JPH09151291A - Resin composition for electrophotographic toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can give a toner which shows excellent charging characteristics even when the composition contains little or no charge modifier and to provide a toner containing the same. SOLUTION: This resin composition for an electrophotographic toner is a resin composition comprising an ethylene polymer (H) having a weight-average molecular weight(Mw) of 200,000-1,000,000 and an Mw/Mn ratio of 8-200 (Mn is the number-average molecular weight) and an ethylene polymer (L) having an Mw of 3,000-20,000. Polymers H and/or L, desirably polymer H should be ethylene polymers obtained by polymerizing ethylene in the presence of a monomer (M) having an ionization potential (IP) and a difference between the highest occupied molecular orbital(HOMO) level and the lowest unoccupied molecular orbital(LUMO) which are obtained by a technique of calculative chemistry of 9.0-15.0eV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for an electrophotographic toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, and an electrophotographic toner containing the same.

[0002]

2. Description of the Related Art In a toner installed in a copying machine or a printer, "charge rising property", that is, a characteristic that the amount of charge of the toner is instantly charged to an appropriate value when the machine such as the copying machine or the printer is started up Is required.
Conventionally, a charge control agent (hereinafter,
It has been common to add a metal-containing dye such as a metal salt of salicylic acid called CCA) to the toner.
However, recently, this CCA contains heavy metals, and since many of them are highly toxic and expensive, the toner resin itself has the function of CCA to reduce the amount of CCA, or to use it at all. Attempts have been made not to do so.

For example, Japanese Patent Publication No. 5-88472 discloses an application of a polymer containing a maleic acid derivative. However, these techniques have a problem in that toner particles become non-uniformly charged, fogging is likely to occur, and developability is poor.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a resin composition for an electrophotographic toner having a fast charge rise and a sufficient charge amount even in a toner not using CCA or a toner having a reduced use amount. The present invention provides an electrophotographic toner containing the above-mentioned toner, which has properties required for an electrophotographic toner, that is, good thermophysical properties, good fixability at high and low temperatures, and does not cause defective phenomena such as offset and blocking. .

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have completed the present invention by defining the electron energy levels of resin constituent components.

That is, according to the present invention, the weight average molecular weight (hereinafter, M
w) is 200,000 to 1,000,000, and the ratio (Mw / Mn) of Mw and number average molecular weight (referred to as Mn) is 8 to 300. 5 to 95 parts by weight of ethylene polymer (H) and Mw is 3 1,000-20,000 ethylene-based polymer (L) 9
A resin composition comprising 5 to 5 parts by weight, wherein the (H) and / or (L) is obtained by an ionization potential (hereinafter referred to as IP) of 10.0 to 15.0 eV and a computational chemical method. Obtained by polymerization in the presence of a monomer (M) having a difference between the highest occupied molecular orbital (hereinafter, referred to as HOMO) level and the lowest unoccupied molecular orbital (hereinafter, referred to as LUMO) level is 9.0 to 15.0 eV. It is a resin composition for electrophotographic toners, which is an ethylene polymer.

The above resin composition preferably has the following constitution.

The monomer (M) is a vinyl polycarboxylic acid,
It should be selected from the group consisting of vinylsilanes and (meth) acryloyloxyalkyldicarboxylic acid esters.

The total amount of the constituent monomers of the ethylene polymer (H) is 100 parts by weight, and the proportion of the monomer (M) in the total amount is 3 to 45 parts by weight.

The (meth) acryloyloxyalkyl dicarboxylic acid esters are represented by the general formula (1)

[0011]

Embedded image (In the formula, m is an integer of 1 to 7, n is an integer of 1 to 3, X is H or CH ₃ , and Y is H, an alkyl group having 1 to 8 carbon atoms or a benzyl group.). Be represented.

The monomer (M) is 1 to 20 parts by weight of at least one monomer selected from the group consisting of maleic anhydride, itaconic anhydride, glutaconic anhydride and 2-carboxycinnamic anhydride. (Meta) represented by general formula (1)
It is composed of at least one kind of acryloyloxyalkyl dicarboxylic acid ester, and the total amount of the monomer M is 3 to 45.
Must be parts by weight.

The ethylene polymer (L) has an acid value (hereinafter referred to as A
V) is 0.5 to 200 mgKOH / g and the weight average molecular weight (Mw) is 8,000 to 20,000. Ethylene polymer (H) and ethylene polymer (L)
A resin composition having a total acid value of 0.5 to 200 m
Must be gKOH / g.

It has a polyfunctional monomer and / or a polyfunctional initiator residue as a constituent of the ethylene polymer (H).

A resin composition comprising an ethylene polymer (H) and an ethylene polymer (L), and having a glass transition temperature (hereinafter referred to as Tg) of 45 to 75 ° C.

The present invention also provides an electrophotographic toner (hereinafter referred to as toner) using the above-mentioned resin composition for electrophotographic toner (hereinafter referred to simply as resin composition).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises ethylene polymers (H) and (L), wherein the ethylene polymer (H) has a weight average molecular weight (Mw) of 200,000 to 1,000,000.
The ratio of Mw and Mn (Mw / Mn) is 8 to 300, preferably 8 to 150.

This is necessary for the toner using the resin composition to have high temperature offset resistance, and Mw is 20.
If it is less than 10,000 and less than Mw / Mn8, high-temperature offset property occurs, which is not preferable, and Mw25 is preferable.
10,000-850,000, Mw / Mn8-150, more preferably 1
It is in the range of 0-40.

