JPS5933460A - Electrostatic latent image developing toner - Google Patents

Abstract

PURPOSE:To obtain a toner not melt attaching without requiring oil coating on a heat roll, and a developed image good in image quality, by using a toner contg. as a main component a thermoplastic resin having the heat capacity difference between the bottom of heat absorption at the glass transition point in DSC and the base line after the peak not above a specified value. CONSTITUTION:The present toner for developing an electrostatic latent image consists essentially of a thermoplastic resin, and the resin has <=6.0X10<-3>cal/g deg.C heat capacity difference between the bottom of the absorption peak at the glass transition peak and the base line after the peak in the differential scanning thermal analysys (DSC) of this resin. The toner has a wide range of nonoffset, since the toner hardly melt attaches to the surface of the heat roll, oil coating is made unnecessary, besides the toner is superior in fixability and heat resistance, and a good quality toner image can be obtained by developing an electrostatic latent image using this toner.

Description

DETAILED DESCRIPTION OF THE INVENTION The inexcusable relates to a 1-ner for use in the current operation of Seiryu Senzuka, which visualizes electrostatic a home.

In general, in electrophotography, 1f! The image formed by the toner is transferred to the reed or transferred (after being poured onto the sheet and then fixed, a clear photographic image can be obtained. Fixing methods include non-contact methods such as so-called infrared fixing, flash fixing, and steam fixed mix, and contact methods such as pressure fixing and heat fixing, but the efficiency is very low. Heat fixing is mainly used.This fixation is carried out by press-contacting the 7ζ image formed by lJl+rollerless tray l・ner and fixing it, but when the sword is melted and the 1ζ top Since it is easy for the toner to adhere to the surface of the loaf when it is unraveled, it is usually done to prevent toner from adhering to the surface of the roller.

However, preventing toner adhesion by applying a lot of paint is not necessarily an easy task, and there are also problems with l/ζ.

The invention was made in view of these problems, and since the non-offset area is wide, there is no need to substantially apply oil to the Mj roller without it being fused to the roller. Electrostatic a-image development has excellent heat resistance for fixing 1 to 11 hours, and is also capable of obtaining toner images of outstanding image quality when developing Seigame late imitations. toner? It is about providing.

The toner for developing an electrostatic latent image of the present invention is a toner for developing an electrostatic latent image, which has a non-plastic resin, a raw resin, and a resin as main components, and comprises differential scanning (calorimetric analysis (DS(:)) of the thermoplastic resin. Of course, the difference in heat capacity between the bottom of the endothermic peak at the transition point and the base line after the peak is less than 6.0 x 10-3 cal/y''C. It can be used as a toner in 14+4 developing countries such as the known one-component developing system or (t) two-component developing system.

tjrJ Ki Hama! 'IiJ plastic 1 raw 1 Oka resin includes vinyl spinning wheel combination, polyesters, polyamides, epoxy J
They include, but are not limited to, copolymers of mIIF4'M and their derivatives.

The thermoplastic resin preferably has a number average molecular weight of 15,000 or less and a weight average molecular weight of 15 (JOOOO or more).

2. The molecular weight of the resin shown in the booklet is determined by gel permeation chromatography (GPC).
The molecular weight was determined as a result of molecular weight measurement. Further, it is preferable that the thermal pJ plastic resin has a glass transition point in the range of 50 to 65'C (failure determination with a differential scanning calorimeter under the condition of a heating rate of 10''c/m'n). If the glass transition point is less than 50°C, the heat resistance will deteriorate, and the toner will solidify easily, resulting in poor storage stability.11, 65°C
This is because, if it exceeds 100 yen, the regularity will deteriorate.

