JPH11171921A - Olefin-based resin and toner for electrophotography using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin usable for a binder resin for a toner for electrophotography, comprising a copolymer consisting of an α-olefin and specific maleic acid anhydride and/or maleic acid anhydride. SOLUTION: This resin comprises a copolymer composed of an α-olefin and maleic acid anhydride and/or a maleic acid ester which is partially, preferably 5-80 mol.% subjected to addition and/or cross-linked with preferably a bifunctional or polyfunctional amino compound by amidation reaction. The copolymer comprises a structural unit A of formula I(R is H or a 1-20C alkyl) and a structural unit B of formula II and/or formula III (R' is a 1-20 alkoxyl) and has 20-150 degree of polymerization, the ratio of structural unit A:B of 20:80 to 80:20 and 60-120 deg.C endothermic peak temperature (different scanning colorimeter).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to amidation of maleic anhydride and / or maleic ester constituting a copolymer of α-olefin and maleic anhydride and / or maleic ester with a compound having an amino group. The present invention relates to an olefin resin which can be used as a binder resin of an electrophotographic toner by reacting, and an electrophotographic toner using the resin, and particularly to an electrophotograph for a copying machine or a printer which employs heat roll fixing. The present invention relates to a toner for use.

[0002]

2. Description of the Related Art Generally, low-molecular-weight polyolefin resins are excellent in cold resistance, heat resistance, chemical resistance, abrasion resistance, etc., and therefore are used as processing improvers in processing rubber, plastics, etc., printing inks and paints. Used as a pigment dispersant, an abrasion resistance / blocking resistance improver, a polishing agent, a release agent, an electric insulating material, a rust inhibitor and the like. In the field of electrophotography, release agents are particularly noted among these applications, and polyolefin resins are widely used as release agents for toners used in copiers and printers to prevent the offset phenomenon. ing. In this case, it is impossible to use the olefin resin itself as a binder resin as a main component of the toner because it is difficult to achieve both the prevention of toner offset and the fixing property. Therefore, in the prior art, the olefin resin must be dispersed and used at a rate of about 1 to 10% with respect to the binder resin as a main component of the toner such as a styrene acrylic copolymer or a polyester resin. Was.

However, when the olefin resin is used in a dispersing manner with respect to the binder resin, the olefin resin such as polyethylene or polypropylene wax having a low molecular weight is non-uniformly dispersed in the binder resin at the time of melt-kneading, and the chargeability is poor. There is a problem that the presence of unstable particles causes a decrease in image density. Further, in order to improve the dispersibility as described above, a method of adding a polyolefin wax having a polar group introduced therein has been studied. However, it has not been possible to obtain sufficiently uniform particles, and the problem has not been solved.

On the other hand, with the spread of printers or copiers in recent years, low energy consumption (reduction of power consumption) mainly for the purpose of dissemination to homes and multifunctionalization has been realized, and the printers and copiers have been located at the border between them. It is desired to increase the speed to spread in the so-called gray area, or to reduce the roll pressure to simplify the fixing roll to reduce the machine cost. Due to the widespread use of copiers equipped with functions and an automatic document feeder, electrophotographic toners used in copiers and printers have not only the above-described offset development prevention (offset resistance), but also low There is a demand for an electrophotographic toner that has excellent fixing strength to transfer paper and can perform low energy fixing even at a fixing temperature. In order to obtain such a low-energy fixable toner, conventionally, a polyolefin wax having a low melting point is blended with the binder resin, or the molecular weight of the binder resin is reduced to obtain a toner for electrophotography. The fixing temperature has been lowered to achieve low energy fixing. However, the technical means of blending the polyolefin wax having a low melting point causes poor dispersion of the binder resin as a main component of the toner as described above, and causes a problem in image characteristics.

On the other hand, when the molecular weight of the binder resin is reduced, the melting point is reduced when the molecular weight of the condensed resin represented by the polyester resin is reduced, but the viscosity is also reduced. There was a problem that occurred. In order to prevent this, it has been proposed to introduce a crosslinked structure to broaden the molecular weight distribution of the polyester resin. However, in this method, although the molecular weight distribution is broadened by cross-linking and the offset phenomenon can be suppressed, there is a problem that the low-temperature fixability deteriorates because the entire molecular weight is increased. For this reason, the glass transition point temperature (Tg) of the binder resin must be lowered for low-temperature fixing, so that blocking tends to occur and the storage stability cannot be satisfied. As described above, the conventional technology could not achieve low-temperature fixability while satisfying offset resistance and storage stability.

