JPS6275644A - Production of toner for developing electrostatic latent image - Google Patents

Abstract

PURPOSE:To improve resistance to PVC contamination and moisture by subjecting a specific radical-polymerizable monomer mixture to a radical polymn. in the presence of the polycondensation product of a dimer acid and aliphat. amine. CONSTITUTION:50-50wt% radical-polymerizable monomer mixture into which 12-28wt% radical-polymerizable monomer having a hydroxyl group is incorporated is subjected to the radical polymn. in the presence of 10-50wt% polycondensation product of the dimer acid and aliphat. amine. The above- mentioned monomer mixture into which 12-28wt% radical-polymerizable monomer having the hydroxyl group and 50-88wt% styrene and/or the substituent thereof are incorporated is preferable. The above-mentioned polycondensation product is preferably melted and is polymerized with such monomer mixture. The polycondensation product having 100-1,000 poise melt viscosity at 140 deg.C is preferable. The toner for which such resin is used has the excellent fixability and shelf stability as well as the good resistance to PVC contamination and moisture. The sharp image having no fogging is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a toner for developing electrostatic latent images used in fields such as electrostatic recording and electrophotography.

More specifically, it is used in this field. Resistance (Prior Art) Conventionally, as a toner for developing an electrostatic latent image that is resistant to PVC staining, a toner containing an epoxy resin and an ester wax (Japanese Unexamined Patent Publication No. 57-96354, hereinafter referred to as toner (
Toners containing a vinyl polymer having a hydroxyl group (hereinafter referred to as toner (It)) are known.

(Problems to be Solved by the Invention) However, although toner (Il) has excellent resistance to 2.C PVC staining, it has the disadvantage of poor moisture resistance.On the other hand, toner (II) PVC stain resistance and moisture resistance are controlled by the content of hydroxyl groups, but if you try to obtain sufficient PVC stain resistance by increasing the amount of hydroxyl groups in the polymer, the moisture resistance will be poor and the opposite will occur. If an attempt is made to maintain good moisture resistance by reducing the number of hydroxyl groups in the polymer, it has the disadvantage of poor PVC stain resistance, that is, it is difficult to improve both PVC stain resistance and moisture resistance. Note that the PVC stain resistance and moisture resistance mentioned here are as follows.

(1) PVC stain resistance Images obtained with toners are sometimes stored, for example, in cases made of soft vinyl chloride polymer (hereinafter referred to as "soft PVC").

The toner image is affected by the plasticizer in the soft PVC.

May cause defects. In addition, the toner itself may be deposited on electrical wiring cords coated with soft PVC in copiers that use electrostatic recording or electrophotography, or in laser beam printers, or Splashed from beam printer.

Otherwise, it may spill and accumulate on surrounding soft PVC floor tiles, wall materials, etc. At this time, the toner is affected by the plasticizer contained in these soft PVC electrical wiring cords, floor tiles, wall materials, etc., and may adhere firmly to these materials. Such a phenomenon should not occur, and the difficulty of such a phenomenon to occur is herein referred to as PVC stain resistance.

(2) Moisture resistance refers to the toner's difficulty in absorbing moisture. If the toner easily absorbs moisture, the amount of charge on the toner decreases significantly when the toner is stopped, which may result in image defects such as fog, toner scattering, etc. when the toner is restarted.

(Means for Solving the Problems) The present invention provides a method for converting 90 to 50% by weight of a radically polymerizable monomer mixture (component A) containing 12 to 38 hydroxyl group-containing radically polymerizable monomers into dimers. The present invention relates to a method for producing a toner for developing electrostatic latent images, which comprises a step of radical polymerization in the presence of 10 to 50% by weight of a polycondensate of an acid and an aliphatic amine (component B).

Component A tends to be a radical having a hydroxyl group, and if it exceeds 38% by weight, the moisture resistance of the toner tends to decrease. Component A contains 88% of other radically polymerizable monomers.
Contains ~62% by weight. As other radically polymerizable monomers, styrene and/or its substituted products can be added to 50% of component A.
It is preferable to contain 88 to 88 times. Styrene and/or
Or by containing 50% by weight or more of the substituted product.