Further, Mw is larger than 1 million, and Mw /
If Mn is larger than 300, the winding property is deteriorated due to the Weisenberg phenomenon, and the fixing temperature is high, which is not preferable. And, in order to fix at a temperature as low as possible, the weight average molecular weight (Mw) of the ethylene polymer (L) is 2
It is required to be 50,000 or less, and more preferably 3,000 to 10,000. Polymer Mw
Is more than 20,000, the melt viscosity at the time of fixing is increased, and the minimum fixing temperature is raised, which is not preferable. If it is less than 3,000, the toner strength is lowered and a large amount of fine powder is generated, which lowers productivity and is not preferable.

The mixing ratio of the ethylene polymer (L) and the ethylene polymer (H) is (L) :( H) = 5.
-95: 95-5, preferably 10-90: 90-1
It is preferably 0, more preferably 15 to 85:85 to 15 in order to keep the balance of blocking property, resin strength and the like when used as a toner. Further, when (H) is excessive, the fixing temperature becomes high, and when (H) is small, the rise of charging and the charging stability decrease.

In the ethylene polymer (H), the difference between the highest occupied molecular orbital (HOMO) level and the lowest unoccupied molecular orbital (LUMO) level obtained by a computational chemical method is 9.0 to 15.
0, preferably 9.0 to 12.5 eV, and a monomer (M) having an ionization potential (IP) value of 10.0 to 15.0, preferably 10.0 to 13.5 eV as a constituent element And the proportion of the monomer (M) is 100 parts by weight of the total constituent monomers, preferably 3 to 45.
Parts by weight, more preferably 6 to 45 parts by weight, more preferably 6 to 40 parts by weight, particularly preferably 8 to 30 parts by weight.

In the above monomer (M), the energy difference between the HOMO level and the LUMO level by the chemical calculation method is 9.0.
It is required to be ˜15.0 eV, and if it is out of this range, the selection range of carriers to be combined is narrowed, which is not preferable.

The value of ionization potential (IP) is required to be 10.0 to 15.0 eV. This is a requirement from the viewpoint of polymer manufacturability.
When it is less than 0.0 eV, the reactivity is too high, and when it is more than 15.0 eV, the reactivity is too low, which is not preferable.

Calculation of various energy levels was carried out as follows.

A semiempirical molecular orbital method program MOP for the unit model structure in which hydrogen is added to the olefin part of each monomer (M) assuming the resin composition state of the monomer (M).
Structural optimization is performed using the AM1 approximation of AC93, and the highest occupied molecular orbital (HOMO) energy level (hereinafter, E (H
OMO)) and the lowest unoccupied molecular orbital (LUMO) energy level (hereinafter referred to as E (LUMO)).

The result obtained by calculation is that of 25 ° C., a molecular isolated system.

Ionization potential (IP), electron affinity (hereinafter referred to as EA), E (HOMO) and E (LUM)
O) energy difference (hereinafter referred to as E (DIFF)),
The work function (hereinafter referred to as WF) was calculated as follows.

IP, EA and E (DIFF) were calculated as follows.

(Calculation of Ionization Potential (IP))
Koopmans' theorem (literature; T. Koopman
s, Physica, 1 , 104 pp (1933)), IP has the same value as E (HOMO), but has the opposite sign, ie, IP = − (E (HOMO)) (1) ) Similarly, EA indicates the same value as E (LUMO) but the sign is opposite, that is, EA = − (E (LUMO)) (2) and E (DIFF) is E (DIFF) = E (LUMO) -E (HOMO) = IP-EA (3) Regarding the work function (WF), the following relational expression (reference;
N. R. Rajopadhye, S .; V. Bhoras
kar, J .; Mater. Sci. Lett. , 5 , 6
03pp (1986)).

WF = E (DIFF) / 2 + EA (4) Specific examples of the monomer (M) include vinyl polyvalent carboxylic acids, vinyl silanes, and the above-mentioned general formula (1). It is roughly classified into (meth) acryloyloxyalkyl dicarboxylic acid esters and other compounds.

