JPH09265208A - Resin composition for toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner resin compsn. and a toner having excellent low temp. fixing property and a wide fixing temp. range, with which an enough stable image can be obtd. even when a fast or small-size electrophotographic copying machine is used. SOLUTION: This resin compsn. for a toner and the toner have specified complex elastic modulus, relaxation elasticity and relaxation time. For example, the absolute value |G*<0> 1 | of the complex elastic modulus measured at 1 rad/sec angular frequency and 0.5% strain amplitude is 10<7> Pa at >=70 deg.C. The absolute value |G*<0> 2 | measured at 100 rad/sec angular frequency and 1% strain amplitude is 5×10<4> at <=135 deg.C. The relaxation elasticity G<0> measured under conditions of 190 deg.C and 450% initial strain in 0.02sec after the strain in added, the period from the time when strain added to the time the relaxation elasticity reaches G<0> /100 is >=0.15sec.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for toner used in electrophotography and the like, and more specifically to a resin composition for toner used in a dry developing method in a method of developing an electrostatic image. The thing and the toner.

[0002]

2. Description of the Related Art In electrophotography and the like, a dry developing system is often used as a method for developing an electrostatic charge image. In this dry development method, triboelectricity is obtained by mixing iron powder, glass beads, or other carrier with fine powder in which a binder resin such as a toner resin contains a colorant such as carbon black and other additives such as a charge control agent. Toner (developer) is used.

In order to obtain a copy, an electrostatic latent image is usually formed on a photoconductor, and triboelectrically-charged toner is electrically attached to the electrostatic latent image to develop it. The toner image is transferred onto a sheet such as a sheet of paper and then fixed by a hot-pressing roller having releasability to the toner to form a permanent visible image.

This type of toner mainly has anti-offset property (the toner adheres to a heat-pressing roller for fixing and does not stain the paper) and low-temperature fixability (the toner firmly adheres to the paper at low temperature). ), Blocking resistance (non-aggregation of toner particles), and image stability (no change in charge amount and uniform image density) are required. Further, a resin composition for toner having good fine pulverizability is also required.

A toner having improved main properties such as anti-offset property, low-temperature fixing property and anti-blocking property is composed of a low molecular weight vinyl resin component and a high molecular weight vinyl resin component. A toner using a resin composition for a toner composed of a styrene polymer or a (meth) acrylic acid ester polymer is widely known (for example, JP-A-56-158340).

[0006]

However, the conventional resin compositions for toners and toners of this kind have good offset resistance, low-temperature fixing property and blocking resistance, and have a certain level of image stability. However, when copying using a high-speed type or small-sized electronic copying machine, which has been in increasing demand in recent years, the above performance is not always sufficiently satisfactory. There is a demand for a toner having further improved properties.

The present invention solves the problems of such conventional resin compositions for toners and toners, and its objects are offset resistance, low temperature fixability,
A resin composition for a toner, which has excellent blocking resistance, particularly excellent low temperature fixing property, a wide fixing temperature range, and a sufficiently stable image can be obtained even when copying using a high-speed type or a small electronic copying machine. To provide goods and toner.

[0008]

The toner resin composition of the present invention has an angular frequency of 1 rad / sec and a strain amplitude of 0.5.
Absolute value of complex elastic modulus measured in% | G ^* ₁ | is 10 ⁷ P
a temperature of 70 ° C or higher and an angular frequency of 100ra
The absolute elastic modulus value | G ^* ₂ | measured at d / sec of 3% strain amplitude is 10 ⁴ Pa at 170 ° C. or lower, and at 190 ° C. and 450% initial strain, the relaxation elastic modulus In the measurement, when the relaxation elastic modulus 0.02 seconds after the strain is applied is G, the time from the application of the strain until the relaxation elastic modulus becomes G / 100 is 0.15 seconds or more. As a feature, the above objective can be achieved.

The toner of the present invention has an angular frequency of 1r.
The temperature at which the absolute value | G ^{* 0} ₁ | of the complex elastic modulus measured at ad / sec and strain amplitude 0.5% is 10 ⁷ Pa is 70 ° C. or higher, the angular frequency is 100 rad / sec, and the strain amplitude 1
Absolute value of complex elastic modulus measured in% | G ^{* 0} ₂ | is 5 × 10
^The temperature at which the pressure reaches ⁴ Pa is 135 ° C or lower, and the temperature is 190
In the measurement of relaxation elastic modulus at ℃, initial strain 450%,
Characterized in that the relaxation modulus after 0.02 seconds from the addition of strain when a G ^0, the time until the relaxation modulus after adding distortion becomes G ^0/100 is greater than or equal to 0.15 seconds Therefore, the above object can be achieved.