[0006]

SUMMARY OF THE INVENTION The present invention is an improvement on the olefin resin of the prior art as described above, and in the field of electrophotography, the resin itself is used as a binder resin as a main component of an electrophotographic toner. Is what makes it possible. An object of the present invention is to provide an electrophotographic toner which can be fixed at a low temperature, does not cause a problem such as an offset phenomenon, and has excellent fixing strength to transfer paper.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a copolymer of an α-olefin and maleic anhydride and / or maleic ester, wherein at least a part of the maleic anhydride and / or maleic ester is an amino compound. Which are added and / or crosslinked by an amidation reaction and an electrophotographic toner using the same.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The olefin-based resin of the present invention is a copolymer of α-olefin and maleic anhydride and / or maleic ester, in which an amino compound is added and reacted by amidation reaction with the maleic anhydride and / or maleic ester. And / or being crosslinked. By performing such a reaction, an amide bond is introduced into the copolymer, and while maintaining a low melting point,
It has become possible to use electrophotographic toner as a binder resin, which has been difficult with conventional techniques. In short, the electrophotographic toner using the olefin resin of the present invention as a binder resin, while maintaining the property of a low melting point, and improving the brittleness that is the property of the binder resin by a hydrogen bond derived from an amide bond, As the toner characteristics, it is possible to satisfy all of the low-temperature fixability, the offset resistance, and the storage stability that cannot be achieved by the conventional technology.

[0009] The olefin resin of the present invention preferably has an amino compound content of 5 to 80 mol% based on maleic anhydride units and maleic ester units. More preferably, it is 10 to 50 mol%. When the amount is less than 5 mol%, introduction of an amide bond is insufficient, and when used as a toner, durability and offset resistance may not be sufficiently imparted. Conversely, 8
If the amount is more than 0 mol%, the hydrogen bonding property due to the amide bond becomes too strong and the resin becomes tough, causing problems such as deterioration of grindability, increase in melting start temperature and increase in melt viscosity, and the characteristics of polyolefin resin. There is a possibility that the toner may be damaged and the low temperature fixability as a toner may not be obtained.

The copolymer of α-olefin and maleic anhydride and / or maleic ester used in the present invention is a differential scanning calorimeter (DSC: manufactured by Seiko Denshi Kogyo KK).
As a result of measurement in the measurement range from 10 ° C. to 200 ° C. by SC-120), the first endothermic peak temperature
The temperature is preferably from 0 to 120C, more preferably from 70 to 100C. When the endothermic peak temperature is lower than 60 ° C., the storage stability of the toner for electrophotography is deteriorated. On the contrary, when the temperature exceeds 120 ° C., it is not suitable for low-temperature fixing.

The method of measuring the endothermic peak temperature in the present invention is calculated according to ASTM D-3418-82. Specifically, 10 to 15 mg of a sample is collected and heated from room temperature to 200 ° C. in a nitrogen atmosphere at a temperature of 10 ° C./mi.
After heating at 200 ° C. and holding at 200 ° C. for 10 minutes, a pretreatment of quenching was performed, and then held again at 10 ° C. for 10 minutes and
The sample is heated to 200 ° C. at a rate of temperature rise of 200 ° C./min and measured.
The peak that appears first at that time is defined as the endothermic peak temperature.

The molecular weight of the copolymer used in the present invention is measured by gel permeation chromatography (hereinafter referred to as GPC). GPC measurement
1 ml of solvent (chloroform) per minute at 25 ° C
And a chloroform sample solution having a concentration of 0.4 gr / dl is injected at a flow rate of 8 mg as a sample weight to measure. Also,
In measuring the molecular weight of a sample, the measurement conditions in which the molecular weight distribution of the sample is within the range in which the logarithm of the molecular weight of the calibration curve created by several kinds of monodisperse polystyrene standard samples and the count number are linear are included. select. In this measurement, the reliability of the measurement was N under the above measurement conditions.
BS706 polystyrene standard sample (Mw = 28.8 × 1
0 ⁴ , Mn = 13.7 × 10 ⁴ , Mw / Mn = 2.1
It can be confirmed by the fact that Mw / Mn in 1) is 2.11 ± 0.10. The degree of polymerization of the copolymer used in the present invention is determined by the molecular weight measured by GPC, the structural unit of the α-olefin and maleic anhydride and / or maleic ester constituting the copolymer, and the proportion of the blending unit. Can be calculated from the following. In this case, the degree of polymerization of the copolymer is 2
It is preferably in the range of 0 to 150. When the degree of polymerization of the copolymer is less than 20, the resin strength becomes extremely small, and even if crosslinking is performed, sufficient resin strength cannot be obtained.
When used as a binder resin for electrophotographic toner, storage stability is impaired. Conversely, if the degree of polymerization of the copolymer is greater than 150, low melting point and low viscosity properties cannot be obtained, and
When used as a binder resin for electrophotographic toner, low-temperature fixability is impaired.

