JP3418518B2 - Resin composition for toner and toner - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for toner used in electrophotography and the like, and more specifically, in a method for developing an electrostatic image, a resin composition for toner used in a dry developing system. The thing and the toner.

[0002]

2. Description of the Related Art A dry developing system is often used as a method for developing an electrostatic image in electrophotography or the like. In this dry development method, a triboelectrically-charged toner (developer) is prepared by mixing a carrier such as iron powder or glass beads into a fine powder containing a colorant such as carbon black in a toner resin as a binder and other additives. Is used.

In order to obtain a copy by the above-mentioned dry developing method, usually, an electrostatic latent image is formed on a photoconductor, and a triboelectrically chargeable toner is electrically adhered to the latent image for development, and this toner image is formed. It is transferred onto a sheet such as a sheet of paper, and is fixed by a heat and pressure roller having releasability to toner to form a permanent visible image.

The basic properties of the toner used in the above-mentioned copying method are anti-offset property (the toner does not adhere to the hot pressing roller for fixing and does not stain the paper), low temperature fixing property (the toner does not stick to the paper at low temperature). In order to efficiently produce a toner, it is required that the resin composition for a toner constituting the toner is easily pulverized. Needed for.

In order to obtain a toner excellent in low temperature fixing property,
Composition improvement has been widely carried out for the purpose of lowering the softening point of toner. As a general method for improving the composition of this kind, there is a method of using a resin for toner having a low softening point as a resin for toner that constitutes most of the toner. However, the toner obtained by this method surely exhibits low-temperature fixability depending on the softening point of the toner resin, but its effect is limited in view of adverse effects on storage stability and offset resistance. That is, if the softening point of the toner resin is lowered too much, the storage stability becomes insufficient and the hot offset resistance also deteriorates.

As a method of lowering the softening point of the toner without impairing the offset resistance, a method of adding a block copolymer containing a rubber component has been proposed. Further, a method of adding a small amount of a low-melting point crystalline compound as a fixing aid to this system in consideration of low-temperature fixing property has been disclosed (JP-A-4-226473).

However, the toner obtained by the above-mentioned method surely shows excellent offset resistance and excellent low-temperature fixing property when a low-melting-point crystalline compound is added. It has been pointed out that since the dispersibility of the coalescence itself is not sufficient, the fixing strength is not sufficient, and the image easily peels off due to stress such as friction.
Furthermore, in the case of copying using a high-speed type or small-sized electronic copying machine, which has been in high demand in recent years, the above performance is not always sufficient, and a toner excellent in low-temperature fixing property and fixing strength is particularly demanded. ing.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems of the above-mentioned conventional toners, and its object is to provide excellent offset resistance, low-temperature fixability, storage stability and pulverizability, and It is an object of the present invention to provide a resin composition for toner having excellent fixing strength and a toner using the resin composition for toner.

[0009]

The resin composition for a toner according to the invention of claim 1 of the present invention (hereinafter referred to as the first invention) comprises a styrene monomer and a (meth) acrylic acid ester-based monomer. a toner resin composition as a main component a vinyl copolymer containing a body as a constituent unit, in the toner resin composition, a styrene having a hydroxyl group at the terminal - olefin - styrene ternary It is characterized by containing a block copolymer.

The invention according to claim 2 of the present invention (hereinafter referred to as the second
The resin composition for a toner according to the invention) comprises a styrene-based monomer and a (meth) acrylic acid ester-based monomer as constituent units, and has an acid value of 1 to 40 KOHmg / g. a toner resin composition composed mainly of a polymer, in the toner resin composition, a styrene having a hydroxyl group at the end - which is characterized by containing a styrenic triblock copolymer - olefin .

The first invention will be described below. The resin composition for a toner of the first invention contains a vinyl-based copolymer containing a styrene-based monomer and a (meth) acrylic acid ester-based monomer as constituent units as a main component.

Examples of the styrene-based monomer include
In addition to styrene, vinyltoluene and α-methylstyrene, halogenated styrene derivatives such as p-chloromethylstyrene and p-chlorostyrene; hydroxylated styrene such as p-hydroxymethylstyrene and 2- (p-vinylphenyl) ethanol. Derivatives: p-nitrostyrene, p-
Nitrated styrene derivative such as (2-nitroethyl) styrene; Cyanated styrene derivative such as p-cyanostyrene, m-cyanostyrene; p-aminostyrene, 3,4-
Examples thereof include amino (including N-containing) styrene derivatives such as diaminostyrene; carboxylated styrene derivatives such as p-vinylbenzoic acid and 3-vinylsalicylic acid.

