.5 weight. The reaction temperature is maintained at 180 to 200°C under a nitrogen stream, and the reaction is allowed to proceed until water distillation stops. When distillation of water stops under normal pressure, the pressure is reduced using an aspirator-1 vacuum pump, etc., and further condensation is carried out.

When the distillation of water stops under reduced pressure, the reaction is stopped and the synthesized polyester is taken out. This polyester has an OH group at the end of the molecule.

Synthesis of amorphous polymer blocks b and c> 1 mol: 400 to 500 μl of the it form and benzene as a solvent
4,4"-azobis-4-cyanovaleric acid having a carboxyl group as an initiator was added at a ratio of 1% by weight to the monomers to form a solution. Polymerization is carried out.The reaction temperature is maintained at 80°C, the temperature at which benzene refluxes, and the reaction is carried out for 5 to 6 hours.After the reaction is stopped, 7 volumes of the liquid are purified by precipitation in methanol, filtered and dried. This polymer has a carboxyl group at the end of the molecule.

[Example 1] 30 parts by weight of the crystalline polymer block A and 70 parts by weight of the amorphous polymer block a were dissolved in a solvent consisting of xylene containing 1 volume of both. Then, while refluxing, 5% by weight of hexamethylene diisocyanate, based on the entire polymer, was added dropwise as a coupling agent. After reacting for 30 to 60 minutes, the solvent was completely distilled off using a 7-spirator, a vacuum pump, etc. to take out the copolymer, thereby obtaining a copolymer. This will be referred to as "Copolymer 1".

The weight average molecular weight of this copolymer 1, the dynamic elastic modulus G',
The dynamic viscosity η' is shown in Table 1 below.

100 parts by weight O carbon black 10 parts by weight Mogull LJ (manufactured by Cabosoto Co., Ltd.) or higher materials were mixed and predispersed, then kneaded with heated rolls, cooled, and then pulverized. A toner with an average particle size of 11p was obtained.
”.

[Example 2] 30 parts by weight of Shibazato Imao Tachido crystalline polymer block B and 70 parts by weight of amorphous polymer block b were added to a solvent made of xylene that dissolves both, and uniformly dissolved. Then, dibutyltin oxide as an esterification catalyst is added to this in a proportion of 0.1% by weight based on the entire polymer, and a condensation reaction is carried out. After the reaction, the solvent and water were completely distilled off using an aspirator-1 vacuum pump or the like to take out the copolymer, thereby obtaining a copolymer. This will be referred to as "Copolymer 2".

Weight average molecule 1Mw of this copolymer 2, dynamic elastic modulus σ,
The dynamic viscosity η is shown in Table 1 below.

A toner having an average particle size of IIn was obtained by treating a substance equal to or greater than Mogul LJ (manufactured by Caponoto Co., Ltd.) in the same manner as in Example 1. .

This will be referred to as "toner 2".

[Example 3] 30 parts by weight of the Shiba Sakakin Seikoku Ritsukai crystalline polymer block C and 70 parts by weight of the amorphous polymer block C were added to a solvent consisting of xylene that dissolves both, and the mixture was uniformly dissolved. Hereinafter, the same treatment as in Example 2 was carried out to obtain a copolymer.

This will be referred to as "Copolymer 3".

Weight average molecular weight of this copolymer 3 -1, dynamic elastic modulus G'
, dynamic viscosity η' are shown in Table 1 below.

Example 1: Copolymer 3100 Parts Heavy 0 Carbon Black 10 parts by weight Mogul LJ (manufactured by Kabonoto Co., Ltd.)
A toner having an average particle size of 11-1 was obtained by processing in the same manner as above. This will be referred to as "toner 3."

[Example 4] Processing was carried out in the same manner as in Example 3 except that the crystalline polymer block C was changed to 10 parts by weight and the amorphous polymer block C was changed to 90 parts by weight. A copolymer was obtained.

1 waviness is defined as "copolymer 4".

The weight average molecule iMw of this copolymer 4, the dynamic elastic modulus σ,
The dynamic viscosity η' is shown in Table 1 below.

Preparation of toner 0 Copolymer 4100 parts by weight 0 Carbon black 10 parts by weight [Mogul Lj (manufactured by Caboft Co., Ltd.) The above substances were treated in the same manner as in Example 1 to obtain a toner having an average particle size of lIn.

