JPS58106553A - Binder used for electrophotographic toner - Google Patents

Abstract

PURPOSE:To obtain a toner binder suitable for high speed fixing not causing offset trouble, by using a specified polyolefin resin together with a vinyl type copolymer, and reacting them with a multifunctional cross-linking compd. to raise >=90 deg.C softening point. CONSTITUTION:A binder resin having >=90 deg.C softening point is obtained by mixing 10-90pts.wt. polyolefin resin A contg. reactive group glycidyl groups or the like, 90-10 pts.wt. vinyl type copolymer B consists of hydroxy-contg. monomer and acrylate, further adding 0-10pts.wt. multifunctional cross-linking compd. C to react the functional groups contained in the resins A, B with this compd. C by heating, and forming 100pts.wt. of A+B+C cross-linked product. This binder of a developer does not cause offset during the fixing operation of pressing and heating, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and useful binder for electrophotographic toners, and more specifically, the present invention relates to a new and useful binder for electrophotographic toner. The present invention relates to a binder obtained by

In recent years, electrophotography has required high-speed recording, and high-speed fixing using heat rolls has become necessary.
At present, a binder resin that simultaneously satisfies storage stability, offset resistance, and fixing properties suitable for such high-speed fixing has not been obtained.

However, as a result of intensive research in view of the above-mentioned current situation, the inventor of the present invention has discovered that it is possible to obtain a toner binder suitable for high-speed fixing that has excellent storage stability and surface 4 offset properties, and has completed the present invention. I ended up letting it happen.

That is, the present invention comprises a polyolefin resin (A) having 10 to 90 parts having a glycidyl group, a hydroxyl group, a carboxyl group or an acid anhydride group, and (b7.Q a glycidyl group-containing monomer alone or together with a hydroxyl group-containing monomer). A functional group-containing monomer that can be combined with one or more monomers selected from monomers, carboxyl group-containing monomers, and acid anhydride group-containing monomers.
~11jf%, (b-2) acrylic ester, methacrylic ester and/or α,β-unsaturated vesicular carboxylic acid dialkyl ester D ~99%, (b-1
) styrene and/or vinyltoluene in a range of D to 99% by weight, and (b-4') O to 50% by weight of other monomers that can be co-combined with each of the above monomers,
And a vinyl copolymer (B) 90-1 [] Yari I obtained by reacting the total monomer amount to 100% by weight
jt portion, and furthermore, at least 1 NLn of functional groups in one molecule that can react with each of the functional groups contained in the above-mentioned components (A) and B) during heating,
and a polyfunctional crosslinkable compound (C) having 2 or more 0-1
0i-jt parts so that the amount of the components (A) and (B) or the components (A), (B) and (C) is 100 parts by weight, and the mixture is reacted. The present invention provides a binder for electrophotographic toner having a softening point of 90°C or higher.

Here, the above polyolefin resin (A) is a copolymer of a glycidyl group-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, or an acid anhydride group-containing monomer and an olefin; saturated carboxylic acid or alpha,
It refers to resins modified with β-unsaturated vesicular carboxylic acids or their anhydrides, and both have glycidyl groups, hydroxyl groups, carboxyl groups, or acid anhydride groups. ) is 90℃ or higher,
Preferably it is 95°C or higher.

If the softening point is lower than 90°C, the storage stability will be poor, so it is best to never use one with a softening point of 70°C or lower.

Typical examples of the olefins mentioned above are:
5- Monoolefins such as ethylene, globylene, butylene and diolefins such as butadiene, and therefore,
The above-mentioned polyolefin resin refers to a single or copolymer of these olefins, and further includes other polymers that can be used in combination with these olefins, such as vinyl acetate, vinyl chloride, and (meth)acrylic ester. It also includes copolymers in which some of these monomers are used in combination.

Furthermore, among the functional group-containing monomers used to obtain both components (B) and (B), typical glycidyl group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and allyl group-containing monomers. Typical hydroxyl group-containing monomers include β-hydroxyethyl (meth)acrylate, β-hydroxyglobil (meth)acrylate, vinyl alcohol or allyl alcohol, etc. As mentioned above, typical carboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and itaconic acid monomer. Typical examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.

Therefore, of the polyolefin tree) JW (A) -
Taking carboxyl group-containing polyolefin resins or acid anhydride group-containing polyolefin resins as an example, the above-mentioned olefins may be used alone or (group 1), and the above seven olefins copolymerizable with these olefins may be used. - may also be copolymerized, or a homopolymer or copolymer of olefins may be halogenated with chlorine, etc., and the above-mentioned carboxyl group-containing monomer or acid anhydride group-containing monomer may be further added to the monomer or copolymer of olefins. Typical polyolefin resins having carboxyl groups or polyolefin resins having acid anhydride groups are those obtained by reaction and modification.