The monomer component α of the copolymer of the present invention
As the olefin, it is preferable to use an α-olefin having 22 or less carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene.
Heptene, 1-octene, 1-nonene, 1-decene, 1
-Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Eicosene, 1-docosene and the like. As the maleic acid ester, an alkyl ester having 20 or less carbon atoms represented by the following formula (3) can be appropriately used. For example, lower dialkyl such as dimethyl maleate, diethyl maleate and dibutyl maleate can be used. Esters are preferably used in the present invention.

The copolymer in the present invention comprises the above-mentioned monomer components, that is, α-olefin and maleic anhydride, α
-Copolymerizing an olefin and a maleic ester or an α-olefin and maleic anhydride and a maleic ester; In this case, the reaction between the α-olefin and maleic anhydride and / or maleic ester is not particularly limited, but is performed in a solvent and performed in the presence of a catalyst such as titanium chloride or triethylammonium. Is preferred. When the α-olefin is a gas, it is preferable to carry out the reaction while maintaining the inside of the reaction system at a constant pressure.

In the present invention, the copolymer is not particularly limited as long as it is a copolymer of an α-olefin and maleic anhydride and / or a maleic ester, and the copolymer has a structure represented by the following formula (1). Unit A,

Embedded image (R in the formula is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) It is preferable that R is a structural unit represented by the following formulas (2) and / or (3).

Embedded image (R ′ in the formula is an alkoxyl group having 1 to 20 carbon atoms) Further, the ratio of the structural units is A: B = 20: 80 to 8
When the copolymer having a ratio of 0:20 is used for the toner for electrophotography, it is preferable because excellent properties such as low-temperature fixability, offset resistance, and storage stability are achieved.

The amino compound used in the reaction of the present invention has an amino group in the molecule as shown below. For example, the aliphatic amino compound includes 1-amino acid.
Aminopropane, 1-aminobutane, 2-amino-2-
Butylpropane, 3- (dimethylamino) propylamine, 3-methoxypropylamine, 1-aminopentane, 1-aminohexane, 1-aminoheptane, 1-aminooctane, 1-aminodecane, 1-aminododecane, 1-amino Hexadecane, 2-ethylhexylamine, stearylamine, laurylamine, 3-amino-
1-propanol, 4-amino-1-butanol, 6-
Amino-1-hexanol, ethylenediamine, 1,2
-Diaminopropane, 1,3-diamino-2,2-dimethylpropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-
Diaminooctane, 1,8-diamino-3,6-dioxaoctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12
-Diaminododecane, polyethylenediamine, polypropylenediamine, diethylenetetramine, propylenediamine, dipropylenetriamine, diethylenetriamine, tetraethylenepentamine, m-hexamethylene-
Examples thereof include triamine, hexamethylenetetramine, bis-aminopropylpiperazine, polyoxyethylenediamine, and polyoxypropylenediamine.