The resin composition for the toner resin composition and toner of the present invention include vinyl resins, polyester resins, epoxy resins, xylene resins, coumarone-indene resins, styrene-butadiene-styrene block copolymer resins, butyral. Resin, terpene resin, rosin,
Petroleum resin or the like is used. Among them, styrene-based polymers, (meth) acrylic acid ester-based polymers and polyester resins that fall into the category of vinyl-based resins are preferable.

These resin components may be either non-crosslinked type or crosslinked type. Further, as these resin components, a single resin may be used, or two or more kinds of resins may be used in combination. When two or more resins are used in combination, these resins may be compatible with each other to have a single-phase structure, or may be incompatible with each other to have a phase-separated structure.

Since the physical properties of the resin component which is incompatible and has a phase-separated structure are strongly influenced by its dispersion shape and size, the resin after sufficiently kneading with a roll mill, a kneader, an extruder or the like is used. The components are used for measuring physical properties.

The toner resin composition of the present invention includes:
In particular, a blended resin in which a low molecular weight styrene- (meth) acrylic acid ester copolymer and a high molecular weight styrene- (meth) acrylic acid ester copolymer are compatibilized at a molecular level. Auxiliary agent (higher alcohol, higher fatty acid, higher fatty acid ester, etc.) for improving low-temperature fixing property that melts at 80 ° C. and / or auxiliary agent for improving fixing strength (rubber-like styrene rubber, acrylic at room temperature) Rubber, olefin rubber, etc.), a blended resin of a low molecular weight styrene polymer and a high molecular weight polyester, an auxiliary agent and / or a fixing strength for improving the low temperature fixability of the blended resin. The thing etc. which mix | blended the auxiliary agent for improving are used suitably.

In the dynamic viscoelasticity test, the toner resin composition of the present invention has an absolute value of complex elastic modulus | G ^* ₁ measured at an angular frequency of 1 rad / sec and a strain amplitude of 0.5%.
The temperature at which | becomes 10 ⁷ Pa is 70 ° C. or higher, and the absolute value of complex elastic modulus | G ^* ₂ | measured at an angular frequency of 100 rad / sec and a strain amplitude of 3% is 10 ⁴ Pa.
In the measurement of the relaxation elastic modulus at 70 ° C. or lower and at a temperature of 190 ° C. and an initial strain of 450%, 0.0 was measured after strain was applied.
When the relaxation elastic modulus after 2 seconds is G, the time from the addition of strain until the relaxation elastic modulus reaches G / 100 must be 0.15 seconds or more.

Here, the complex elastic modulus and relaxation elastic modulus of the resin composition for toner are measured by a dynamic viscoelasticity tester (viscoelasticity spectrometer), for example, RM manufactured by Rheometrics.
Measured by S-800. In the measurement of the relaxation elastic modulus, 0.02 seconds after the strain is applied means substantially the moment when the strain is applied.

Absolute value of the complex elastic modulus | G^* ₁| Is 10
⁷If the temperature at which Pa is less than 70 ° C., the resulting toner
Blocking resistance of the film becomes insufficient. Especially complex elasticity
Absolute value of rate | G^* ₁| Is 10⁷The temperature to reach Pa is 75 ° C
The above is preferred. The absolute value of the complex elastic modulus | G^*
_Two| Is 10^FourIf the temperature of Pa exceeds 170 ° C,
The low temperature fixability of the obtained toner becomes insufficient. Especially the complex
Absolute value of elastic modulus | G^* _Two| Is 10^FourThe temperature that becomes Pa is 1
It is preferably 40 ° C or lower. Also, after adding distortion
It takes less than 0.15 seconds until the sex rate reaches G / 100
Is insufficient in the offset resistance of the toner.
The contact temperature range cannot be obtained. In particular, the relaxation elastic modulus is G
The time to reach / 100 is preferably in the range of 0.2 to 2 seconds.
New

The toner resin composition of the present invention has the specific complex elastic modulus, relaxation elastic modulus and relaxation time as described above.

Using such a resin composition for toner,
To obtain the toner of the present invention, for example, a conventional toner additive such as a colorant and a charge control agent is blended with the toner resin composition as described above, and this is roll-milled.
A method of kneading using a kneader, an extruder or the like, then cooling and finely pulverizing is adopted.