The vinyl polycarboxylic acid includes the following. Regarding the numerical value in parentheses described after the compound name, the former is IP and the latter is E (DIFF). (1) 2-dodecenedicarboxylic acid, (IP = 10.2,
E (DIFF) = 10.4) (2) trans-butenedicarboxylic acid, (10.4,
10.0) (3) 3,5-pyrazole dicarboxylic acid, (10.1,
9.5) (4) 1,2,3-propylene tricarboxylic acid, (1
1.6, 11.0) (5) 3-butene-1,2,3-tricarboxylic acid, (1
0.9, 10.8) (6) 3-methoxy-5-methyl-4-oxo-2,5
-Hexadienoic acid. (10.4, 10.8) Moreover, the following are mentioned as vinylsilanes. (7) Methacryloxymethyltrimethylsilane, (1
0.3, 11.6) (8) Trimethylsilyl methacrylate, (10.5,
11.4) (9) Tris (trimethylsiloxy) -3-methacryloxypropylsilane, (10.3 11.9) (10) Methacryloxypropylmethyldiethoxysilane, (10.8, 10.9) (11 ) Acryloxytrimethylsilane, (10.9,
11.2) (12) Bistrimethylsilyl itaconate, (10.
9, 11.9) (13) (methacryloxymethyl) bis (trimethylsiloxy) methylsilane, (12.6, 10.8) (14) 2- (trimethylsiloxy) ethylmethacrylate (10.4, 12.0) (15) 2- (acryloxyethoxy) trimethylsilane, (11.1, 10.4) (16) 3-methacryloxypropyltrimethoxysilane, (12.4, 10.3) (17) 3- (methacryloxy) ) Propyltriethoxysilane, (13.8, 9.4) (18) 3-methacryloxypropyl bis (trimethylsiloxy) methylsilane, (11.8, 10.4) (19) (3-acryloxypropyl) methyl Bis (trimethylsiloxy) silane, (12.1, 10.
6) (20) (3-acryloxypropyl) dimethylmethoxysilane, (13.4, 10.2) (21) (3-acryloxypropyl) tris (trimethylsiloxy) silane, (10.5, 11.8) (22) (3-acryloxypropyl) trimethoxysilane, (11.8, 10.6) (23) O- (trimethylsilyl) acrylate. (1
0.3, 11.6) The (meth) acryloyloxyalkyldicarboxylic acid esters represented by the general formula (1) can be exemplified as follows. (24) 2-methacryloyloxymethyl malonic acid,
(10.8, 10.4) (25) 2-methacryloyloxyethyl malonic acid,
(10.6, 10.5) (26) 2-methacryloyloxypropyl malonic acid,
(10.5, 10.2) (27) 2-methacryloyloxymethyl succinic acid,
(11.5, 10.4) (28) 2-methacryloyloxyethyl succinic acid,
(11. 3, 10.5) (29) 2-methacryloyloxypropyl succinic acid,
(11.0, 10.2) (30) 2-methacryloyloxymethyl glutaric acid,
(11.8, 11.2) (31) 2-methacryloyloxyethyl glutaric acid,
(11.5, 10.4) (32) 2-methacryloyloxypropyl glutaric acid, (11.4, 10.9) (33) 2-acryloylmethyl malonic acid, (10.
9, 10.5) (34) 2-acryloylethylmalonic acid, (10.
8, 10.5) (35) 2-acryloylpropyl malonic acid, (10.
4, 10.2) (36) 2-acryloylmethyl succinic acid, (11.
4, 10.5) (37) 2-acryloylethyl succinic acid, (11.
2, 10.5) (38) 2-acryloylpropyl succinic acid, (11.
1, 10.3) (39) 2-acryloylmethyl glutaric acid, (11.
6, 10.8) (40) 2-acryloylethyl glutaric acid, (11.
5, 10.6) (41) 2-acryloylpropyl glutaric acid, (1
1.2, 10.5) and so on. Among them, the use of 2-methacryloyloxyethylsuccinic acid is particularly effective.

At least one selected from the group consisting of at least one kind of (meth) acryloyloxyalkyldicarboxylic acid ester represented by the above general formula (1) and maleic anhydride, glutaconic anhydride and 2-carboxysuccinic acid. The most preferred embodiment is the combined use of 1 to 20 parts by weight of the seed monomer.

Further, other compounds include the following. (42) 2-Hexanoic acid, (10.3, 9.8) (43) 2-octenoic acid, (10.2, 9.9) (44) Glycol methacrylate, (10.4, 1)
0.2) (45) dihydroxymaleic acid, (11.6, 1
2.2) (46) 2,3-epoxypropyl methacrylate, (1
1.2, 12.2) (47) 2,3-epoxypropyl acrylate, (1
1.4, 12.6) (48) Ethyl 3-amino-4-pyrazolecarboxylic acid, (10.5, 9.9) (49) 3-Amino-4-pyrazolecarboxylic acid, (1
0.4, 9.6) (50) 3-Methylenedihydro-2 (3H) -furanone, (10.8, 9.8) (51) Dimethylethylidene malonate, (11.3,
12.0) (52) methyl 2-butenoate 3-trimethylsiloxane, (11.1, 10.8) (53) diethyl ethylidene malonate, (10.8,
11.1) (54) Diethyl isopropylidene malonate, (10.
6, 10.7) (55) Diethyl ethoxymethylene malonate, (10.
9, 10.4) (56) Ethyl 3,3-diethoxy acrylate, (1
1.2, 10.6) (57) 2-cyanoethyl acrylate, (11.4,
10.9) (58) ethoxyethoxyethyl acrylate, (1
1.9, 10.8) (59) Isooctadecylsuccinic anhydride, (11.
7, 11.4) (60) 2,2,6-trimethyl-4H-1,3-dioxin-4-one, (10.9, 11.9) (61) monobutyl maleate, (11.3, 12.
1) (62) Dioctyl fumarate, (11.2, 12.
1) (63) glutaconic acid, (11.3, 10.1) (64) maleic anhydride, (11.8, 11.9) (65) dimethylitaconic acid, (13.4, 10.
2) (66) (E) -2-octadecenoic anhydride, (11.
8, 10.6) (67) 2- (2-methoxyethoxy) ethyl acrylate, (12.2, 10.8) (68) 2-methylenesuccinic acid, (10.8, 1)
1.1) (69) 2 furanylmethyl acrylate, (12.4,
13.6) (70) isopropylidene succinic acid, (11.2, 1
0.8) (71) Methyl 3-acetoxycyclotonate. (10.
8, 11.4) The above-mentioned monomer (M) may be contained in any of (H) and (L) of the ethylene polymer,
More preferably, it is included in (H). The ethylene polymer (L) has an Mw of 20,000 or less and an acid value (AV) of 0.5 to 200 mgKOH / g, preferably 0.5 to 150 mgKOH / g.

A polymer having an acid value (AV) of less than 0.5 mgKOH / g is not preferable because it is difficult to satisfy the charge rising property and stability when used as a toner, but the acid value (AV) is 200 mgKOH. If it is larger than / g, the hygroscopicity of the toner becomes large and blocking occurs, which is not preferable.