Toner's main division is Yama 1iJ plastic 1 life sphere; 1 effect I)
The heat capacity difference (△C) between the endothermic peak J part at the glass transition point in SC and the base line after the peak is 6.0 x I
Q-3cal/f/ 'C or less, 0, △
C (f3.OX 10-3 cat/y''C) This is because in the case of 7ζ using thermoplastic monomer resin outside this range, the non-off-foot area of the toner becomes narrow, so 7J1. In addition to making it easier for the toner to be fused onto the surface of the heat roller, it also prevents fogging and filmink development from occurring when used in a powder@transfer-type "photographic development laboratory 1" in an electrophotographic photocopier. It is Naru・Ra. This tide! The capacitance difference (ΔC) is determined based on the differential scanning calorific value 7IllJ. Akari Ki＠
The heat capacity difference (ΔC) shown therein was determined as a result of differential ρ analysis using a differential scanning calorimeter (SSC-56O5) manufactured by Daini Yukosha. Note that the measurement of this heat capacity difference (△C) can also be applied in almost the same way even if the toner is placed on the eye body.
It is also considered desirable that C) be within the above range. 11ζ, t'qrJ) When using a mixture of one finger of porcelain as a plastic ceramic resin, it is important that the heat capacity difference (△C) of the entire mixed resin is within the range of 011. However, depending on the case, some resins outside the scope of IRJ may be used for this purpose.

By the way, the heat capacity difference (△C) in nIJ Note 1 is obtained as a result of differential thermal analysis, and specifically,
It is calculated from the following formula based on the output of the calorimeter shown in the figure.

3 X M S: output shift of calorimeter (Ilv) 1 (: device constant (mcal/mV-sec) B: external temperature sensitivity ('C/min) M: sample mass (my) The vertical axis represents the output of the differential scanning calorimeter, the horizontal axis represents the output of the differential scanning calorimeter, and the curve in the figure represents the change over time in the output during differential thermal analysis.

Incidentally, flesh-colored Al1, etc. 2 may be dispersed in advance in the plastic resin. For polishing, it is sufficient to use carphone blacks such as furnace plaque, channel black, and acetylene black, which are commonly used. Dye may be used in combination with coloring and shaving, which also serves as antistatic shaving. Obi'l1iL8fII? AJ Qi 11, For example, let's take a representative example of positively charging toner (t,!-g), or oil-based dyeing of nigrosine thread oil black, Crystal Bai Mashitsu I, etc. Metal complex dyes such as baratin dyes and offsol dyes are representative examples of negatively chargeable dyes. If necessary, it is appropriate to mix and disperse 2 to 20 parts of perilla perilla to 1 part of unused plastic (10<10%) caramel.

Below, 1, an example of non-invention will be described.

Example 1 Styrene-acrylic copolymer resin [number average molecule h1 (Mn
): l 2,50o, heavy nail average molecular weight (MW):
195,3001,11/ la, zk transition point (”' g
): 58'C1mM amount difference (ΔG): 5.9
X 10-3 cal / fl” (2 (ascension 1 degree, J
O°C/rTIin ) ) 10 (Jm-
Fit part carbon black (manufactured by Mitsubishi Chemical Industries, Ltd. MA#
100) 6 parts by weight oil-soluble dye of nigrosine thread (Orien I, Kagaku Co., Ltd. Bontron N-o6) 4 = Abeuchi iJ composition After thoroughly grinding and mixing in a Keball mill, 150 parts by weight
The mixture was sufficiently kneaded with a Miki roll set at 'C, and after cooling, it was pulverized with a Sierra 1-masher, and the coarse powder and powder were removed by classification, resulting in a toner with an average particle size of 127 zm.

About this toner, after its manufacture, 168 hours! ] After the time has elapsed, scan the scanning calorimeter (SSC-560SJ)
Differential thermal analysis was carried out using P! and p! of the absorption peak at the glass transition point and p! of the peak after the peak! The difference in capacity is
5.8×10-3 cal/9'CT8
7e.

Example 2 Polyester thread resin CMn: 6,200, MW: 251
．． 100, Tg: 62°C1△C: 4.9 Xl0-
3cal/9'C (heating rate 10°C/min
)) 100 times 9 parts''#Jo0 4nf parts /[B soluble dye of chromium alloy (Bontron S-34J3 manufactured by Orient Chemical R1)
A 1-toner with an average particle size of 13 μm was obtained (7c), and this toner was subjected to differential S analysis in the same manner as in Example 1. It was found that the p3 ratio between the bottom of the endothermic peak at the glass transition point and the base line after the peak was Quantity difference X/f, 4sxlo-3cal/p
'c.