As the colorant, carbon black,
Pigments or dyes commonly used for this type of toner such as chrome yellow and aniline blue are used. Also,
As the charge control agent, a dye control agent composed of a dye such as nigrosine, spirone black (manufactured by Hodogaya Chemical Co., Ltd.) or other phthalocyanine pigments is used. Further, polypropylene wax, low molecular weight polyethylene, other aliphatic amides, bisaliphatic amides, metal soaps, paraffins and the like, which have a releasing action on the fixing roller of a copying machine, may be blended.

Hydrophobic silica or the like may be added later in order to improve the fluidity of the toner particles. Further, in order to obtain a magnetic toner, magnetic powder made of iron or zinc such as magnetite, ferrite or hematite, or an alloy or compound showing ferromagnetism such as zinc, cobalt, nickel or manganese may be mixed.

In the dynamic viscoelasticity test, the toner of the present invention has an angular frequency of 1 rad / sec and a strain amplitude of 0.5.
Absolute value of complex elastic modulus measured in% | G ^{* 0} ₁ | is 10 ⁷ P
a temperature of 70 ° C or higher and an angular frequency of 100ra
Absolute value | G ^{* 0} ₂ | of the complex elastic modulus measured at d / sec and strain amplitude of 1% is 5 × 10 ⁴ Pa, the temperature is 135 ° C. or lower, and relaxation is performed at a temperature of 190 ° C. and an initial strain of 450%. in the measurement of the elastic modulus, when the relaxation modulus after 0.02 seconds from the addition of strain to the G ^0, the relaxation modulus from addition of distortion the time until the G ^0/100 0.15 seconds Must be above.

Here, the complex elastic modulus and relaxation elastic modulus of the toner are measured by a dynamic viscoelasticity testing device (viscoelasticity spectrometer), for example, RMS-800 manufactured by Rheometrics. In the measurement of the relaxation elastic modulus, 0.02 seconds after the strain is applied means substantially the moment when the strain is applied.

The absolute value of the complex elastic modulus | G ^{* 0} ₁ | is 10
^{If the} temperature at which the pressure reaches ⁷ Pa is less than 70 ° C., the blocking resistance of the resulting toner will be insufficient. In particular, the temperature at which the absolute value of complex elastic modulus | G ^{* 0} ₁ | becomes 10 ⁷ Pa is 75 ° C.
The above is preferred. Also, the absolute value of the complex elastic modulus | G ^{* 0}
_{When the} temperature at which ₂ | becomes 5 × 10 ⁴ Pa exceeds 135 ° C., the low temperature fixability of the obtained toner becomes insufficient. Particularly, the temperature at which the absolute value of complex elastic modulus | G ^{* 0} ₂ | becomes 5 × 10 ⁴ Pa is preferably 125 ° C. or lower. Further, the time until the relaxation modulus after adding distortion becomes G ^0/100 is less than 0.15 seconds, insufficient offset resistance of the toner can not be obtained sufficiently wide fixing temperature range. In particular, the time until the relaxation elastic modulus reaches G ^0/100 is 0.
The range of 2 to 2 seconds is preferable.

The toner of the present invention has the specific complex elastic modulus, relaxation elastic modulus and relaxation time as described above.

(Function) Toner blocking occurs because the mobility of the molecules constituting the toner particles is increased by heat and the entanglement with the constituent molecules of the toner particles in contact with each other occurs, and the toner is resistant to blocking. Is the mobility of the molecules of the resin composition for toner or the toner,
That is, it has been found that there is a relation with hardness, and it can be evaluated by the absolute value | G ^* | of the complex elastic modulus.

Therefore, the absolute value of complex elastic modulus | G ^* ₁ | measured at an angular frequency of 1 rad / sec and a strain amplitude of 0.5%.
There the temperature to be 10 ⁷ Pa is using the toner resin composition above 70 ° C., it has been found that blocking of the toner is improved. Also, the absolute value of the complex elastic modulus measured at an angular frequency of 1 rad / sec and a strain amplitude of 0.5% | G ^{* 0} ₁ |
It was found that even when a toner having a temperature of 10 ⁷ Pa of 70 ° C. or higher is used, the blocking resistance of the toner is improved.