Further, in the resin composition comprising the ethylene polymer (H) and the ethylene polymer (L) of the present invention, the total acid value is 200 mgKOH / g or less, preferably 0.5 to.
It is required to be 150 mgKOH / g. When the total acid value (TAV) is larger than 200 mgKOH / g, the hygroscopicity of the toner becomes large, and blocking occurs, which is not preferable.

As the monomers for obtaining the ethylene polymers (L) and (H) of the present invention, styrene monomers such as styrene, α-methylstyrene, halogenated styrene, vinyltoluene, 4 -Sulfonamide styrene, 4-styrene sulfonic acid, etc .; Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , Benzyl (meth) acrylate, furfuryl (meth) acrylate, (meth) acrylic Hydroxyethyl, (meth) hydroxybutyl acrylate, (meth) acrylic acid dimethyl amino methyl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylate, 2-ethylhexyl (meth) 2-chloroethyl acrylic acid;
As itaconic acid esters, for example, dimethyl itaconic acid, dipropyl itaconic acid, butyl itaconic acid, dioctyl itaconic acid, diamyl itaconic acid and the like; as unsaturated carboxylic acids and unsaturated dicarboxylic acids, for example, (meth) acrylic acid, cinnamic acid, maleic acid Acids, fumaric acid, itaconic acid, etc .; Maleic acid esters and fumaric acid esters, for example, those having a linear or branched alkyl group having 1 to 8 carbon atoms, diethyl maleate, dipropyl maleate, dibutyl maleate, malein Acid dipentyl, dihexyl maleate, diheptyl maleate, dioctyl maleate, ethylbutyl maleate,
Ethyl octyl maleate, butyl octyl maleate, butyl hexyl maleate, pentyl octyl maleate, diethyl fumarate, dipropyl fumarate,
Dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, diheptyl fumarate, dioctyl fumarate, ethyl butyl fumarate, ethyl octyl fumarate, butyl octyl fumarate, butyl hexyl fumarate, pentyl octyl fumarate, etc .; other; 2-vinyl Examples thereof include, but are not limited to, naphthalene, itaconic anhydride, maleic anhydride, and the like.

Examples of the polyfunctional monomer and the polyfunctional initiator include styrene type monomers such as divinylbenzene acrylic polyfunctional monomers such as 1,3-butylene glycol diacrylate. 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate,
Polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, polypropylene glycol diacrylate, N, N'-methylenebisacrylamide, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, 1,4-butane Examples of methacrylic acid-based polyfunctional monomers such as diol diacrylate include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. Ethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene Len glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) ) Propane, aluminum methacrylate, calcium methacrylate, zinc methacrylate, magnesium methacrylate, etc. Examples of peroxides include t-butylperoxymethacrylate, t-butylperoxycrotonate, di (t-butylperoxy) fumarate, t -Butyl peroxyallyl carbonate, pertrimellitic acid tri-t
-Butyl ester, pertrimellitic acid tri-t-amino ester, pertrimellitic acid tri-t-hexyl ester, pertrimellitic acid tri-t-1,1,3,3-tetramethylbutyl ester, pertrimerit Acid tri-t-
Cumyl ester, pertrimellitic acid tri-t- (p-isopropyl) cumyl ester, pertrimesic acid tri-t
-Butyl ester, pertrimesic acid tri-t-amyl ester, pertrimesic acid tri-t-hexyl ester,
Pertrimesic acid tri-t-1,1,3,3-tetramethylbutyl ester, pertrimesic acid tri-t-cumyl ester, pertrimesic acid tri-t- (p-isopropyl) cumyl ester, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 2,2-
Bis (4,4-di-t-hexylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-) t-octylperoxycyclohexyl) propane, 2,2-bis (4,4-di-α-cumylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl)
Butane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) butane and others; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate, ethylene glycol Examples thereof include diglycidyl ether acrylate, and at least one of them is used.

The ethylene-based polymers (H) and (L) are preferably polymerized as follows.

Polymerization Method of Ethylene Polymer (H) Bulk Polymerization: At this stage, a total amount or a part of the monomer (M) and a combination of other copolymerizable monomers or other copolymerizable monomers are polymerized. Polymerization is carried out at a temperature of 90 to 120 ° C. The polymerization rate at this stage is adjusted to 45 to 55%.

Solvent Dilution: The above polymerization product is diluted with 30 to 70 parts by weight of a solvent such as toluene or xylene with respect to 100 parts by weight of the monomer.

Addition: All or part of the remaining monomer (M) is added at once.

Solution polymerization: The total amount of the remaining monomer (M), a solvent such as toluene or xylene, and a catalyst are continuously added dropwise to the above system at a temperature of 100 to 140 ° C. for 5 to 10 hours.

Post-polymerization: Same as solution polymerization or +
Thermal polymerization is performed at a temperature range of 10 ° C. for 1 to 3 hours.

Polymerization of residual monomer: A catalyst is added at a temperature of 70 to 110 ° C. to complete the polymerization so that the polymerization rate becomes 97 to 100%.

Polymerization Method of Ethylene Polymer (L) Solution Polymerization: 50-200 parts by weight of a solvent such as toluene or xylene is charged into the reaction system, and the total amount of the monomer (M) is 100-140 ° C. Alternatively, a combination of a part and other copolymerizable monomer or a mixture of other copolymerizable monomer and catalyst is continuously added dropwise over 5 to 10 hours.

Post-polymerization: same as solution polymerization or +
Thermal polymerization is performed at a temperature range of 10 ° C. for 1 to 3 hours.

Polymerization of residual monomer: A catalyst is added at a temperature of 70 to 110 ° C. to complete the polymerization so that the polymerization rate becomes 97 to 100%.