Examples of the aromatic amino compound include aniline, p-aminoacetanilide, p-aminobenzoic acid, ethyl p-aminobenzoate, o-aminophenol, m-aminophenol, p-aminophenol, p-aminophenol, and p-aminophenol.
-Aminobenzaldehyde, o-phenylenediamine,
m-phenylenediamine, p-phenylenediamine,
1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,
4-diaminobenzoic acid, 3,5-diaminobenzoic acid,
3,3′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4′-diaminobenzophenone,
2,2'-ethylenedianiline, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 3,6-diaminocarbazole, 2,4-diamino Chlorobenzene, 2,5-diaminochlorobenzene, 3,5-diaminochlorobenzene, 2,4-diaminobenzene, 2,5-diamino-4
-Chlorotoluene, 2,4-diamino-6-chloropyrimidine, 2,4-diamino-6-chloro-1,3,5-
Triazine, 4,4'-diamino-3,3'-dichlorodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3'-diamino-4,
4'-dihydroxybiphenyl, 4,4'-diamino-
3,3′-dihydroxybiphenyl, 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane, 4,4′-diamino-2,2′-dimethylbibenzyl, 2,4- Diaminodiphenylamine, 4,
4'-diamino-1,2-diphenylethane, 4,4 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 2,7-diaminofluorene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 1,2-diamino-4-nitrobenzene , 1,3-diaminoxylene, diaminodiphenylsulfone, 3,3'-diaminobenzidine, 2,4'-diamino-6-dimethylamino-1,3,5-triazine and the like.

The alicyclic amino compounds include 1,1
2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4 ′
-Diaminodicyclohexylmethane, 1,4-diaminomethylcyclohexane, isophoronediamine and the like. In addition, each modified compound of the above-mentioned aliphatic amine compound, aromatic amine compound, and alicyclic amine compound can also be used.

Further, a polyamide resin can be used as an amino compound, and specifically, an amine-terminated type obtained by condensation polymerization of a diamine and a dicarboxylic acid and at least one terminal of which is an amino group can be used. Nylon 66, Nylon 610, Nylon 612, 8-type nylon, polyethylene oxylated nylon, non-crystalline nylon (transparent nylon), alcohol-soluble polyamide resin, polymerized fatty acid polyamide resin, liquid polyamide resin, modified aliphatic polyamide resin, aminopolyamide Examples of the resin include aliphatic polyamide resins such as polyamideamine, which is a condensate of a resin and a dimer acid (dimer fatty acid) with an aliphatic polyamine.

It is preferable to use a bifunctional or more functional amino compound among the above-mentioned amino compounds, since a crosslinked structure is formed and more excellent improvement in resin strength is achieved. In particular, when an aliphatic amino compound is used, crosslinking can be performed without impairing the low melting point and the low melt viscosity, which are characteristics of the olefin resin, so that particularly favorable characteristics can be obtained. In addition, it is preferable that 5 to 80 mol% of the maleic anhydride and / or maleic ester is crosslinked, since a low melting point and a low melt viscosity and good resin strength can be obtained. In addition, an aliphatic polyamide resin can also be used as the aliphatic amino compound. In this case, the amine value of the aliphatic polyamide resin used is
Preferably it is in the range of 20-500 mg KOH.
When the amine value is less than 20, the reactivity of the α-olefin with the copolymer of maleic anhydride and / or maleic ester is reduced because the number of terminal amino groups at the reaction site is small, and the resin strength is improved by crosslinking. Effect is not obtained. Conversely, when the amine value is larger than 500, the control of the crosslinking reaction becomes difficult and the crosslinking proceeds excessively, so that the melting start temperature and the melt viscosity of the olefin-based resin after crosslinking also increase, which is a characteristic of the olefin-based resin. Undesirably, properties such as low melting point and low melt viscosity are impaired, and desired properties cannot be obtained.

The olefin-based resin of the present invention is obtained by adding and / or cross-linking the above-mentioned amino compound to at least a part of the maleic anhydride and / or maleic ester. That is, the addition and / or cross-linking structure is an olefin-based resin having one or more structures represented by the following formulas (4), (5), (6) and (7).

Embedded image

Embedded image (Wherein X and Y are structural units other than the amino group of the amino compound)

The method for producing an olefin resin of the present invention comprises:
Mixing the above-mentioned copolymer of α-olefin and maleic anhydride or maleic acid ester with an amino compound, and forming a mixture of maleic anhydride and / or maleic acid ester,
The compound can be produced by forming an amide bond by reaction with an amino group of an amino compound.

Next, the electrophotographic toner of the present invention will be described. The electrophotographic toner of the present invention uses the above-mentioned olefin resin as a binder. Here, in addition to the above-mentioned preferred composition and characteristics of the olefin resin, the melting start temperature of the olefin resin is 60
It is preferable that it is -120 degreeC. More preferably,
70-100 ° C. If the melting start temperature is lower than 60 ° C., the preservability is impaired, and if it exceeds 120 ° C., the problem that the low-temperature fixability is impaired tends to occur. In order to control the melting start temperature of the olefin resin within such a range, the resin composition and the conditions of the crosslinking reaction may be appropriately adjusted.