Further, the fixing of the toner is carried out by melting and deforming the toner particles with a hot pressing roller to increase the contact area with the paper, and the low temperature fixing property of the toner depends on the resin composition for toner or the deformation of the toner. It has been found that there is a relationship with ease and this can also be evaluated by the absolute value | G ^* | of the complex elastic modulus.

Therefore, the angular frequency is 100 rad / sec,
Absolute value of complex elastic modulus measured at a strain amplitude of 3% | G ^* ₂ |
It was found that the low temperature fixability of the toner is improved by using a toner resin composition having a temperature of 10 ⁴ Pa of 170 ° C. or less. Further, when a toner whose temperature at which the absolute value | G ^{* 0} ₂ | of the complex elastic modulus measured at an angular frequency of 100 rad / sec and a strain amplitude of 1% is 5 × 10 ⁴ Pa is 135 ° C. or lower, the toner is fixed at a low temperature. It was found that the sex is improved.

On the other hand, toner offset occurs when the cohesive force of the melted toner is smaller than the adhesive force between the toner and the hot pressing roller, and the offset resistance of the toner depends on the cohesive force of the toner resin composition or the toner. It has been found that there is a relationship between the size and the length of relaxation time of the toner resin composition or toner under large deformation.

Therefore, the temperature is 190 ° C. and the initial strain is 450%.
In the measurement of the relaxation elastic modulus at 0.
When the relaxation elastic modulus after 02 seconds is G, the time from the addition of strain until the relaxation elastic modulus becomes G / 100 is 0.15.
It has been found that the offset resistance of the toner is improved by using a toner resin composition having a viscosity of at least 2 seconds. Further, in the measurement of the relaxation elastic modulus at a temperature of 190 ° C. and an initial strain of 450%, the relaxation elastic modulus 0.02 seconds after the strain is applied is G.
^{When 0} is set, the relaxation elastic modulus is G ^0/1 after the strain is applied.
It has been found that the offset resistance of the toner is improved even when a toner having a time until it reaches 00 is 0.15 seconds or more is used.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples of the present invention will be described below. Example 1 Production of Resin Composition for Toner A spiral stirrer, a reflux condenser, a nitrogen introducing pipe, and a thermocouple for temperature measurement were attached to a 3 liter cylindrical reactor, and 100 parts by weight of toluene and 10,000 of the weight average molecular weight were attached to this. 100 parts by weight of styrene-methyl methacrylate copolymer (component ratio: former 75% by weight / latter 25% by weight), styrene-n-butyl acrylate copolymer having a weight average molecular weight of 810,000 (component ratio: former 90% by weight / 10 parts by weight of the latter (10% by weight) and 10 parts by weight of polyethylene wax having a weight average molecular weight of 800 and a melting point of 80 ° C. were added and heated to the boiling point of toluene while purging with nitrogen, and the boiling state of toluene was maintained for 4 hours. The weight average molecular weight of the copolymer is a value measured by gel permeation chromatography (GPC) method.

Then, the reflux condenser was removed and a pressure reducing device was attached, and the mixture was heated to 140 to 170 ° C. to distill off toluene,
A resin composition for toner comprising the above two kinds of copolymers and wax was obtained. This toner resin composition is composed of styrene-
The wax had a phase-separated structure in which a wax formed domains in a matrix in which a methyl methacrylate copolymer and a styrene-n-butyl acrylate copolymer were compatible.

In this toner resin composition, the temperature at which the absolute value | G ^* ₁ | of the complex elastic modulus measured at an angular frequency of 1 rad / sec and a strain amplitude of 0.5% is 10 ⁷ Pa is 7
6 ° C. Also, the angular frequency is 100 rad / sec,
Absolute value of complex elastic modulus measured at a strain amplitude of 3% | G ^* ₂ |
The temperature at which the pressure reaches 10 ⁴ Pa was 126 ° C. further,
In the measurement of the relaxation elastic modulus at a temperature of 190 ° C. and an initial strain of 450%, when G is the relaxation elastic modulus 0.02 seconds after the strain is applied, the relaxation elastic modulus is G / 1 after the strain is applied.
The time to reach 00 was 0.25 seconds.

Manufacture of Toner 100 parts by weight of the above resin composition for toner, 6 parts by weight of carbon black (MA-100: manufactured by Mitsubishi Kasei), 1 part by weight of Spiron Black TRH (manufactured by Hodogaya Chemical Co., Ltd.),
3 parts by weight of polypropylene wax (Viscor 660P: manufactured by Sanyo Kasei Co., Ltd.) were melt-kneaded in a roll mill, cooled and coarsely pulverized, and then finely pulverized and further classified in a jet mill.
A toner powder having an average particle size of about 11 μm was obtained. To this toner powder, 0.3 part by weight of hydrophobic silica powder (R-972: manufactured by Nippon Aerosil Co., Ltd.) was post-added (externally added) to obtain a toner.