If necessary, the binder resin may be, for example, polyvinyl chloride, polyolefin resin, polyester resin, polyvinyl butyral, polyurethane resin, polyamide resin, as long as the effect of the present invention is not impaired.
You may add rosin, a terpene resin, a phenol resin, an epoxy resin, a paraffin wax, etc.

The amount of the mixed resin of the ethylene polymers (H) and (L) in the present invention is usually 50 in the total amount of the toner.
Is in the range of up to 95% by weight.

A low molecular weight polyolefin wax may be added to the resin composition of the present invention in order to improve the physical properties of the resin composition. The low molecular weight polyolefin wax may be either an unmodified polyolefin wax or a modified polyolefin wax in which a modifying component is blocked or grafted with respect to an olefin component.

The addition amount is preferably 5 to 20% by weight in the total amount of toner.

Specific examples of the polyolefin wax include "Viscole 660P" and "Viscole 550P".
(Hereinafter, manufactured by Sanyo Kasei), "Polyethylene 6A" (manufactured by Allied Chemical Co., Ltd.), "High Wax 400P", "High Wax 100P", "High Wax 200P", "High Wax 320P", "High Wax 220P",
"High Wax 2203P", "High Wax 4202"
P ”(above, Mitsui Petrochemical Co., Ltd.),“ Hoechst Wax P
E520 ”,“ Hoechst wax PE130 ”,“ Hoechst wax PE190 ”(above, manufactured by Hoechst Japan) and the like, as well as polyethylene wax block-polymerized or graft-copolymerized with methyl methacrylate, butyl methacrylate Polyethylene wax which is block-copolymerized or graft-copolymerized with, and polyethylene wax which is block-copolymerized or graft-copolymerized with styrene can be mentioned. These polyolefin waxes are usually mixed with the resin composition at the time of melt kneading in the production of toner, but may be added at the time of polymerizing one of the ethylene-based polymers or removing the solvent.

Toners using the resin composition of the present invention include
Usually a colorant is used. Examples of colorants that can be used include black pigments such as carbon black, acetylene black, lamp black, and magnetite, yellow lead, yellow iron oxide, Hansa Yellow G, quinoline yellow lake, permanent yellow, NCG molybdenum orange, vulcan orange, indance. Ren, Brilliant Orange G
Known pigments such as K, red iron oxide, brilliant carmine 6B, fryzarin lake, fast violet B, cobalt blue, alkali blue lake, phthalocyanine blue, pigment green B, fast sky blue, malachite green lake, titanium oxide and zinc white can be mentioned. The amount is usually 5 to 300 parts by weight based on 100 parts by weight of the resin composition. To the resin composition of the present invention, a pigment dispersant, an offset preventing agent, etc. are appropriately selected and added, and the resulting mixture can be made into a toner by a known method.

That is, the resin composition containing the above-mentioned various additives was premixed in a Henschel mixer, kneaded in a molten state in a kneader such as a kneader, cooled, and then finely pulverized using a jet pulverizer. The particles are classified by a classifier, and particles in the range of 8.0 to 20.0 μm are usually collected to obtain a toner.

In order to obtain a magnetic toner, magnetic powder may be contained. Such magnetic powders include ferromagnetic substances magnetized in a magnetic field, powders of iron, nickel, cobalt, etc., or alloys such as magnetite, ferrite, etc. The ratio of the magnetic powders in the total amount of toner is 15-70
% By weight.

Further, a release agent as described below may be appropriately used in the resin composition of the present invention during polymerization / solvent removal or during melting / kneading. The release agent referred to here is in contact with the fixing roller at the time of fixing to reduce friction, improve releasability,
Alternatively, a substance having a function of improving fluidity at the time of melting, for example, paraffin waxes, higher (saturated straight chain) fatty acids (C12 to C50), higher alcohols (C8 to C8)
32), fatty acid metal salts, fatty acid amides, metal soaps, polyhydric alcohols and the like.

In the toner relating to the present invention, a colorant and a powder fluidity modifier may be mixed (externally added) if necessary.

In order to prevent the toner particles from coagulating with each other and improve the powder fluidity, a powder fluidity improver such as Teflon fine powder may be added.

[0059]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, "parts" means parts by weight unless otherwise specified.

(Production Example of Ethylene Polymer (H)) Production Examples 1 to 10 A 5 L four-necked flask was equipped with a cooling pipe, a thermometer, a nitrogen introducing pipe and a stirring device, and 75.0 parts of styrene and maleic acid were added. After charging 25.0 parts of monobutyl acidate, the internal temperature was raised to 120 ° C., and then the temperature was kept at the same temperature, and bulk polymerization was carried out for 8.4 hours. Then
50 parts of xylene and 0.3 parts of divinylbenzene were added and mixed and dissolved in advance with t-butyl peroxide 3.0.
Parts, xylene 50.0 parts and divinylbenzene 0.2 parts were continuously added dropwise over 7.5 hours while maintaining the temperature at 130 ° C., and then the reaction was continued for 1 hour to complete the polymerization to obtain a polymer 1.

Polymers 2 to 10 were also obtained under the production conditions shown in Table 1 in the same manner as in Production Example 1.

Production Example 11 (Practical Production Example) A polymer 11 was obtained in the same manner as in Production Example 1 except that the bulk polymerization time was changed to 6.5 hours.

Production Example 12 (Practical Production Example) Polymer 12 was obtained in the same manner as in Production Example 1 except that the amount of divinylbenzene used was 0.4 part.