Example 3 Nuthylene acrylic resin (Ajn: 10,200
, MW: 211,400. Tg:59°C1AC:46
X 10-3cal/y”C(-ti1%f[I Q
'c/min)) 100 parts carbon black (manufactured by Mitsubishi Chemical Corporation 84Δ#8)
A toner having an average particle size of 11 μm was obtained in the same manner as in Example 1 using the composition having the above-mentioned loading ratio. When this toner was subjected to M thermal analysis in the same manner as in Example 1, the difference in heat capacity between the bottom of the Harikoshi peak at glass transition point 1 and the base line after the peak was 4.4X10-3 cal/y'''C. Rarely.

Comparative Example 1 7-tyrene-butadiene thread resin [number average molecular weight (Mn: 1
5,100. MW: 124,500. Tg: 62°C'
, ,6C:6:7XI O-” cal/y'C(
1fflJ degrees of elevation 10°C/n1in))
A toner having an average particle diameter of 1271 m was obtained in the same manner as in Example 1 using a composition having a self-coating ratio of 100 [Setting part MARI U O-6mm Bonn 1-Ron N-064 Claw part r3rJ period. When this toner was subjected to water jug analysis in the same manner as in Example 1, the difference in heat capacity between the bottom of the absorption peak at the glass transition point and the base line after the peak was 6.5 x 10-3 cal/
p″Cr rarely.

Comparative Example 2 Nutylene acrylic resin [Pufymanphyto manufactured by Gutdeyer Co., Ltd. ACMn: 37,5 Q Q, Mw: 1
19,3υO1Tg:er25°C1,ivc:x4.
.

X 10' cal /f"C (heating method E 10"C
/ rnin]] 85 parts by weight polynutylene resin [Picolastic A-75 manufactured by Pico Co., Ltd.
Mn: 3,000. MW: 4,000. 'Ig:44°
C1ΔC: 17. OX 10'cal/li"C
(Temperature raising method iI Q'C/1nin))
15] i[part M A , 93
5-ply J-edge part Nigrosine thread oil black (manufactured by Orien Ile Gakusha Bon 1-ron N-05) 5 parts 2 pieces of +'1M of the above-mentioned blended comb, carried out f 111
According to the proverb, the average grain size was 13 μm LJ). When this toner was subjected to differential thermal analysis in the same manner as in Example 1, the glass transition point was 565''C.
'7J) The difference in heat capacity between the bottom of the endothermic peak at the glass transition point and the base line after the peak is 14.3X10-3 cal/y.
°C″c heat 7m. 17ζ, this toner 2, i, 'l
-11' (71-hydrofuran) with a molten sword b
The insoluble matter was removed by acclimatization, and the molecular weight of the soluble matter was measured by G PCT.1, Mn: 8,200. Mw: 1
10,400Th/'c.

Comparative Example 3 Nutylene/acrylic unceramic resin [Imanac Chemical Co., Ltd.
1Q X-195, Δ4n: 24,300. M.W.
:40,8(JO1'l-g :64"C1△C:1
88×10-3 Cal/y”C (JA [in speed KI
O'C/min)) 1.00i Sarato Carbon Black (Carbon Black #44, manufactured by Mitsubishi Chemical Industries, Ltd.) 6 parts by weight Nicrosine thread oil four rack (Manufactured by Orien 1ltf Co., Ltd. Nigrosinba 7 E, X) Parts by weight miJ Using the composition with the above blending ratio, according to the manufacturing method of Example 1, the average particle size was 14.
False 1ζ μm toner. Regarding this toner, Example 1
Perform differential thermal analysis in the same manner as 7? :, Tokoro, Gala 7,
The thermal valley between the endothermic peak () at the transition point and the & line after the peak was 18.8 x 10-3ca, I/g'C.

(Manufacturing method of carrier) Prioride AC100 Commercial triiron tetroxide (Mabico Black BL-5 manufactured by Titan Kogyo Co., Ltd.)
00) 200 parts by weight MA #8
5
Knead the composition of 6 parts niJ in the mixing ratio and make powder 111
(・Classified to obtain magnetic raw material with an average particle size of 21 μm) ζ.

(Preparation of phenomenon agent) To 9975 parts by weight of each toner, add 025 parts by weight of silica Nippon Aerosil Morinaka Silica R-972, particle size Jl 1m or less and mix thoroughly. After 1ζ, each toner and ILJ carrier klo: 1'00 A two-component thread magnetic development g++e was prepared by mixing thoroughly at a batch ratio of 7ζ.