With this toner, the angular frequency is 1 rad /
The temperature at which the absolute value of the complex elastic modulus | G ^{* 0} ₁ | measured at sec and a strain amplitude of 0.5% was 10 ⁷ Pa was 75 ° C. or higher. Further, the absolute value of complex elastic modulus | G ^{* 0} ₂ | measured at an angular frequency of 100 rad / sec and a strain amplitude of 1% is 5 × 1.
The temperature at which it reached 0 ⁴ Pa was 117 ° C. Furthermore, in the measurement of the relaxation elastic modulus at a temperature of 190 ° C. and an initial strain of 450%, the relaxation elastic modulus 0.02 seconds after the strain was applied was G.
^{When 0} is set, the relaxation elastic modulus is G ^0/1 after the strain is applied.
The time to reach 00 was 0.22 seconds.

Evaluation of Toner Performance With respect to the above toner, the low temperature fixing property of the toner and the storage stability of the toner were evaluated by the following methods. As a result, the fixing temperature range was 119 ° C to 200 ° C (or higher), the low-temperature fixing property was excellent, and the fixing temperature range was wide. Further, the storage stability of the toner was good (toner passage rate 99%).

<Low-Temperature Fixing Property of Toner> 4 parts by weight of toner and 96 parts by weight of iron powder carrier having an average particle size of about 50 to 80 μm are uniformly mixed to prepare a developer, which is used for electrophotographic copying. A fixing test was carried out by a machine to determine the fixing temperature range.

In the fixing test, copying is performed by changing the set temperature of the heat-pressing roller for fixing of the electrophotographic copying machine step by step, and no offset (double image) is generated. When the density of the copied image was less than 10% when rubbed with an eraser, the fixability was determined to be good, and the range was set as the fixing temperature range. The electrophotographic copying machine used was a VIVACE 310 manufactured by Fuji Xerox Co., Ltd.
It is modified so that the temperature of the hot pressing roller for fixing can be changed within a range of about 100 to 200 ° C.

<Toner storage stability> 1 g of 10 g of toner
Take it in a 00 ml sample bottle and leave it in a constant temperature bath at 50 ° C for 8 hours. Then, pass this toner through a sieve with an opening of 250 μm, and the toner storage stability is good when the toner passage rate is 95% or more. And

The complex elastic modulus and the relaxation elastic modulus were measured under the following conditions. - complex modulus | G ^* ₁ | and | G ^{* 0} ₁ | measuring apparatus: manufactured by Rheometric Scientific Inc. RMS-800 jig: diameter 25 mm, disk - disk jig heating rate temperature: 2 ° C. / minute angular frequency: 1 rad / sec strain amplitude: 0.5% · complex modulus | G ^* ₂ | and | G ^{* 0} ₂ | measuring apparatus: manufactured by Rheometric Scientific Inc. RMS-800 jig: diameter 25 mm, disk - disk jig heating Velocity temperature: 3 ° C./min Angular frequency: 100 rad / sec Strain amplitude: 3% and 1% ・ Measurement of relaxation elastic modulus G and G ⁰ Device: RMS-800 manufactured by Rheometrics Jig: Diameter 25 mm, cone-disk healing Ingredient temperature: 190 ° C Initial strain: 450%

Example 2 A 3 liter cylindrical reactor was equipped with a spiral stirrer, a reflux condenser, a nitrogen inlet tube, and a thermocouple for measuring temperature. To this, 100 parts by weight of toluene and styrene-methyl having a weight average molecular weight of 10,000 were attached. Methacrylate-hydroxyethyl methacrylate copolymer (component ratio: 75% by weight / 10% by weight / 15
% By weight) 100 parts by weight, styrene-n-butyl acrylate copolymer having a weight average molecular weight of 810,000 (component ratio: 90% by weight / 10% by weight) 10 parts by weight, weight average molecular weight 800
Then, 10 parts by weight of a polyethylene wax having a melting point of 80 ° C. and 2 parts by weight of a styrene block copolymer (S-EB-S rubber) (Clayton G1726: manufactured by Shell Co.) are added and heated to the boiling point of toluene while purging with nitrogen, and the toluene is boiled. The maintained state was maintained for 4 hours.