Production Example 13 (Practical Production Example) Polymer 13 was produced in the same manner as in Production Example 1 except that the internal temperature of the bulk polymerization was 100 ° C. and the amount of divinylbenzene (added) was 0.4 part. Got

Production Example 14 (Comparative Production Example) Polymer 14 was obtained in the same manner as in Production Example 1, except that the bulk polymerization time was changed to 3.5 hours and the continuous dropping time was changed to 6.0 hours. It was

Production Example 15 (Comparative Production Example) Production Example 1 except that the bulk polymerization time was changed to 8.5 hours and the amount of divinylbenzene (added) used was 0.5 part.
Polymer 15 was obtained by the same method as described above.

Production Example 16 (Practical Production Example) Polymer 16 was obtained in the same manner as in Production Example 1 except that the amount of divinylbenzene (added) used was 0.1 part.

Production Example 17 (Practical Production Example) A polymer 17 was obtained in the same manner as in Production Example 1 except that the amount of divinylbenzene (added) used was 0.4 part.

Production Example 18 (Practical Production Example) A polymer 18 was obtained in the same manner as in Production Example 1 except that the amount of divinylbenzene (added) used was 0.8 part.

Production Example 19 (Comparative Production Example) Polymer 19 was obtained in the same manner as in Production Example 1 except that the amount of divinylbenzene (added) used was 0.0 parts.

Production Example 20 (Comparative Production Example) A polymer 20 was obtained in the same manner as in Production Example 1 except that the amount of divinylbenzene (added) used was 5.0 parts.

(Production Example of Ethylene Polymer (L)) Production Example 21 (Practical Production Example) In a 5 L four-necked flask equipped with a cooling tube, a thermometer, a nitrogen introducing tube and a stirrer, a xylene solvent of 100.0 was added. Prepare the department,
While introducing nitrogen, the temperature was raised to the reflux temperature, and styrene 9
A mixed solution of 5.0 parts, 5.0 parts of methacrylic acid and 10.0 parts of t-butylperoxy-2-ethylhexanoate was continuously added dropwise over 6.5 hours, and after post-polymerization for 1 hour, the rest was left. Monomer polymerization was performed to obtain a polymer 21 having Mw of 5,600.

Production Example 22 (Practical Production Example) A polymer 22 was obtained in the same manner as in Production Example 21 except that the amount of xylene solvent (charge) was 150 parts.

Production Example 23 (Practical Production Example) A polymer 23 was obtained in the same manner as in Production Example 21 except that the amount of t-butylperoxy-2-ethylhexanoate used was 7.0 parts.

Production Example 24 (Practical Production Example) The amount of xylene solvent (charged) was 50 parts, and the amount of t-butylperoxy-2-ethylhexanoate used was 6.0.
Polymer 24 was obtained in the same manner as in Production Example 21 except that the parts were used.

Production Example 25 (Comparative Production Example) The amount of xylene solvent (preparation) was 150 parts, and the amount of t-butylperoxy-2-ethylhexanoate used was 1.
Polymer 25 was obtained in the same manner as in Production Example 21 except that the amount was 8.0 parts.

Production Example 26 (Comparative Production Example) The amount of xylene solvent (charged) was 50 parts, and the amount of t-butylperoxy-2-ethylhexanoate used was 3.0.
Polymer 26 was obtained in the same manner as in Production Example 21 except that the parts were used.

Production Example 27 (Practical Production Example) The monomer composition was 99.8 parts of styrene and 0.2 of methacrylic acid.
Polymer 27 was obtained in the same manner as in Production Example 21 except that the parts were used.

Production Example 28 (Executive Production Example) The monomer composition was 97.7 parts of styrene and 2.3 of methacrylic acid.
Polymer 28 was obtained in the same manner as in Production Example 21 except that the parts were used.

Production Example 29 (Practical Production Example) The monomer composition was 79.0 parts of styrene and 21.
A polymer 29 was obtained in the same manner as in Production Example 21 except that the amount was 0 part.

Production Example 30 (Comparative Production Example) A polymer 30 was obtained in the same manner as in Production Example 21 except that the monomer composition was 100.0 parts by weight of styrene.

Production Example 31 (Comparative Production Example) The monomer composition was 67.5 parts of styrene and 32.
A polymer 31 was obtained in the same manner as in Production Example 21 except that the amount was 5 parts.

The physical properties of the ethylene polymers (H) and (L) obtained in the above Production Examples were measured as follows.

Measurement of molecular weight: The molecular weight was determined by GPC using a commercially available monodisperse standard polystyrene as a standard, tetrahydrofuran as a solvent and a refractometer as a detector.

Detector SHODEX RI SE-31 column A-80M x 2 + KF-802 solvent solvent THF (tetrahydrofuran) discharge rate 1.2 ml / min sample 0.25% THF solution

Measurement of charge amount: The charge amount of the ethylene polymer was measured by powderizing and solidifying the ethylene polymer, making the particle size 3 mmφ with a commercially available crusher, and 50% volume by a crush plate jet crusher. Finely pulverized to have an average particle size of 25 μm or less, and then a wind-powered classifier was used to obtain a charge measurement sample (R) having a volume average particle size of 5 to 25 μm. Pair 2 (R / C =
98/2) and mixed at a temperature of 22 ° C and a relative humidity of 55.
% With a tumbler shaker mixer,
A sample was sampled at an arbitrary time and the charge amount was measured by a blow-off charge amount measuring device.

Measurement of acid value of ethylene-based polymer: A sample precisely weighed was dissolved in a neutralized xylene / n-butanol mixed solvent and titrated with a previously standardized alcohol solution of 0.1N-sodium hydroxide, From the neutralization amount, it was calculated by the following formula.