This will be referred to as "toner 4".

(Example 5) Sori Risseiko Manufacturing Example 3, except that the crystalline polymer Pro, Ri C was changed to 70 parts by weight, and the amorphous polymer block C was changed to 30 parts by weight. A polymer was obtained.

This is referred to as "Copolymer 5".

Weight average molecule 1Mw of this copolymer 5, dynamic elastic modulus σ,
The dynamic viscosity η' is shown in Table 1 below.

A toner having an average particle size of llym was obtained by treating a material equal to or greater than Mogul LJ (manufactured by Capot Co., Ltd.) in the same manner as in Example 1. .This is called "Toner 5J."

[Comparative Example 1] 30 parts of the furnace copolymer crystalline polymer block A and 70 parts by weight of the amorphous polymer block d were placed in a solvent consisting of xylene that dissolved both. The mixture was dissolved and treated in the same manner as in Example 1 to obtain a copolymer. This is referred to as "comparative copolymer 1."

The weight average molecular weight 5, dynamic elastic modulus G', and dynamic viscosity η' of this ratio/membrane copolymer 1 are shown in Table 1 below.

Manufacture of Comparative Toner 0 Comparative Copolymer 1100 parts by weight 0 Carbon Brass 10 parts by weight "Mogul LJ" (Cabonoto Co., Ltd.) Got toner.

This is referred to as "comparative toner 1."

[Comparative Example 2] Comparison The same treatment was performed as in Example 3, except that the crystalline polymer block C was changed to 80 parts by weight, and the amorphous polymer block C was changed to 20 parts by weight. A polymer was obtained.

This is referred to as "comparative copolymer 2."

The weight average molecular N axis, dynamic elastic modulus σ, and dynamic viscosity η′ of this comparative copolymer 2 are shown in Table 1 below.

Manufacture of toner for ovens 2100 parts by weight of copolymer for comparison 0 Parts by weight of carbon blank 10 parts by weight "Mogul Lj" (manufactured by CABOFT) The above substances were treated in the same manner as in Example 1 to obtain an average particle size of 11
A toner of μ was obtained. This is referred to as "comparative toner 2."

Photo-photography test> Two parts by weight of each toner obtained in the above Examples and Comparative Examples and 98 parts by weight of resin liquid rgI iron powder carrier with an average particle size of 100μ were mixed to form a total of seven types of developers. The electrophotographic copying machine rU-Bix is prepared using these developers.
1600J (manufactured by Konishiroku Photo Industry Co., Ltd.) to form and develop an electrostatic image, transfer the resulting toner image onto transfer paper, and then fix it with a fixing device that uses a hot roller fixing method to form a copied image. A real photographic test was conducted to measure the lowest set temperature of the heating roller that is capable of fixing (minimum fixing temperature) and the lowest set temperature of the heating roller that causes the offset phenomenon (offset occurrence temperature).

The results are also shown in Table 1 below.

Storage test> Each toner was left in an atmosphere with a temperature of 40°C and a relative humidity of 55% for 2 hours, and depending on whether blocking occurred or not,
The quality of storage stability was determined.

The results are also shown in Table 1 below.

As can be understood from the results in Table 1, toners 1 to 5 according to the present invention all have a low minimum fixing temperature and a low offset occurrence of 21 degrees. It is possible to form a good image without any lag, and it also has excellent anti-blocking properties and has excellent storage stability as a powder.

On the other hand, according to Comparative Toner 1, the crystalline polymer block and the amorphous polymer block used to form the copolymer have poor compatibility, and therefore the offset generation temperature is low. Image stains caused by the offset phenomenon were observed at L2, making it impossible to obtain a good image, and the blocking resistance was poor, resulting in poor storage stability.

Claims (1)

[Claims] 1) Contains as a binder a copolymer formed by chemically bonding at least one crystalline polymer block and at least one amorphous polymer block, and the crystalline polymer block has a melting point of 40 to 120. °C, and the amorphous polymer block is substantially incompatible with the crystalline polymer block and has a glass transition temperature at least 10 °C above the melting point of the crystalline polymer block;
A toner for electrostatic image development for thermal roller fixing having excellent anti-offset properties, wherein the content of the crystalline polymer block in the copolymer is 10% by weight or more and less than 70% by weight.