Regarding the melting start temperature of the resin of the present invention,
Elevated flow tester (CFT-50, manufactured by Shimadzu Corporation)
0) using the following measurement conditions. (Measurement conditions) Plunger: 1 cm ² Die diameter: 1 mm Die length: 1 mm Load: 20 kgF Preheating temperature: 50 to 80 ° C Preheating time: 300 sec Heating rate: 6 ° C / min

The electrophotographic toner of the present invention contains at least the olefin resin described above and a colorant, and may use other resins, magnetic materials, charge control agents, and other additives as necessary. It can be manufactured by mixing these raw materials, hot-melt kneading, pulverizing, and classifying. For example, a super mixer or the like is used for mixing, a single screw extruder kneader, a twin screw extruder kneader, an extruder, a roller mixer, a Banbury mixer, a pressure kneader or the like is used for hot melt kneading, and a jet mill or a classifier is used for pulverization. For this, a dry air classifier or the like can be appropriately used.

As the binder resin of the electrophotographic toner of the present invention, other resins such as a styrene resin, a styrene acrylic copolymer resin, a polyester resin, and a polyethylene resin may be used together with the olefin resin of the present invention, if necessary. Resins such as resin, epoxy resin, silicone resin, polyamide resin, and polyurethane resin may be blended.
In this case, the compounding amount of the other resin is preferably 50% by weight or less in order not to impair the low-temperature fixability, the anti-offset property, and the storage stability of the toner using the olefin resin.

The coloring agents used in the present invention include carbon black, aniline blue, phthalocyanine blue,
Quinoline yellow, malachite green, lamp black, rhodamine-B, quinacridone and the like. The amount of the colorant added is 1 to 20% by weight based on the binder resin. As the charge control agent, a nigrosine dye, an ammonium salt, a pyridinium salt, an azine or the like for a positively charged toner is added in an amount of 0.1 to 10% by weight based on the binder resin. As the charge control agent for the negatively charged toner, a chromium complex, an iron complex, or the like is used. When the negative chargeability is too strong, it is possible to control the neutralization by adding the positive chargeability control agent.

Since the olefin resin used in the electrophotographic toner of the present invention itself has good releasability, it is not particularly necessary to add a release agent such as a wax. It is possible.

The magnetic material used in the electrophotographic toner of the present invention may be a ferromagnetic metal or alloy such as ferrite, magnetite, cobalt, nickel or the like, a compound containing these elements, or a ferromagnetic compound. Alloys that do not contain elements but become ferromagnetic when subjected to a suitable heat treatment, such as manganese-copper-aluminum, manganese-copper-tin and other alloys of the type called Heusler alloys containing manganese and copper, or Chromium dioxide and others can be mentioned. These magnetic materials are uniformly dispersed in the binder resin in the form of fine powder having an average particle size of 0.1 to 1 micron. The content of the toner 1
20 to 70 parts by weight per 100 parts by weight, preferably 40 to 70 parts by weight
70 parts by weight.

The toner for electrophotography of the present invention is mixed with a carrier comprising ferrite powder, iron powder and the like to form a two-component developer. When a magnetic substance is contained, it is used as a one-component developer as it is without mixing with a carrier, or used as a two-component developer when mixed with a carrier. Is also good. Furthermore, the present invention is also applicable to a non-magnetic one-component developing method.

[0031]

EXAMPLES The present invention will be described in more detail with reference to synthetic examples of the resin used in the present invention and examples of the present invention, but the present invention is not limited to these examples. In the examples, parts are parts by weight. <Synthesis Example 1> 500 g of a copolymer of 1-dodecene and maleic anhydride in a molar ratio of 1: 1 (molecular weight 10,000, endothermic peak temperature 73 ° C, saponification value 421.9 mgKOH / g)
And 57.1 g of 1,12-diaminododecane (0.28
5 mol, 15.2 mol% based on maleic anhydride) was placed in a glass 2-liter 4-neck flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet tube, and heated with a mantle heater to react at 160 ° C. After heating and stirring at a temperature under a nitrogen stream for 1 hour, the mixture was taken out in a molten state to obtain an olefin resin (resin A) of the present invention. The melting start temperature of this resin was 79 ° C. <Synthesis Example 2> 500 g of a copolymer of 1-eicosene and maleic anhydride at a molar ratio of 2: 1 (molecular weight: 12,000, endothermic peak temperature: 78 ° C, saponification value: 170.5 mgKOH / g)
And 15.8 g (0.18 mol, 23.7 mol% based on maleic anhydride) of 1,4-diaminobutane were placed in a glass 2-liter four-necked flask, and the same operation as in Synthesis Example 1 was carried out. An olefin resin (resin B) of the present invention was obtained. The melting start temperature of this resin was 80 ° C.