[0088] (F is a factor of an alcohol solution of 0.1N-sodium hydroxide)

Examples 1 to 24 and Comparative Examples 1 to 13 In these Examples and Comparative Examples, the corresponding ethylene polymers shown in any of Tables 2-1 to 2-6 obtained as described above. The polymer solution of (H) and the polymer of ethylene polymer (L) were mixed in the ratio shown in the same table, and the solvent was removed to obtain a binder resin.

Next, 100 parts of the binder resin, 10 parts of carbon black, 5 parts of polypropylene wax, and other necessary components were premixed with a Henschel mixer, and after kneading at 170 ° C. using a biaxial kneader, Cooled, coarsely pulverized, finely pulverized and classified by a classifier to obtain a particle size of 5.0 to 25.0μ.
m was obtained.

Using the above toner, the charge rising property and the like were evaluated. (I) Evaluation of charge rising property 1 g of toner and carrier iron powder (F95 manufactured by Powder Tech Co., Ltd.)
-100) 49 g with a tumbler shaker mixer 1
Minutes and 60 minutes after mixing and stirring, the triboelectric charge amount was measured by a blow-off charge amount measuring device manufactured by Toshiba Chemical Co., and the ratio of the charge amounts at 1 minute and 60 minutes of mixing and stirring (expressed as Q1 and Q60, respectively) was calculated. It was evaluated by T).

T = (Q60 / Q1) A: T ≦ 2 B: 2 <T ≦ 3.5 C: 3.5 <T (ii) Charge stability (S) Under low temperature and low humidity (15 ° C., 35%) Charge amount (QL
L) and the amount of charge (QHH) under high temperature and high humidity (35 ° C, 75%) are expressed by the ratio (absolute value) of the following calculation formula,
The charge stability was evaluated.

S = (QLL-QHH) / QLL A: S ≦ 0.2 B: 0.2 <S ≦ 0.4 C: 0.4 <S (iii) Fixability of solid black portion of 2 cm × 2 cm The toner layer on the image is tested by Gakushin-type friction fastness tester (manufactured by Daiei Kagaku Seisakusho Co., Ltd.)
The optical density of the toner layer measured by an ink densitometer after rubbing 50 times with a sand eraser at a load of 250 g / cm ² is 7
Minimum thermo roll temperature (TG) required to exceed 0%
Was evaluated. The appropriate value for the electrophotographic toner was set to 150 ° C. or lower.

The measurement results of the physical properties of each toner are shown in Table 2-1 to Table 2-1.
2-6.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

[0100]

[Table 6]

[0101]

[Table 7]

[0102]

[Table 8]

Production Examples 32 to 41 (Production of Ethylene Polymer (H)) A four-necked flask was equipped with a cooling tube, a thermometer, a nitrogen introducing tube and a stirrer, and 65.0 parts of styrene monomer and fumar. Charge 20.0 parts of dioctyl acid and 5.0 parts of maleic anhydride,
After the internal temperature was raised to 110 ° C., the temperature was kept at the same temperature to carry out bulk polymerization 7.
It was carried out for 3 hours (bulk polymerization). Next, 0.2 part of divinylbenzene, 70 parts of xylene (diluting solvent) and 5 parts of maleic anhydride were added (additional monomer), and 0.3 parts of di-t-butyl peroxide that had been mixed and dissolved in advance and 30 parts of xylene were added. Parts, 0.1 part of divinylbenzene and 5.0 parts of 2-methacryloyloxyethyl succinic acid were continuously added dropwise over 7.0 hours while maintaining the reaction system at 130 ° C. (solution polymerization), and then the reaction was continued for 1 hour. (Post-polymerization), if the styrene monomer remains, the polymerization of the residual monomer is terminated and the polymer 32
I got The Mw value of the obtained polymer was 345,000.

Polymers 33 to 41 were obtained in the same manner as in Production Example 32 under the production conditions shown in Table 3.

[0105]

[Table 9]

Production Examples 42 to 45 (Production of Ethylene Polymer (L)) A 5 L four-necked flask equipped with a cooling pipe, a thermometer, a nitrogen introducing pipe and a stirrer was charged with 100.0 parts of xylene solvent.
The temperature was raised to the reflux temperature while introducing nitrogen, and 95.0 parts of styrene monomer, 5.0 parts of methacrylic acid and 10.0 parts of t-butylperoxy-2-ethylhexanoate were added to 6.5 parts.
Continuous dropping was carried out over a period of time, and then the reaction was continued for 1 hour to carry out residual monomer polymerization to obtain a polymer 42.

Polymers 43 to 45 were obtained in the same manner as in Production Example 42 under the production conditions shown in Table 4. The values of Mw and acid value of the obtained polymer are also shown in Table 4.

[0108]

[Table 10]

Examples 25 to 33 and Comparative Examples 14 to 19 In each of these Examples and Comparative Examples, the corresponding ethylene polymer (H) shown in Table 5 or Table 6 obtained as described above was prepared. The polymer solution and the polymer of the ethylene polymer (L) were mixed in the ratio shown in the same table, and the solvent was removed to obtain a binder resin.

Next, 100 parts of the binder resin, 10 parts of carbon black, 5 parts of polypropylene wax and other necessary components were premixed with a Henschel mixer, and after kneading at 170 ° C. using a biaxial kneader, Cool, coarsely pulverize, finely pulverize, and classify with a classifier to obtain a particle size of 6.0-1.
An electrophotographic toner of 8.0 μm was obtained.