Then, the reflux condenser was removed and a decompression device was attached, and the mixture was heated to 140 to 170 ° C. to distill off toluene,
A resin composition for toner comprising the above two kinds of copolymers, wax and S-EB-S rubber was obtained. In this resin composition for toner, a wax and S-EB-S have domains in a matrix in which a styrene-methyl methacrylate-hydroxyethyl methacrylate copolymer and a styrene-n-butyl acrylate copolymer are compatible. It had the formed phase separation structure.

In this toner resin composition, the temperature at which the absolute value of complex elastic modulus | G ^* ₁ | becomes 10 ⁷ Pa is 77.
° C. In addition, the absolute value of complex elastic modulus | G ^* ₂ |
The temperature at which it reached 0 ⁴ Pa was 122 ° C. Furthermore, the time required for the relaxation elastic modulus to reach G / 100 was 0.21 seconds.

Other than using this toner resin composition
Was carried out in the same manner as in Example 1 to obtain a toner. This toner
, The absolute value of complex elastic modulus | G^{* 0} ₁| Is 10⁷Pa
The temperature at which was 75 ° C. or higher. Also, the complex elastic modulus
Absolute value ｜ G^{* 0} _TwoIs 5 × 10 ^FourThe temperature at which Pa is 115
It was ℃. Furthermore, the relaxation elastic modulus is G⁰/ 100
Time was 0.20 seconds.

The fixing temperature range is 115 ° C to 195 ° C.
Thus, the low temperature fixability was excellent and the fixing temperature range was wide. Further, the storage stability of the toner was good (toner sieve passing ratio of 98%).

Example 3 A 3 liter cylindrical reactor was equipped with a spiral stirrer, a reflux condenser, a nitrogen inlet tube, and a thermocouple for measuring temperature. To this, 100 parts by weight of toluene and 100 parts by weight of polystyrene having a weight average molecular weight of 10,000 were attached. Parts, 15 parts by weight of polystyrene having a weight average molecular weight of 750,000, 10 parts by weight of behenyl alcohol, 2 parts by weight of styrene block copolymer (S-EB-S rubber) (Kreighton G1726: manufactured by Shell Co.), and boiling point of toluene while purging with nitrogen. The mixture was heated to 40 ° C., and the boiling state of toluene was maintained for 4 hours.

Then, the reflux condenser was removed and a decompression device was attached, and the mixture was heated to 140 to 170 ° C. to distill off toluene,
A resin composition for toner comprising the above-mentioned two kinds of polymers, behenyl and S-EB-S rubber was obtained. This toner resin composition had a phase-separated structure in which behenyl alcohol and S-EB-S formed domains in a matrix in which low-molecular weight polystyrene and high-molecular weight polystyrene were compatible.

In this resin composition for toner, the temperature at which the absolute value of complex elastic modulus | G ^* ₁ | becomes 10 ⁷ Pa is 73.
° C. In addition, the absolute value of complex elastic modulus | G ^* ₂ |
The temperature at which it reached 0 ⁴ Pa was 125 ° C. Furthermore, the time required for the relaxation elastic modulus to reach G / 100 was 0.24 seconds.

A toner was obtained in the same manner as in Example 1 except that this toner resin composition was used. In this toner, the absolute value of complex elastic modulus | G ^{* 0} ₁ | is 10 ⁷ Pa
The temperature at which this was 74 ° C was The temperature at which the absolute value of the complex elastic modulus | G ^{* 0} ₂ | became 5 × 10 ⁴ Pa was 117 ° C. Furthermore, the relaxation modulus is the time until the G ^0/100 0.21 seconds.

The fixing temperature range is 120 ° C to 200 ° C.
(Above), the low temperature fixability was excellent and the fixing temperature range was wide. Further, the storage stability of the toner was good (toner sieve pass ratio: 97%).

Comparative Example 1 A 3 liter cylindrical reactor was equipped with a spiral stirrer, a reflux condenser, a nitrogen inlet tube, and a thermocouple for measuring temperature. To this, 100 parts by weight of toluene and styrene-methyl having a weight average molecular weight of 10,000 were attached. Methacrylate-n-butyl acrylate copolymer (component ratio: 75% by weight / 10% by weight / 15% by weight)
100 parts by weight of styrene having a weight average molecular weight of 810,000-n-
Butyl acrylate copolymer (component ratio: 90% by weight / 1
15 parts by weight, 10 parts by weight of polyethylene wax having a weight average molecular weight of 800 and a melting point of 80 ° C. are added,
It was heated to the boiling point of toluene while purging with nitrogen, and the boiling state of toluene was maintained for 4 hours.