Synthesis Example 3 500 g of a 1: 1 copolymer of 1-hexadecene and dimethyl maleate (molecular weight: 950)
0, endothermic peak temperature 72 ° C, ester value 304.9 mg
KOH / g) and p-phenylenediamine 23.4 g
(0.225 mol, 16.
6 mol%) in a glass 2-liter 4-neck flask,
By the same operation as in Synthesis Example 1, the olefin resin (Resin C) of the present invention was obtained. The melting start temperature of this resin is 73
° C.

Synthesis Example 4 500 g of a copolymer of 1-octadecene and diethyl maleate in a molar ratio of 1: 2.5 (molecular weight 9800, endothermic peak temperature 70 ° C., ester value 40)
7.8 mg KOH / g) and 52.6 g of 4,4′-diaminodicyclohexylmethane (0.25 mol, 13.8 mol% based on diethyl maleate) were placed in a glass 2-liter four-necked flask, and the synthesis example was obtained. By the same operation as in 1, the olefin-based resin (resin D) of the present invention was obtained. The melting start temperature of this resin was 74 ° C.

Synthesis Example 5 500 g of a copolymer of 1-butene and maleic anhydride at a molar ratio of 3: 1 (molecular weight 6500,
Endothermic peak temperature 80 ° C, saponification value 421.9mgKOH
/ G) and an aliphatic polyamide resin (manufactured by Henkel Hakusui,
Trade name: Versamide 125, amine value 350mgKOH
/ G) 90 g (14.9 mol% based on maleic anhydride)
Was placed in a glass 2-liter four-necked flask, and the same operation as in Synthesis Example 1 was performed to obtain an olefin resin (Resin E) of the present invention. The melting start temperature of this resin is 83 ° C.
Met.

Synthesis Example 6 500 g of a copolymer of 1-dodecene and diethyl maleate in a molar ratio of 1: 1 (molecular weight: 10
000, endothermic peak temperature 75 ° C, ester value 330.1
mg KOH / g) and 1-aminohexadecane
5 g (1 mol, 34 mol% based on diethyl maleate) was placed in a glass 2-liter four-necked flask, and an olefin-based resin (resin F) was obtained in the same manner as in Synthesis Example 1. The melting start temperature of this resin was 70 ° C.

<Comparative Synthesis Example 1> 500 g of a copolymer of styrene and maleic anhydride having a molar ratio of 1: 1 (molecular weight: 500
0, saponification value 555.5 mgKOH / g, glass transition temperature 65 ° C), and 80.1 g of 1,12-diaminododecane
(0.4 mol, 16.2 mol% based on maleic anhydride) was placed in a glass 2-liter four-necked flask, and a resin for comparison (resin G) was obtained in the same manner as in Synthesis Example 1. . The melting start temperature of this resin was 135 ° C. <Comparative Synthesis Example 2> 500 g of a copolymer of 1-hexadecene and acrylic acid at a molar ratio of 2: 1 (molecular weight 7000, endothermic peak temperature 78 ° C, acid value 107.9 mgKOH / g),
34.6 g of 1,8-diaminooctane (0.24 mol,
(50 mol% based on acrylic acid) was placed in a glass four-necked flask, and a resin for comparison (resin H) was obtained in the same manner as in Synthesis Example 1. The melting start temperature of this resin is 79
° C.

Next, the resin of each of the above Synthesis Examples and Comparative Synthesis Example was mixed with the other raw materials in the following mixing ratio using a super mixer, kneaded with a melt, kneaded, and crushed and classified to obtain an average particle diameter of 11%.
After obtaining μm particles, 0.3 parts of hydrophobic silica (trade name: R-972, manufactured by Nippon Aerosil Co., Ltd.) was adhered to the particles using a Henschel mixer to obtain a negatively chargeable electrophotographic toner. <Example 1> Resin A 100 parts Carbon black 6.5 parts (MA-100, manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (TRH, manufactured by Hodogaya Chemical Industry Co., Ltd.)