Using the above toner, the charge rising property and fixing property were evaluated as described above. Further, the environmental stability (moisture resistance stability) of the charge amount of the above toner was evaluated as follows.

Environmental stability of charge amount (moisture resistance stability); Charge amount (QLL) under low temperature and low humidity (15 ° C., 35%) and charge amount (QH) under high temperature and high humidity (35 ° C., 75%).
The difference in H) was expressed as a percentage (S; absolute value) in the following calculation formula and evaluated.

S = (QLL-QHH) / QLL × 100 (%) A ++: S ≦ 2.5 A ++: 2.5 <S ≦ 6.0 A +: 6.0 <S ≦ 20.0 Physical properties of each of the above toners The measurement results of are shown in Table 5 and Table 6.

The above-mentioned evaluation method is the evaluation method in the most preferred embodiment of the present invention, and it is described in (i) above.
The dimension is different from the charging stability (S) of i).

[0115]

[Table 11]

[0116]

[Table 12] Production Examples 46 to 49 (Production of Ethylene Polymer (H)) Polymers 46 to 49 were obtained under the production conditions shown in Table 7 in the same manner as in Production Example 32.

[0117]

[Table 13] Production Examples 50 to 51 (Production of Ethylene Polymer (L)) Polymers 50 to 51 were obtained under the production conditions shown in Table 8 in the same manner as in Production Example 42.

[0118]

[Table 14]

Examples 34 to 38 In each of these Examples and Comparative Examples, a polymer solution of the corresponding ethylene-based polymer (H) shown in Table 9 and the ethylene-based polymer (L The polymer of 1) was mixed in the ratio shown in the same table, and the solvent was removed to obtain a binder resin. This binder resin was prepared into an electrophotographic toner according to the procedure of Example 24.

Using the toners obtained as described above, their charge rising property, charge environmental stability and fixing property were evaluated in the same manner as in Example 24.

[0121]

[Table 15]

Reference Examples 1-2 An experiment was conducted on the experimental results when the amount of the monomer (M) was outside the preferred quantitative range of the present invention. The following table shows the production of the ethylene polymer (H) used and the physical properties of the toner using the same.

[0123]

[Table 16]

[0124]

[Table 17] However, the charging stability is the above (ii) charging stability (S)
According to the evaluation method of.

[0125]

By using the above-mentioned resin composition of the present invention, sufficient charging characteristics (charging stability, rising property) can be obtained even in a toner containing no charge control agent (CCA) or in a reduced toner composition. It is possible to obtain an electrophotographic toner which can be provided and at the same time has good thermophysical properties required as a toner, good fixability at high temperature and low temperature, and does not cause defective phenomena such as offset and blocking. .

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[Procedure amendment]

[Submission date] November 25, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction contents]

[0098]

[Table 4]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0115]

[Table 11]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0121

[Correction method] Change

[Correction contents]

[0121]

[Table 15]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0123

[Correction method] Change

[Correction contents]

[0123]

[Table 16]

Claims (10)

[Claims] 1. A weight average molecular weight (Mw) of 200,000 to 10
It is 0,000, and the ratio of Mw and number average molecular weight (Mn) (Mw /
Ethylene-based polymer (H) having Mn of 8 to 300
A resin composition comprising 95 to 5 parts by weight of an ethylene polymer (L) having an Mw of 3,000 to 20,000 and 95 to 5 parts by weight, and the (H) and / or (L) is 10.
In the presence of a monomer (M) having an ionization potential of 0 to 15.0 eV and a difference between the highest unoccupied orbital level and the lowest unoccupied orbital level obtained by a computational chemical method is 9.0 to 15.0 eV. A resin composition for an electrophotographic toner, which is an ethylene-based polymer obtained by polymerization. 2. The resin composition according to claim 1, wherein the monomer (M) is selected from vinyl polycarboxylic acids, vinyl silanes, and (meth) acryloyloxyalkyldicarboxylic acid esters. 3. The monomer (M) is an ethylene polymer (H)
The resin composition according to claim 1, which is contained in an amount of 3 to 45 parts by weight in 100 parts by weight of the monomer constituting the. 4. A (meth) acryloyloxyalkyl dicarboxylic acid ester is represented by the general formula (1): (In the formula, m is an integer of 1 to 7, n is an integer of 1 to 3, X means H and CH ₃ , and Y is H, an alkyl group having 1 to 8 carbon atoms or a benzyl group.). Claim 2 represented
The resin composition as described in the above. 5. The monomer (M) is 1 to 20 weight parts of at least one monomer selected from the group consisting of maleic anhydride, itaconic anhydride, glutaconic anhydride and 2-carboxycinnamic anhydride. Part and at least one kind of (meth) acryloyloxyalkyldicarboxylic acid ester represented by the general formula (1), and the total amount of the monomer M is 3 to 4
The resin composition according to claim 3, which is 5 parts by weight. 6. The acid value of the ethylene polymer (L) is 0.5.
The resin composition according to claim 1, which is about 200 mgKOH / g. 7. The total acid value of the resin composition comprising the ethylene polymer (H) and the ethylene polymer (L) is 0.5 to 20.
The resin composition according to claim 1, which has an amount of 0 mgKOH / g. 8. The resin composition according to claim 1, wherein the resin composition comprising the ethylene polymer (H) and the ethylene polymer (L) has a glass transition temperature (Tg) of 45 to 75 ° C. 9. The resin composition according to claim 1, which contains a polyfunctional monomer and / or a polyfunctional initiator as a constituent component of the ethylene polymer (H). 10. An electrophotographic toner containing the resin composition for electrophotographic toner according to claim 1.