Then, the reflux condenser was removed and a decompression device was attached, and the mixture was heated to 140 to 170 ° C. to distill off the toluene,
A resin composition for toner comprising the above two kinds of polymers and wax was obtained. This toner resin composition has a phase-separated structure in which a wax forms a domain in a matrix in which a styrene-methyl methacrylate-n-butyl acrylate copolymer and a styrene-n-butyl acrylate copolymer are compatible. I was taking it.

In this toner resin composition, the temperature at which the absolute value of complex elastic modulus | G ^* ₁ | becomes 10 ⁷ Pa is 67.
° C. In addition, the absolute value of complex elastic modulus | G ^* ₂ |
The temperature at which it reached 0 ⁴ Pa was 120 ° C. Furthermore, the time required for the relaxation elastic modulus to reach G / 100 was 0.25 seconds.

A toner was obtained in the same manner as in Example 1 except that this toner resin composition was used. In this toner, the absolute value of complex elastic modulus | G ^{* 0} ₁ | is 10 ⁷ Pa
The temperature at which was 65 ° C. The temperature at which the absolute value of complex elastic modulus | G ^{* 0} ₂ | was 5 × 10 ⁴ Pa was 113 ° C. Furthermore, the relaxation modulus is the time until the G ^0/100 was 0.22 seconds.

The fixing temperature range is 113 ° C to 200 ° C.
Thus, the low temperature fixability was excellent and the fixing temperature range was wide. However, the storage stability of the toner was poor at a toner passage rate of 87%.

Comparative Example 2 A 3 liter cylindrical reactor was equipped with a spiral stirrer, a reflux condenser, a nitrogen inlet tube, and a thermocouple for measuring temperature. To this, 100 parts by weight of toluene and styrene-methyl having a weight average molecular weight of 10,000 were attached. Methacrylate-n-butyl acrylate copolymer (component ratio: 75% by weight / 20% by weight / 5% by weight) 1
00 parts by weight, 15 parts by weight of a styrene-methyl methacrylate-n-butyl acrylate copolymer having a weight average molecular weight of 470,000 (component ratio: 85% by weight / 10% by weight / 5% by weight) were added, and toluene was added while purging with nitrogen. The mixture was heated to the boiling point and the boiling state of toluene was maintained for 4 hours.

Then, the reflux condenser was removed and a pressure reducing device was attached, and the mixture was heated to 140 to 170 ° C. to distill off the toluene,
A resin composition for toner comprising the above two copolymers was obtained. This resin composition for toner comprises a low molecular weight styrene-
Methyl methacrylate-n-butyl acrylate copolymer and high molecular weight styrene-methyl methacrylate-n-
It was compatible with the butyl acrylate copolymer and had a single-phase structure.

In this resin composition for toner, the temperature at which the absolute value of complex elastic modulus | G ^* ₁ | becomes 10 ⁷ Pa is 76.
° C. In addition, the absolute value of complex elastic modulus | G ^* ₂ |
The temperature at which the pressure was 0 ⁴ Pa was 135 ° C. Furthermore, the time required for the relaxation elastic modulus to reach G / 100 was 0.11 seconds.

A toner was obtained in the same manner as in Example 1 except that this toner resin composition was used. In this toner, the absolute value of complex elastic modulus | G ^{* 0} ₁ | is 10 ⁷ Pa
The temperature at which was 76 ° C. The temperature at which the absolute value of the complex elastic modulus | G ^{* 0} ₂ | became 5 × 10 ⁴ Pa was 120 ° C. Furthermore, the relaxation modulus is the time until the G ^0/100 was 0.10 seconds.

The fixing temperature range is 125 ° C to 150 ° C.
The fixing temperature range was narrow although the low temperature fixing property was excellent. In addition, the storage stability of the toner was good (toner sieving rate 99%).