Since component A dissolves component B, component A and B
The components are more uniform, which is more preferable for achieving the object of the present invention. For this purpose, when polymerizing component A, B
It is preferable to dissolve the lf component in the A component. A radically polymerizable monomer having a hydroxyl group when styrene and/or its substituted product is contained in 50 to 88% of styrene per 12 minutes.

A radically polymerizable monomer other than styrene and its substituted products can be contained in component A in an amount of 0 to 38 weight percent.

Examples of the radically polymerizable monomer having a hydroxyl group include hydroxyalkyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. , allyl alcohol, etc.

The above-mentioned styrene substitutes include α-methylstyrene,
Examples of radically polymerizable monomers other than p-methylstyrene p-tert-border include alkyl methacrylates (methyl methacrylate, propyl methacrylate,
butyl methacrylate, etc.), alkyl acrylates (methyl acrylate, ethyl acrylate, propyl acrylate,
butyl acrylate, etc.).

Methacrylic acid, acrylic acid, glycidyl methacrylate,
Contains glycidyl acrylate, vinyl acetate, etc.

In the present invention, component B is a dimer acid and 2 such as ethylene diamine, propylene diamine, hexamethylene diamine, and 1,7-diaminohebutane.

1.8-diaminooctane, 1.9-diaminononane.

It is polycondensed with aliphatic amines such as 1.10-diaminodecane, 1.12-diaminododecane, and diethylenetriamine. Also, examples include stearic acid, oleic acid, sebacic acid, and succinic acid.

Small amounts of aliphatic carboxylic acids such as adipic acid and dodecanedioic acid can also be used in combination with dimer acids.

Such polycondensates are also included within the scope of the present invention.

In the present invention, component B has a melt viscosity of 1 at 140°C.
00-1. It is desirable that it be in the OOO poise range.

Although this is not necessarily an essential requirement to achieve the two effects of the present invention, namely, the effect of improving both PVC stain resistance and moisture resistance, it improves both the fixing properties and storage stability of the toner. It is necessary for An example of component B within the above melt viscosity range is Tomide Donna 558. Tomide ◆509. ) - Mydna 394. )-Might◆3
90 (all product names, Fuji Kasei Kogyo ■Ria), etc.

In the present invention, component A and component B are blended such that the weight ratio of component A/component B is 90/10 to 50,150. If this ratio exceeds 90/10, the vinyl chloride stain resistance and moisture resistance will decrease, and if it is less than 50,150, the fluidity of the toner will tend to decrease significantly. The weight ratio of component A/B Fii is preferably 85/15 to 65/35.

In the present invention, component B is dissolved in component A.

This is then subjected to radical polymerization, and as the radical polymerization method, a bulk polymerization method, a suspension polymerization method, etc. can be used. Furthermore, if necessary, a mixed solvent of an aromatic hydrocarbon such as toluene or xylene and an alcohol such as inbutanol or isopropanol may be added to radically polymerize Ac1 in the presence of component B. . Note that suspension polymerization is preferred from the viewpoints of ease of control of heat of double polymerization and ease of post-treatment after double polymerization. As a polymerization catalyst.

Examples include radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile, and redox polymerization initiators. Suspension polymerization is carried out at a temperature of about 80 to 90°C in water containing a suspending agent such as polyvinyl alcohol or tricalcium phosphate, and optionally an anionic surfactant such as sodium dodecylbenzenesulfonate. It is preferable to do so.

The resin obtained by the above polymerization has a melt viscosity of 1. It is desirable that the glass transition temperature be within the range of OOO to 10,000 poise and within the range of 55 to 70°C. Although these controls are not necessarily essential for achieving the two effects of the present invention, namely, improving both PVC stain resistance and moisture resistance, they improve toner fixability and storage stability. It is necessary to make both of them good. In addition, the melt viscosity was determined to be 140 using the Flo Tester method.
Measurement was carried out under the following conditions: constant temperature of °C, pressure of 10 kgf/cm9 + Thai nozzle dimensions of 0.5 a Imφ x 11 TII11. Glass transition temperature was determined using thermo-mechanical analysis method, penetration mode, load tB
Ogf, measured at a temperature increase rate of 10° C./min.