Example Each of the above-mentioned phenomenon agents was thoroughly stirred and sufficiently charged, and the charge amount of the toner was added. The results were consistent with those shown in Table 1.

Table 1 Examples Each developing laboratory 11 was used as a two-component thread porcelain developer? The fused air brush imager used is a total of 1,711 particles transfer type, loaded into an electrophotographic photographic machine, and the electrostatic latent image on the photosensitive layer is imaged, fixing strength, high offset generation temperature The temperature offset temperature was measured and the results are shown in Table 2. In addition, Example 1
As for the current generation J prepared using the toners of Examples 1 to 3, the electrostatic latent sphere was 10 times the length of the CdS thread photoreceptor using a photoreceptor [11]. :, Examples 2 and 3
Regarding the 1-ner IJ and the current operational #ilJ, the photocopier cO' is fully equipped with Se thread photoreceptors, where the silent diving whale is completely covered.
] Of course, I played Tenu 1~. The fixing device of OD and OD are both 50mm diameter with 1ml of tetrafluoroethylene/perfluoroalkyl vinyl ether joint (manufactured by Roro Chemical Co., Ltd.). The system speed (J
The circumferential speed of the drum made by Morimitsu is 130rrvn/Sec.

The fixing strength was measured at a part of the copy image wrinkles (fault density of the I-ner image) fixed on a 11mm paper cover at a fixing temperature of 170"C. - A load of 11 (9 times 3 reciprocations was applied to sand rubber (manufactured by Lion Corporation) for 1 day, n1 of 1 time) The rate of change in soybean density was substituted and expressed in %.

Also, n1it heat 77 is each 1i---5! vi50
Pour into CC glass sample bottle and heat at 50°C for 241 hours.
Heat 1tti4J, then take it out and let it cool for 1ζ
After that, I turned the bottle upside down, checked the missing pages of the 1st bottle, and poured 7 CO.
The evaluation criteria were: those that fell immediately without condensation due to total heat;
It started falling in about 5 to 15 seconds, and the 7ζ thing started falling, and it started to fall from 30 to 30 seconds.
The one that starts falling after about 60 seconds is used as 1ζ. In both cases, the length is soft and easily deteriorates due to external force.

Table 2 Examples Regarding developers prepared using each toner, copying machine (
Using the D-Ashita song, a series of 60,000 copies were printed, and tenuto was printed. In addition, Shunsha [11, [11 is equipped with an oil-coated 1i iso structure as a fixing device] for the developing j prepared using the toner of Comparative Example 3) ζ device sound used / ζ
Other than that, the one in niJ was used -[:1.

The results are shown in Table 3. In the table, ◎ is extremely good, ○ is good, and △ is fair (indicates that some cuff marks are present on both sides of the print, or that some filming is observed on the surface of the photoreceptor.) , × indicates poor (indicates a state in which fogging or filming is significant to a degree that is unsuitable for practical use).

As is clear from the results in Table 3 and Table 3, the toner according to the invention does not need to be completely coated with oil on the fixing heating roller, since the non-offset area is wide, the fixing roller 11ζ, in which toner adhesion to the surface of
Even if the foot M temperature is set to 1.70"c, which is one degree higher than the conventional setting, the fixing strength is high and the sword has excellent heat resistance. 2. The present invention When an electrostatic latent image is recorded using a 1ζ development process prepared using a toner of 1000, no filming development occurs in which the toner fuses to the capri or photosensitive surface.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the output change of a differential scanning calorimeter during differential thermal analysis of a thermoplastic resin. Patent Applicant: Minolta Camera Co., Ltd. Fi1 Representative Patent Attorney: Aohaku Ao and 2 others Figure 1 (sec)

Claims (1)

[Claims] (1) 1- for Shizukame Senzuka development whose main component is thermoplastic resin
The difference in heat capacity between the bottom of the endothermic peak at the Gafnu transition point and the base line after the peak in the differential scanning heat analysis of Kejikunjibojiang is 6.0X10-3 cal/f.
A toner for cultivating Seiryu A statues, characterized by having a toner of /'C or less.