Example 2 Resin B 100 parts Carbon black 6.5 parts (MA-600 manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (Bontron S-34 manufactured by Orient Chemical Co., Ltd.)

Example 3 Resin C 100 parts Carbon black 6.5 parts (MA-100 manufactured by Mitsubishi Chemical Corporation) Iron-based complex dye 2 parts (T-77 manufactured by Hodogaya Chemical Industry Co., Ltd.)

Example 4 Resin D 100 parts Carbon black 6.5 parts (MA-600 manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (Bontron S-34 manufactured by Orient Chemical Company)

<Example 5> Resin E 100 parts Carbon black 6.5 parts (MA-100 manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (TRH manufactured by Hodogaya Chemical Industry Co., Ltd.)

Example 6 Resin F 100 parts Carbon black 6.5 parts (MA-100, manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (TRH, manufactured by Hodogaya Chemical Industry Co., Ltd.)

Comparative Example 1 Resin G 100 parts Carbon black 6.5 parts (MA-100 manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (Bontron S-34 manufactured by Orient Chemical Co., Ltd.)

<Comparative Example 2> Resin H 100 parts Carbon black 6.5 parts (MA-600 manufactured by Mitsubishi Chemical Corporation) Iron-based complex salt dye 2 parts (T-77 manufactured by Hodogaya Chemical Industry Co., Ltd.)

Comparative Example 3 Copolymer of 1-dodecene and maleic anhydride in Synthesis Example 1 100 parts Carbon black 6.5 parts (MA-100 manufactured by Mitsubishi Chemical Corporation) Chromium complex salt dye 2 parts (Orient Chemical Co., Ltd.) Bontron S-34)

<Comparative Example 4> 100 parts of polyester resin (D-001 manufactured by Nippon Carbide Industry Co., Ltd.) 6.5 parts of carbon black (MA-600 manufactured by Mitsubishi Chemical Corporation) 2 parts of chromium complex salt dye (manufactured by Orient Chemical Company Bontron S-34)

The following evaluations were made for the above Examples and Comparative Examples. (1) Fixing temperature range 4 parts of the toner for electrophotography obtained in the above Examples and Comparative Examples and 96 parts of a ferrite carrier without a resin coating (trade name: FL-1020, manufactured by Powder Tech) are mixed. And a two-component developer. Next, using the developer, a plurality of unfixed belt-shaped images each having a length of 2 cm and a width of 5 cm were formed on A4 transfer paper using a commercially available copying machine (Z-133 manufactured by Sanyo Electric Co., Ltd.). Next, a fixing device in which a heat fixing roll having a surface layer formed of Teflon and a pressure fixing roll having a surface layer formed of silicone rubber rotate in pairs, a roll pressure of 1 kg / cm ² and a roll speed of 200 m.
m / sec, and the surface temperature of the heat-fixing roll was increased stepwise by 5 ° C. to fix the toner image of the transfer paper having the unfixed image at each surface temperature. . At this time, by observing whether or not the toner image is fixed and whether or not the toner stain is caused by the offset in the margin, the maximum value and the minimum value of the temperature region where the fixation of the toner image is sufficient and the margin is not stained are performed. Is the fixing temperature width. Since the fixing device is set at a maximum of 230 ° C.,
When good at 30 ° C, it was evaluated as 230 ° C or higher.

(2) Fixing Strength The surface temperature of the heat fixing roll of the fixing machine was set to 130 ° C., and the toner image on the transfer paper on which the unfixed image was formed was fixed. Then, after measuring the image density of the formed fixed image using a reflection densitometer (RD-914, manufactured by Macbeth), the fixed image was rubbed with a cotton pad with a fastness tester (load: 300 g / load). cm ² , 5 reciprocations), and the image density of the rubbed portion was measured in the same manner.
From the obtained measured values, the fixing strength was calculated according to the following formula, and was used as an index for the low-temperature fixing toner. Table 1 shows the results. Fixing strength (%) = (image density of fixed image after rubbing / image density before rubbing) × 100

[0049]

[Table 1]