The thus obtained resin, colorant and/or magnetic powder, and additives as necessary are mixed, melted and kneaded, then crushed, and further classified as necessary for use in developing electrostatic latent images. It is considered a toner. As the above mixing method, there is a method in which a colorant and/or magnetic powder and additives are present as necessary during the polymerization. When suspension polymerization is used, in some cases, only classification is performed without melt mixing. It can be used as a toner for developing electrostatic latent images.

Among the above-mentioned mixing methods, as a mechanical method, there is a method of mixing the materials using a W cone, a blender, a Zhenschel mixer, or the like. As a melt kneading method.

Pressure kneader, Banbury mixer 2pA roll.

There is a method of kneading at a temperature where the resin melts using an extruder or the like, and the above mixing step may be omitted and melt kneading may be performed. The above pulverization method is as follows.

There are methods using a feather mill, bottle mill, pulverizer, nommer mill, air jet mill, etc. Furthermore, as a nine-classification method, there is a method of sieving using an AccuCut, Alpine classifier, zigzag classifier, etc.

Colorants include carbon black, phthalocyanine blue, phthalocyanine green, Hansa Yellow, Rhodamine 6G Lake, and Watching Red Ba, and it is best to use them in an amount of 0.5 to 15% by weight based on the total toner. preferable.

Examples of the magnetic powder include magnetic materials such as magnetite and ferrite, which can be incorporated to form a magnetic toner. The magnetic powder is 35 to 65% by weight based on the entire toner.
It is preferable to use it within the range of .

Other additives include primary ones.

As charge control agents, nigrosine dyes, fatty acid-modified nigrosine dyes, polyamine resins (trade name AFP-B, manufactured by Orient Kagaku Kogyo ■), dibutyltin oxide, dioctyltin oxide, zinc oxide, chromium complexes of salicylic acid derivatives, metals of azo compounds ( There are complexes such as manganese, chromium, iron, nickel, etc., and the amount is 0 to 0 for the entire toner.
It can be used within a range of 10% by weight depending on the purpose. In order to exhibit the effect of addition, the amount is preferably 0.5% by weight or more based on the entire toner.

Polyethylene wax as an anti-offset agent.

Release agents such as polypropylene wax, ester wax, and amide wax are contained within the range of 0 to 5% by weight based on the entire toner, and butadiene rubber.

A rubbery substance such as styrene/butadiene rubber or acrylic rubber can be used in an amount of 0 to 15% by weight based on the entire toner. To achieve the effect of addition,
The release agent is preferably 0.5% by weight or more based on the total toner, and the rubbery substance is preferably 3% or more by weight based on the total toner.

As a toner fluidity improver, hydrophobic 7-liquid can be added in an amount of 0 to 0.5% by weight based on the total toner. K, which exhibits the effect of addition, is preferably 0.05 weight % or more based on the entire toner.

(Example) Next, an example of the present invention will be shown.

Example 1 80 parts by weight of a mixture of radically polymerizable monomers of 65.3% by weight of styrene, 9.0% by weight of butyl acrylate and 25.7% by weight of 2-human axypyl methacrylate were mixed with Tomidena 394 (commercial product). given name.

Added 20 parts by weight of a polycondensed metal compound of dimer acid and aliphatic amines manufactured by Fuji Kasei Kogyo ■ (melt viscosity at 140°C: 190 Boise) and completely dissolved it at 50 to 60°C over 1 hour. . To this, 5.6 parts by weight of benzoyl peroxide was added, and then 0.3% polyvinyl alcohol aqueous solution containing trace amounts of sodium chloride and sodium nitrite was added.
After adding 200ii parts of I and raising the temperature to 90°C,
Suspension polymerization was carried out for a period of time. The obtained resin (hereinafter,
The melt viscosity of resin (1) at 140°C is r2X
The glass transition temperature was 58°C.

The above resin (I) ss weight%, carbon black≠44 (
Product name: Carbon black manufactured by Mitsubishi Chemical Corporation) 10i
A mixture consisting of 3% by weight of Oil Black SO (trade name, nigrosine dye manufactured by Orient Kagaku Kogyo ■), and 2% by weight of Viscol 660P (trade name, polypropylene wax manufactured by Sanyo Chemical Industries ■) was put into an extruder. After melt-kneading the mixture at a temperature of about 100°C and extruding it into a plate shape, it is roughly pulverized, further pulverized with an air jet mill, and then classified with a zigzag classifier to obtain particles with a particle size of 5 to 3.
A fixed image of toner A was obtained by reversal development using Selex 900 (trade name, copying machine manufactured by Copia ■).

Quality PVC sheet (0.5mm thickness) and 50°C, 1ooog
The sheets were brought into contact for 200 hours under a pressure of f/cm2, and then the sheet and toner image were peeled off, and the condition of toner stains on the sheet was visually observed. The results are summarized in Table 1.

Next, as an experiment to test the toner transfer efficiency, we used Selex 900.
After 1 reversal development and transfer, the amount of toner remaining on the photoreceptor after transfer was planned using the following method.

That is, the toner on the photoreceptor before and after transfer is peeled off using Scotch tape (manufactured by Minnesota Mining and Manufacturing), and the density of each toner adhering to the Scotch tape is measured using a microphotometer MP hi-2 model. (It was measured using Union Optical (ceramic)) and expressed as the transfer efficiency of the following formula (1). This is summarized in Table 1.

Here, T I)o: Toner density on the photoreceptor before transfer D = Toner density on the photoreceptor after transfer Next, as a test of the moisture resistance of the toner, 20°C, 93φRH
The saturated moisture absorption amount of the toner (dry M amount of the toner (ratio of weight increase at saturated moisture absorption of the toner to 2 weight ratio) was measured. This is shown in Table 1.

Comparative Example 1 In Example 1, the radically polymerizable monomer mixture was
Toner B was prepared in exactly the same manner as in Example 1, except that 5 parts by weight and 5 parts by weight of Tomide≠394 were used. Toner B
The toner was evaluated for its resistance to vinyl chloride staining, moisture resistance, and transfer efficiency, and the results are summarized in Table 1.

Comparative Example 2 Toner C was prepared in exactly the same manner as in Example 1, except that 100 parts by weight of the radically polymerizable monomer mixture was used instead of Tomide≠394. Toner C
The toner was evaluated for its resistance to vinyl chloride staining, moisture resistance, and transfer efficiency, and the results are summarized in Table 1.

Comparative Example 3 In Example 1, Epicor 1-1007 (trade name, Yuka-Ciel Epoxy ■) was used instead of 85% by weight of resin CI).
65% by weight of epoxy resin) and Epicoat 100
4 (trade name, epoxy resin manufactured by Yuka-Ciel Epoxy ■) at 20% by weight.

Toner D was prepared in exactly the same manner as in Example 1.

Regarding Toner D, the toner's resistance to vinyl chloride staining, moisture resistance, and transfer efficiency were evaluated and summarized in Table 1. In addition.

The melt viscosity of Ep1004 (7) at 140°C was 250 voids. In addition, Ep1007 is 65 parts by weight and Ep1007 is 65 parts by weight.
The melt viscosity of the 004;6E2 OMn part mixture at 140°C was 1500 voids, and the glass transition temperature was 58C.

(Effects of the Invention) According to the present invention, it is possible to obtain a toner for electrostatic latent images having excellent resistance to vinyl chloride staining and moisture resistance.

Agent: Patent attorney Kunihiko Wakabayashi.

Claims (1)

[Claims] 1. Radical polymerizable monomer having hydroxyl group 1
A radically polymerizable monomer mixture (A component) containing 2 to 38 wt. A method for producing a toner for developing electrostatic latent images, the method comprising a step of polymerizing. 2. The electrostatic charge according to claim 1, wherein component A contains 12 to 38% by weight of a radically polymerizable monomer having a hydroxyl group and 50 to 88% by weight of styrene and/or its substituted product. A method for producing toner for latent image development. 3. The method for producing a toner for developing electrostatic latent images according to claim 2, which comprises dissolving component B in component A and polymerizing component A. 4. Component B has a melt viscosity of 100 to 1,000 at 140°C
A method for producing a toner for developing an electrostatic latent image according to claim 1, 2, or 3, which is a toner manufactured by Poise.