Comparative Example 3 A 3 liter cylindrical reactor was equipped with a spiral stirrer, a reflux condenser, a nitrogen inlet tube, and a thermocouple for measuring temperature. To this, 100 parts by weight of toluene and styrene-methyl having a weight average molecular weight of 10,000 were attached. Methacrylate-hydroxyethyl acrylate copolymer (component ratio: 75 wt% / 10 wt% / 15 wt%) 100 parts by weight, styrene-n-butyl acrylate copolymer having a weight average molecular weight of 810,000 (component ratio: 90 wt% / 10% by weight) 35 parts by weight, polyethylene wax having a melting point of 80 ° C. 5 parts by weight, styrene block copolymer (S
2 parts by weight of (EB-S rubber) (Kreton G1726: manufactured by Shell Co.) was added, and the mixture was heated to the boiling point of toluene while purging with nitrogen, and the boiling state of toluene was maintained for 4 hours.

Thereafter, the reflux condenser was removed and a pressure reducing device was attached, and the mixture was heated to 140 to 170 ° C. to distill off toluene,
A resin composition for toner comprising the above two kinds of copolymers, wax and S-EB-S rubber was obtained. This toner resin composition is a matrix in which a styrene-methyl methacrylate-hydroxyethyl acrylate copolymer and a styrene-n-butyl acrylate copolymer are compatible.
The wax and S-EB-S rubber had a phase-separated structure in which domains were formed.

In this resin composition for toner, the temperature at which the absolute value of complex elastic modulus | G ^* ₁ | becomes 10 ⁷ Pa is 81.
° C. In addition, the absolute value of complex elastic modulus | G ^* ₂ |
The temperature at which the pressure was 0 ⁴ Pa was 172 ° C. Furthermore, the time required for the relaxation elastic modulus to reach G / 100 was 0.53 seconds.

A toner was obtained in the same manner as in Example 1 except that this toner resin composition was used. In this toner, the absolute value of complex elastic modulus | G ^{* 0} ₁ | is 10 ⁷ Pa
Was 77 ° C. The temperature at which the absolute value of complex elastic modulus | G ^{* 0} ₂ became 5 × 10 ⁴ Pa was 136 ° C. Furthermore, the relaxation modulus is the time until the G ^0/100 0.51 seconds.

The fixing temperature range is 155 ° C to 200 ° C.
At (above), the low temperature fixability was poor. In addition, the storage stability of the toner was good (toner sieving rate 99%).

The results of each Example and each Comparative Example are summarized in Table 1 above.

[0067]

[Table 1]

[0068]

The resin composition for a toner and the toner of the present invention are constituted as described above and have a specific complex elastic modulus, relaxation elastic modulus and relaxation time, whereby the anti-offset property and the low temperature fixing can be achieved. Excellent in stability and blocking resistance, particularly excellent in low-temperature fixing property, wide fixing temperature range, and sufficiently stable image can be obtained even when copying using a high-speed type or small electronic copying machine. Has a great effect.

Therefore, according to the resin composition for a toner and the toner of the present invention, it is possible to sufficiently meet the increasing demands in recent years, such as high speed copying, downsizing, and energy saving.

Claims (2)

[Claims] 1. The absolute value of complex elastic modulus | G ^* ₁ | measured at an angular frequency of 1 rad / sec and a strain amplitude of 0.5% is 1.
The temperature at which the pressure reaches 0 ⁷ Pa is 70 ° C or higher and the angular frequency is 10
The temperature at which the absolute value of the complex elastic modulus | G ^* ₂ | measured at 0 rad / sec and a strain amplitude of 3% is 10 ⁴ Pa is 170 ° C.
In the measurement of the relaxation elastic modulus at a temperature of 190 ° C. and an initial strain of 450% below, when the relaxation elastic modulus 0.02 seconds after the strain is applied is G, the relaxation elastic modulus after the strain is applied is A resin composition for toner, wherein the time until it reaches G / 100 is 0.15 seconds or more. 2. The absolute value of complex elastic modulus | G ^{* 0} ₁ | measured at an angular frequency of 1 rad / sec and a strain amplitude of 0.5% is 1.
The temperature at which the pressure reaches 0 ⁷ Pa is 70 ° C or higher and the angular frequency is 10
The temperature at which the absolute value | G ^{* 0} ₂ | of the complex elastic modulus measured at ⁰ rad / sec and a strain amplitude of 1% is 5 × 10 ⁴ Pa is 13
In the measurement of the relaxation elastic modulus at 5 ° C. or less and at a temperature of 190 ° C. and an initial strain of 450%, 0.02 after the strain is applied.
When the relaxation modulus after seconds was G ^0, the time the relaxation modulus after adding distortion to the G ^0/100 0.15
Toner characterized by being over a second.