As is clear from the results shown in Table 1, the fixing temperature range of the electrophotographic toner using the olefin resin of the present invention was 100 ° C., except for Example 6 in which no crosslinking was performed.
It was confirmed that the toner had the above width, was fixed in the range of 100 to 110 ° C. on the low temperature side, had no offset generation up to a high temperature, and had excellent offset resistance. Further, the electrophotographic toners of Examples 1 to 6 of the present invention were all 13
Since the fixing strength at a fixing temperature of 0 ° C. is 80% or more and has a practically sufficient fixing strength, it was confirmed that the fixing ability was excellent at low temperature. Furthermore, the image density of the developed image was sufficient, and there was no fogging of the non-image portion, which was practically sufficient. On the other hand, the electrophotographic toners of Comparative Examples were all inferior in offset resistance and could not obtain a fixing temperature range. Further, regarding the fixing strength, all the toners of the comparative examples were inferior in low-temperature fixability, and could not be evaluated at 130 ° C. due to occurrence of offset or unfixed.

Further, a continuous copy test of up to 10,000 sheets was performed using each developer and the copying machine using the electrophotographic toner of the embodiment prepared in the evaluation of the fixing temperature range described in (1) above. Was. As a result, in all the examples, when the frictional charge was from the initial to 10,000 sheets by the blow-off frictional charge measuring device (manufactured by Toshiba Chemical Co., Ltd.), -2.
The value changes in the range of 5 μc / g to −29 μc / g, and the image density also changes during the continuous copying from the initial stage to 10,000 sheets.
4 or more, and a color difference meter (Z-100 manufactured by Nippon Denshoku Co., Ltd.)
The background fog of the non-image portion measured by 1DP) was 0.6 or less, and it was confirmed that there was no practical problem. Further, even when the electrophotographic toner of each example was left at 50 ° C. for 2 days, no occurrence of blocking or caking was observed, and the toner had good storage stability.

[0052]

According to the olefin resin of the present invention, an amide bond is introduced into a copolymer of an α-olefin and maleic anhydride and / or a maleic ester by reaction with an amino compound. Can be used as a binder resin as a main component of an electrophotographic toner. In addition, while maintaining the low melting point and low melt viscosity, it is possible to impart excellent offset resistance, without impairing the storage stability, which could not be achieved by the conventional technology, An electrophotographic toner having excellent low-temperature fixability and satisfying offset resistance can be obtained. Therefore, when the present invention is applied to a copying machine, a printer, or the like, the power consumption can be reduced, which is extremely effective for reducing the mechanical cost by reducing the pressure of the roll, increasing the copying speed, and the like. Furthermore, the olefin-based resin of the present invention has physical properties that the compatibility with other resins and the solubility in a solvent are greatly improved, which was impossible with a conventional olefin-based resin. Thus, the present invention has an operational effect that enables the application of the present invention to be developed.

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Claims (9)

[Claims] 1. A copolymer of an α-olefin and maleic anhydride and / or maleic ester, wherein an amino compound is added to at least a part of the maleic anhydride and / or maleic ester. Olefin resin. 2. The olefin system according to claim 1, wherein the amino compound is a bifunctional or higher functional amino compound, and at least a part of the maleic anhydride and / or maleic ester is crosslinked. resin. 3. The copolymer comprises a structural unit A represented by the following formula (1): (Wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It comprises a structural unit B represented by the following formula (2) and / or (3), and has a polymerization degree of 20 to 150. The olefin resin according to claim 1 or 2, wherein Embedded image (R ′ in the formula is an alkoxyl group having 1 to 20 carbon atoms) 4. The olefin resin according to claim 3, wherein the ratio of the structural unit A to the structural unit B is A: B = 20: 80 to 80:20. 5. The olefin resin according to claim 1, wherein an endothermic peak temperature of the copolymer measured by a differential scanning calorimeter is 60 to 120 ° C. 6. The olefin resin according to claim 2, wherein 5 to 80 mol% of the maleic anhydride and / or maleic ester is crosslinked. 7. The olefin resin according to claim 2, wherein the bifunctional or higher functional amino compound is an aliphatic amine compound. 8. The bifunctional or higher functional amino compound is an aliphatic polyamide resin having an amine value of 20 to 500 mg.
The olefin resin according to any one of claims 2 to 7, wherein the olefin resin is KOH / g. 9. An electrophotographic toner comprising at least a colorant and the olefin resin according to claim 1. Description: