JPS58149059A - Toner composition for developing electrostatic latent image - Google Patents

Abstract

PURPOSE:To improve a toner compsn. consisting of a colorant and a resin for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, etc., by combining an amorphous polymer with a crystalline polymer. CONSTITUTION:A toner compsn. consists of an amorphous polymer having <=110 deg.C glass transition point (Tg) and a crystalline polymer having <=110 deg.C m.p. (Tm), and a ratio of the total org. matters to the total inorg. matters is 1-2, and the amorphous polymer is a homopolymer or a copolymer of a vinyl compound, and a homo- or copolymer of (meth)acrylate is especially suitable, and as the crystalline polymer polyester, polyether, polycarbonate, polyacidanhydride, and the like resins, especially, 1,4-butandiol-adipic acid polyester, 1,6-hexandiol- adipic acid or succinic acid polyester, and polyethylene oxide are suitable. Various known colorants can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner for developing electrostatic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like.

Many conventional electrophotographic methods have been described in U.S. Pat. A scratch is formed, and then #latent is developed using toner (colored resin powder), and if necessary, the scratch is transferred to paper or the like, and then fixed by heating or solvent vapor to obtain a copy. Examples of methods for visualizing latent electrical flaws with toner include the magnetic brush method described in U.S. Pat. It has been known. The cascade method uses toner and glass beads with a coarser particle size as carriers, and the mixture of these toner and carrier (developer) is sprinkled onto the photoreceptor, while the magnetic brush method uses magnetic powder such as iron powder. used as a carrier,
This is a method of moving carriers using magnetic force. In either method, the toner particles are charged by friction between the carrier and the toner, and the toner particles are caused to adhere to the electrolyte particles by electrical attraction.

Normally, toner is manufactured by mixing and kneading resins, colorants, etc., and then pulverizing and classifying the toner. From the viewpoint of pulverizability, it is preferable to use a toner that can be easily pulverized at room temperature to about aoC. On the other hand, toner fixation is achieved using general K I, which is below the discoloration temperature of the paper.
The fixing process is carried out at a temperature of about 0-/min θC, and it is preferable to use a material that exhibits good fixing properties at such a temperature.

Among crystalline polymers, resins that generally satisfy the fixing temperature have a low glass transition point and are difficult to grind, which poses a burden to toner production. On the other hand, amorphous polymers can be easily pulverized at the above room temperature to feed θC, and also at /θ to /O
Many resins exhibit good fixing properties at C.

Therefore, amorphous polymers such as styrene resins and epoxy resins have conventionally been used as toner resins.

As the number of copies increases, the toner particles become more and more destroyed, and these fine particles scatter inside the copying machine, contaminating the optical system, and coating the surface of the carrier, which makes it difficult to clean the photoreceptor, making it impossible to obtain sufficient triboelectrification. A decrease in the image density of the copy and the occurrence of background stains (fogging) are observed.

Furthermore, it sticks to and stains the PVC tiles in the office where the copying machine is rented and the soft PVC film used to protect and store copies.

Furthermore, when the resin softened in the fixing process is cooled, the amorphous polymer turns into a glassy state and exhibits a glassy luster, but this luster is so pronounced that it is believed to cause eye fatigue.

Prior to the present invention, as a result of intensive study to provide a toner composition improved in the above points, the glass transition point was /10 (a combination of the following amorphous polymer and a crystalline polymer with a melting point of 110C or less). Moreover, they discovered that the desired objective could be achieved by adjusting the ratio of organic to inorganic properties in the entire resin to a specific range, and thus completed the present invention.

That is, the gist of the present invention is a toner composition for electrostatic latent scars comprising a colorant and a resin.

The resin consists essentially of an amorphous polymer having a glass transition point of 110C or less and a crystalline polymer having a melting point of ttOC or less, and the ratio of organic to inorganic (organic/inorganic) of the entire resin is The present invention relates to a toner composition for developing electrostatic latent scratches, characterized in that the content (inorganic) is / to -.

To explain the present invention below, the resin constituting the toner composition of the present invention is an amorphous polymer having a glass transition a (Tr) of 1/θC or less and a crystalline polymer having a melting point (Tm) of 1OC or less. molecules as essential components.

The amorphous polymer of the present invention has Ty/107:
Good tL< is -to~/10C,I! Preferably for tf, NaQ is 1 at 90C, and the softening point is 0~/! OC1 preferably 17) θ~/301::, degree of polymerization is 10~
10. θθ0. Preferably %/θθ~! , θθ0 are used.

For example, methyl acrylate, ether acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, phenyl acrylate, acrylic! Examples include single or copolymers of (meth)acrylic esters such as p-methoxyphenyl and phenyl acrylate, and vinyl compounds such as vinyl acetate and vinyl propionate. In particular, copolymers of (meth)acrylic esters are suitable.

Examples of these amorphous polymers include mixtures of polypropyl methacrylate and polymethyl methacrylate, ternary mixtures of polypropyl acrylate and polymethyl methacrylate, etc., as appropriate. .

The crystalline polymer of the present invention has a Tm of 110C or less.

Preferably, da θ~/10C, particularly preferably.

! Ty is usually -100 to -JOC1, preferably -6θ to -Hiro θC.

For example, condensate of succinic acid and/, G-hexanediol + (aH, w coo-+ca, i oocq, condensate of toetelene glycol adipate ±←a, Hco.

C,H,OOC)-, condensate of adipic acid and/, 4A-butanediol+(C111,'+-cOo(OH,
Arrow oocte, condensate of adipic acid and/, ≦-hexanediol + (CHt)aao〇-(CjH, 9-000 piece, condensate of adipic acid and m-hydroxymethylbenzyl alcohol - H0Htk resin; polymerization of ethylene oxide Polyethylene oxide obtained by polymerizing *○Ht+i0h, polyether obtained by polymerizing acetone+0 (CHs)
polyether resin such as to-crucible; /, reaction product of 6-hexanediol and 7-osgene -(-(OH,), 0CO
O) Polycarbonate resin; Polyacid anhydride obtained by polymerizing speric anhydride -@, OH, 5000
Examples include polyacid anhydride resins such as 004 and the like. n in the above formula varies depending on the fixing method of the copying machine, but is usually lθ~s, 0θ0, preferably io.

~ko, o　o　o are preferable.

Particularly preferred are /, %-condensate of butanediol and adipic acid, /, condensate of 6-hexanediol and adipic acid or succinic acid, and polyethylene oxide.

The above-mentioned amorphous polymer and crystalline polymer are appropriately selected and combined so that the overall resin has a ratio of 0/~0, preferably 7.1~7.1. If the OA is smaller than l by 9, the moisture resistance of the resulting toner will deteriorate.

The image quality becomes poor at high temperatures and high humidity, and if the O/X ratio is greater than 0, the adhesiveness to the soft PVC film increases.

Note that the organicity and inorganicity of the resin in the present invention are values calculated according to "Region of Chemistry = Volume 1, No. IO, 7/Day 7 Co! Page, 1?Tough Year".

The ratio of the amorphous polymer to the crystalline polymer used is such that the resulting resin has a Ty of j0C or more, preferably! Usually, the amorphous polymer is 74 to 10 parts by weight, preferably r0 to 0C, so that θ to 0C. 30 to 30 parts by weight of crystalline polymer per part by weight of O
j parts by weight, preferably appropriately selected from the range of -0 to 70 parts by weight. However, if the amount of crystalline polymer used is too large, the effect of reducing the gloss of copies will improve.

This increases the burden on the crushing process during toner production.

On the other hand, if the amount used is too small, the effects of the present invention will not be achieved, so it is preferable to use it within the above range.

Various known colorants can be used as the colorant constituting the toner composition of the present invention.

For example, carbon black, acetylene black, Hansa Yellow G, cadmium yellow.

Molybdenum orange, permanent orange, red iron, rhodamine lake B, fast violet B, methyl violet lake, dark blue, phthalocyanine blue,
Examples include chrome green, pigment green B, zinc oxide, titanium oxide, nigrosine I material, methylene blue, rose bengal, quinoline yellow, and ultramarine/blue.

These colorants are usually used in an amount of about 1-10 parts by weight per 10 θ parts by weight of the resin.

A toner composition can be obtained by mixing, crushing, and classifying the above resin and colorant according to a conventional method.

EXAMPLES The present invention will be further explained in detail by giving examples below.

In the examples, "part" indicates 1 part by weight.

Example 1 Methyl methacrylate (0/I = /, J)? 90 parts of an amorphous polymer of Ty90C obtained by copolymerizing θ part and 20 parts of phenyl acrylate (0/Eco, 1) and 1. Tm40C crystalline polyester resin obtained by polycondensation of nibutanediol and adipic acid (0/I
=, /, 7) 70 parts 0/I of grouper resin, 3 parts of nigrosine dye (% Oil Black BS', manufactured by Orient Chemical Co., Ltd.) and 3 parts of carbon black (#JO).

Manufactured by Mitsubishi Kasei)! After mixing, kneading was carried out.

After cooling and solidifying, it is coarsely crushed and then finely crushed in a Gen) mill.

Toner having a particle size of j to 30 μm was classified.

The softening point (ring and ball method) of this toner is /30C.

Tf　Fi70　CTEHTS*.

I prepared a developer from this toner and iron powder for 'U B1x' 100 manufactured by Konishiroku Co., Ltd., and made copies using a U B1xr00 copier, and even after copying 20,000 sheets, I was able to obtain clear copies with no capri or glare. Ta.

In addition, the obtained copy is adhered to a soft PVC film,
After that, I removed the copy, but the toner still stuck to the PVC film.

Example In Example 1, Ty? 0 (:Amorphous polymer (0/engine = /, u
) I 0 part, /, T obtained by polycondensing 6-hexanediol and succinic acid! 11rC crystalline polyester resin Wfl (0/I = 1.'7) 70 parts and/or Tm4θC crystalline polycarbonate resin obtained by reacting 6-hexanediol with phosgene (
A toner was obtained in the same manner as in Example 1, except that a resin consisting of 0 parts of 0/work =: /, / ) and having an O/work of Haj was used. The resulting toner had a softening point of 13jC and a Tf of TataC.

Copying was carried out using this toner in the same manner as in Example 1, but after making 10,000 copies, a clear copy was obtained. In addition, the adhesiveness to soft PVC film was not dull.

Example 3 Tyr obtained by copolymerizing 70 parts of methyl methacrylate and 30 parts of ethyl methacrylate in Example/
CQ:) 9 parts of amorphous polymer (0/engine = i, u) and polyethylene oxide of Tm66C (0/engine = 2
．． θ) O/I consisting of 10 parts is 8! A toner was obtained in the same manner as in Example except that the following resin was used. The resulting toner had a softening point of 13IC and a Ty of 7QC.

Copying was carried out using this toner in the same manner as in Example 1, and the results were the same as in Examples 1 and -.

A good copy is available to my friend. Furthermore, the life of the developer was also good.

Example In Example 1, an amorphous polymer of Ty Otsu 3C (0/E = y, t) obtained by copolymerizing 30 parts of methyl methacrylate and 70 parts of ethyl methacrylate! T obtained by polycondensing θ part and adipine alcohol/6-hexanediol
IE j d C crystalline polyester resin (0/work=
2.0) A toner was obtained in the same manner as in Example, except that a resin with an O/I of 20 parts was used. The obtained toner had a softening point of 13θC and a Tf of 4°C.

When copying was performed using this toner in the same manner as in Example, good copies were obtained. In addition, no adhesion to soft PVC film was observed.

In Comparative Example/Example/, fi Tf≦ obtained by copolymerizing 6 parts of styrene and 3 parts of n-butyl methacrylate as a resin.
A toner was obtained in the same manner as in Example 1, except that 100 parts of IC amorphous polymer (0/engine = 7..2) was used. The resulting toner had a softening point of /l/C and a Tt of 6C.

Copying was carried out using this toner in the same manner as in Example 1, the resulting copy was brought into close contact with a soft PVC film, and then the copy was peeled off. There was significant adhesion in large areas.

In addition, the image quality of the resulting copies was noticeably glaring in areas where a large amount of toner was deposited.

In Comparative Example/Example/, an amorphous epoxy resin (trade name,
Ehicoat'#100μ, Mitsubishi Yuka Co., Ltd.) Ro part and amorphous xylene resin (trade name, dicanol
B10/, manufactured by Mitsubishi Gas Chemical Co., Ltd.) - ○/engine consisting of 0 parts is approximately λ,! A toner was obtained in the same manner as in Example 1 except that the following resin was used.

The obtained toner had a softening point of 10IC and a Ty of 9 parts %C.

When copies were made using this toner in the same manner as in Example 1, the surface of the carrier was contaminated with the toner after 1000 copies were made, and a satisfactory image quality could no longer be obtained. It is presumed that the toner was broken at the grain interface during friction with the carrier because the compatibility between the epoxy resin and the xylene resin was not very good.

Claims (1)

[Claims] (11) In a toner composition for developing an electrostatic latent image consisting of a colorant and a resin, the #resin is substantially composed of an amorphous polymer having a glass transition point of 110C or lower and a crystalline polymer having a melting point of θC or lower. 1. A toner composition for electromagnetic printing, characterized in that the organic to inorganic ratio (organic/inorganic) of the entire resin is 1-1.