Although polyolefin resins having functional groups other than those described above can also be obtained by such a method, it is preferable to use the olefins alone or in combination,
It is preferable to copolymerize these olefins with other monomers that can be copolymerized with them.

On the other hand, the above-mentioned vinyl co-tetrapolymer (B) essentially contains the monomer (b-1) containing each of the above-mentioned functional groups, and further contains an acrylic ester, a methacrylic ester and/or an α,β-union. In addition to using either or both of the saturated dicarboxylic acid dialkyl ester (b-2) and styrene and/or vinyltoluene (b-3), if necessary, other monomers that can be copolymerized with each of these monomers are used. These monomers (b-4) are also used to copolymerize. Among these, typical monomers (b-2) include methyl (meth)acrylate, (meth) ) Ethyl acrylate, (meth)
Isopropyl acrylate, butyl (meth)acrylate,
Esters of (meth)acrylic acid such as 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate or benzyl (meth)acrylate and dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl maleate, maleic acid. and dialkyl esters of α,β-unsaturated dicarboxylic acids such as diethyl acid or diptyl maleate.

Further, typical examples of the monomer (b-4) include vinyl halide, vinyl acetate, acrylonitrile, and acrylamide.

9- The component (B) contains each of the above-mentioned monomers, 1 to 10% of monomer (b-1), and 0% of monomer (b-2) and/or monomer (b-3).
The monomer (b-4
) in a range of 0 to 50%, but in this case, the monomers (b-1') and (b-2
), even if it is obtained only from nanatsuma (b-1) and (
Monomer (b-1) may be obtained only from monomer (b-3).
), (b-2), and (b-3), and furthermore, monomer (b-4) may be obtained by combining these three monomers or each combination of the three monomers. Therefore, in any combination, it is a matter of course that the monomers are selected and used so that the alt of the monomers is 100%.

In addition, the above-described components (A) and (B) can each be obtained by known and commonly used methods. That is, in the case of component CB), any of solution polymerization, suspension polymerization or emulsion polymerization may be used, but in the case of component (A), suspension polymerization or emulsion polymerization is preferred.

The binder of the present invention is obtained by blending the thus obtained components (A) and (B) in a range of 10 to 90 parts by weight, respectively, so that the total amount is 10 parts by weight, here? - a functional group in component (A) and (B)
In combination with the functional groups in the components, these (A),
(B) When both components undergo a crosslinking reaction with each other, no further crosslinking is required, so there is no need to use the polyfunctional crosslinkable compound (C).

In the present invention, the component (C) is used in such a form, and is capable of reacting with each functional group contained in the components (A) and (B) described above during heating, for example. Functional groups such as carboxyl groups, isocyanate groups, glycidyl groups, hydroxyl groups, or amine groups in one molecule are referred to as those having two or more functional groups in one molecule, but typical examples include ortho-
, iso- or terephthalic acid or trimellitic acid; C2-C4 alkylene dicarboxylic acids such as oxalic acid, adipic acid or sebacic acid; toluene diisocyanate, inphorone diisocyanate or hexamethylene diisocyanate. or multi-cylindrical isocyanate compounds derived from these diisocyanates; amino acids such as glycine, aspartic acid, lysine tryptophan or amine benzoic acid; hydroxy acids such as hydroxybenzoic acid; ethylene glycol, propylene glycol, butylene glycol, hexamethylene Polyhydric alcohols such as glycol, glycerin, pentaerythritol, trimethylolethane, trimethylolpropane or )\idrogine; polyhydric amines such as diaminodiphenylmethane; or an average of two or more hydroxyl groups in one molecule , epoxy group, glycidyl group, amide 7
There are polyepoxy resins, polyester resins, polyamide resins, polyurethane resins, and polyvinyl resins containing one or more types of carboxyl groups, carboxyl groups, or isocyanate groups, and these epoxy resins include bisphenol-type epoxy resins, glycerin diglycidyl ether, or roseoxybenzoin. Included are polyepoxy compounds such as acid diglycidyl ester ethers.

It is preferable that the component (C) is used so as to be partially crosslinked with the component (A) and component (B) described above, or through the component (C). When components (A) and (B) each have a functional group capable of crosslinking with each other, the use of component (C) is not necessarily required.

The amount of the component (C) used is the total binder jt1
It is appropriate to use 0 to 10 parts by weight, preferably 0 to 5 parts by weight, in the 00 rainbow 13-- parts. This makes it unsuitable as a toner resin.

(The reactions of (A) and (B) above, and (A
), (B) and (C) can be carried out even in the presence of other components other than the resin constituting the toner, such as carbon black, or in the presence of no other components other than this resin. It can be done in any situation.

When producing a toner using the binder of the present invention, the above two components (A) and (B), or the three components (A), (B) and (C) and a colorant are used. In addition, polystyrene resin, acrylic resin, coumaron resin,
There is absolutely no problem in mixing known and commonly used natural or synthetic resins such as xylene resins, epoxy resins, polyester resins, polyamide resins, rosin-modified polymers, 14-leic acid resins or waxes, or additives such as charge control agents.・.

By using the thus obtained binder of the present invention, it is possible to obtain a toner with good offset resistance suitable for high-speed fixing with a heat roll and good storage stability.

Next, the present invention will be specifically explained using reference examples and examples.

In the following, all parts and percentages are based on weight unless otherwise specified.

Reference example 1 (Preparation example of functional group-containing polyolefin resin) 2
In the fourth flask of 1, add [Js-GJ (Mitsui Toatsu Chemical)
Polypropylene) 300,9. ) Luor 1,000
#.

14 g of maleic anhydride and 2 g of ditertiary-butyl peroxide were charged and reacted at 140°C with stirring for 3 hours. The solvent was removed under reduced pressure to obtain a solid resin (
A-1) was obtained. The softening point of this resin was 135°C.

Reference Example 2 (same as above) [Superchron 773HJ (Sanyo Kokusaku Balfu Washi chlorinated polypropylene; toluene solution with salt accumulation rate of 32% and non-volatile content of 45%) 1,000. ! iJ and anhydrous maleic l [5 g were charged into a 27 quart flask and reacted at 80°C for 12 hours.

This resin solution was precipitated with acetone and dried under reduced pressure to obtain a solid resin (A-2). The softening point of this resin is 118℃
Met.

Reference Example 3 (same as above) [Noprene BC3BJ (ethylene-propylene copolymer manufactured by Mitsubishi Yuka ■) 3oo, p, 4 g of methacrylic acid, 1,000 g of toluo-A and 2 g of tert-butyl barogycypenzoate After charging into the fourth flask of No. 21 and reacting at 80°C for 12 hours, remove the solvent under reduced pressure to obtain a solid resin Reference Example 4 (same as above).
, ooog, vinyl acetate 2,000ON, vinyl benzoate 2,000,9, glycidyl methacrylate) 190I!
, Colloidal palladium (01% aqueous solution) 20g, "Emar O" (Daiichi Kogyo Seiyaku ■, sodium lauryl sulfate) 1
2 ([and 20 g of hydroxyethyl cellulose were charged, propylene was blown into the autoclave twice to remove air, and the propylene pressure was increased to 100 g.
kg/c+/ and heated to 40°C.

Next, a catalyst solution prepared by dissolving 200I of potassium superconcentrate in 500g of ion-exchanged water was added dropwise over a period of 6 hours while a reaction was carried out to obtain 32% vinyl acetate and 62% vinyl benzoate.
%, propylene 64% and glycidyl methacrylate-1
- A copolymer containing 25H was obtained.

Thereafter, saline solution was added to this co-rectangular mixture to precipitate MQ, washed with water and dried to obtain a solid resin (A-4).

Reference Example 5 (Example of Preparation of Vinyl Coelectrical Copolymer Containing Functional Groups) Into a flask equipped with a stirring device and a reflux condenser at a temperature of W1°, 670 parts of xylene was charged and heated to 120°C, and then 650 parts of styrene and methacrylic A mixture consisting of 300 parts of n-butyl acid, 50 parts of methacrylic acid, and 15 parts of azobisisobutyronitrile was added dropwise with stirring over 6 hours, and was further maintained at the same temperature for 15 hours to react, and then the pressure was reduced. The solvent was removed below to obtain a solid resin (B-1).

Reference Example 6 (same as above) When charging xylene, 50 parts of maleic anhydride was also charged, and the amount of styrene was set to 600 parts, and the amount of n-butyl methacrylate was set to 650 parts. A solid resin (B-2) was obtained in the same manner as in Reference Example 5, except that methacrylic acid was omitted.

Reference Example 7 (same as above) 600 parts of styrene and 65 parts of n-butyl methacrylate
The procedure was repeated in the same manner as in Reference Example 5, except that the same amount of β-hydroxyethyl methacrylate was used in place of methacrylic acid, and the solid [fat (B-3 ) was obtained.

Silkworm Example 8 (same as above) Reference Example 7 except that the same amount of glycidyl methacrylate was used instead of β-hydroxyethyl methacrylate.
1 A solid resin (B-4) was obtained in the same manner.

Example 1 To 100 parts of (A-1) obtained in Reference Example 1, Reference Example 6 was added.
100 parts of (B-2) obtained in (B-2) and 1.5 parts of neopentyl glycol were added, mixed with a Henshil mixer, and then reacted at 210°C for 1 hour.

The softening point of the resin described here was 140°C.

Next, 8 parts of carbon black was kneaded with a heated roll per 100 g of this resin, cooled and pulverized to a powder of 5 to 25 mμ.
I got a new toner. When this toner was used for high-speed copying and continuous copying, stable images were obtained even after 24 hours of continuous use. Furthermore, offset resistance and storage stability were also good.

Example 2 To 100 parts of (A-3) obtained in Reference Example 6 and ioo parts of (R-1) obtained in Reference Example 5, 1 Ebicuron 4050J (epoxy resin manufactured by Inu Nippon Ink Chemical Industry ■);
After adding 6 parts of epoxy AT900-i, ooo) and mixing with a Henschel mixer, the mixture was reacted at 180°C for 50 minutes. The softening point of the resin obtained here was 132°C. Except for using this resin, the same treatments and operations as in Example 1 were performed, and as a result, a stable image was obtained, and this product also had good offset resistance and storage stability.

Example 6 Resin (A-1) obtained in Reference Example 2 was used instead of resin (A-1).
-2) was carried out in the same manner as in Example 1, except that the same amount was used, and a stable image was obtained, and this product also had good offset resistance and storage stability.

Example 4 The same procedure as in Example 1 was carried out except that 15 parts of neopentyl glycol was replaced by 6 parts of 1 Laccamite N-1561M (Polyamide 21-dead resin manufactured by Inu Nippon Ink Chemical Co., Ltd.). However, the binder obtained also had good offset resistance and storage stability.

Example 5 200 parts of the resin (A-4) obtained in Reference Example 4, 100 parts of Jugetsuji (13-4) that had been quenched in Reference Example 8, and 1.5 parts of terephthalic acid were mixed into Henschel After sufficient stirring with a mixer, the resin was reacted at 180°C for 1 hour, and the resulting resin had a softening point of 125°C. A stable image was obtained by carrying out the same procedure as in Example 1 except for using this resin, and this product had good anti-offset properties and anti-blocking properties.

Example 6 [Eval El)-EJ [■Cura VH Ethylene-vinyl alcohol copolymer Before vinyl alcohol content = about 60%
] 15 parts and the resin (B-3) obtained in Reference Example 7 84
．． After thoroughly mixing 3 parts 22-, 0.7 parts of inphorone diisocyanate was further added, stirred well with a Henschel mixer, and reacted at 170 to 180°C for 30 minutes. The softening point of the resin obtained here was 145°C. Except for using this resin, the same treatment and operation as in Example 1 were repeated, and a stable image was obtained, and this product had good offset resistance and surface 4-bronogging properties. .

Example 7 100 parts of the resin (A-1) obtained in Reference Example 1 and 20 parts of the resin (B-4) obtained in Reference Example 8 were sufficiently stirred with a Henschel mixer, and the mixture was heated to 160 to 180°C. The reaction was carried out for 6 parts. At this point, the softening point of the fat was 135°C. When the same operations as in Example 1 were repeated for the samples other than 9 in which this resin was used, stable images were obtained, and these samples also had good anti-offset properties and anti-blocking properties.

Patent applicant: Dainippon Ink Chemical Industry Co., Ltd. 23-

Claims (1)

Scope of Claims: (A) 10 to 90 parts by weight of a polyolefin resin having a glycidyl group, hydroxyl group, carboxyl group or acid anhydride group and having a softening point of 90° C. or higher. (B) Glycidyl group-containing monomer alone or in combination with one or more monomers selected from hydroxyl group-containing monomers, carboxyl group-containing monomers, and acid anhydride group-containing monomers (b-1)
101% by weight, 0 to 99% by weight of acrylic ester, methacrylic ester and/or α,β-unsaturated dicarboxylic acid dialkyl ester (b-2), 0% of styrene and/or vinyltoluene (b-3)
~99% deuterium, and 0~50% of other monomers (b-4) that are copolymerizable with each of the above monomers.
Vinyl copolymer obtained by reacting within the range and such that the total amount of monomers is 100 & it% 90~
(C) contains at least one functional group in each molecule that can react with each of the functional groups contained in the above-mentioned components (A) and (B) upon heating, and , 0 to 10 parts by weight of a polyfunctional crosslinking compound having two or more of them in a total amount of 100 parts by weight, and the resulting binder has a softening point of 90° C. or higher and is obtained by reacting the binder with a polyfunctional crosslinking compound having 0 to 10 parts by weight in a total amount of 100 parts by weight.