Examples of the (meth) acrylic acid ester type monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
N-Butyl (meth) acrylate, isobutyl (meth) acrylate, n-octyl (meth) acrylate, (meth)
Dodecyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, chloroethyl (meth) acrylate,
2-Hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, N, N (meth) acrylic acid
-(Meth) acrylic acid esters such as dimethylaminoethyl; dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, dimethyl fumarate, and dimethyl itaconate.

The vinyl-based copolymer contains, in addition to the styrene-based monomer and the (meth) acrylic acid ester-based monomer,
Vinyl-based monomers may be added, and examples of such vinyl-based monomers include vinyl esters such as vinyl acetate and vinyl propionate; ethylene, propylene,
Unsaturated monoolefins such as butylene and isobutylene;
Diene vinyl monomers such as butadiene and isoprene; halogenated ethylenes such as chloroethylene and fluoroethylene; unsaturated carboxylic acids such as (meth) acrylic acid, α-ethylacrylic acid and crotonic acid; fumaric acid, maleic acid , Unsaturated dicarboxylic acids such as itaconic acid and citraconic acid; (meth) acrylonitrile derivatives such as (meth) acrylonitrile and chloroacrylonitrile; (meth) acrylamide, dimethylacrylamide, N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide (Meth) acrylamide derivatives such as; vinylpyrrolidone, 4-vinylpyridine, vinyl monomers having a heterocycle such as 4-vinyltetrahydrofuran, and the like, and these may be used alone or in combination of two or more. You may use together.

In the above resin composition for toner, the vinyl-based copolymer containing styrene-based monomer and (meth) acrylic acid ester-based monomer as main components is a low-molecular weight polymer component and a high-molecular weight polymer component. It is preferable to contain and.

The low molecular weight polymer component preferably has a weight average molecular weight (Mw) of 3,000 to 50,000, a softening point (Tf) of 150 ° C. or lower, and a glass transition point (Tg) of 50 ° C. or higher. The component ratio in the copolymer is 60-
95% by weight is preferred.

If the weight average molecular weight (Mw) of the low molecular weight polymer component exceeds 50,000, the pulverizability may decrease, and if it is less than 3000, the glass transition point (T
Storage stability may decrease due to the decrease of g). If the softening point (Tf) of the low molecular weight polymer component is higher than 150 ° C, sufficient low-temperature fixability may not be obtained, and if the glass transition point (Tg) is less than 50 ° C, storage stability will be reduced. I have something to do.

The component ratio of the above low molecular weight polymer component is 6
If it is less than 0% by weight, the pulverizability and low-temperature fixability may be lowered, and if it is more than 95% by weight, the offset resistance may be lowered.

The high molecular weight polymer component has a weight average molecular weight (Mw) of 100,000 to 5,000,000 and a softening point (Tf).
Is preferably 150 ° C. or higher and the glass transition point (Tg) is 50 ° C. or higher, and the component ratio of the high molecular weight polymer component in the vinyl copolymer is preferably 40 to 5% by weight.

The weight average molecular weight (Mw) of the high molecular weight polymer component is less than 100,000 or the softening point (Tf) is 150 ° C.
When it is less than 1, the offset resistance may be deteriorated. If the component ratio of the high molecular weight polymer component is more than 40% by weight, the pulverizability and low temperature fixability may be lowered, and if it is less than 5% by weight, the offset resistance may be lowered.

[0021] The styrene - olefin - styrene triblock copolymer (hereinafter, referred to as triblock copolymer) include are used those having a hydroxyl group at the terminal. The hydroxyl group is necessary to be present in at least one end of the triblock copolymer may be present at both ends.

The triblock copolymer, when no hydroxyl group at the end, and affinity decrease in the vinyl copolymer constituting the toner resin, that the offset resistance is degraded In addition, in a system containing a low-melting point crystalline compound, the dispersibility of the low-melting point crystalline compound in the resin composition may decrease, and storage stability may decrease.

Further, the ternary block copolymer preferably has a polystyrene content of 5 to 80% by weight and a styrene-equivalent number average molecular weight of 1,000 to 500,000.

When the polystyrene content in the ternary block copolymer is less than 5% by weight, the affinity between the ternary block copolymer and the vinyl copolymer is lowered and the offset resistance is lowered. In addition, in a system containing a low melting point crystalline compound, the dispersibility of the low melting point crystalline compound in the resin composition for toner may be lowered, and the storage stability may be lowered.

When the polystyrene content in the ternary block copolymer is more than 80% by weight, the effect of improving the offset resistance is not easily exhibited, and in the system containing the low melting point crystalline compound, The dispersibility of the low-melting-point crystalline compound in the toner resin composition may decrease, and storage stability may decrease.

The styrene-equivalent number average molecular weight is 10
When it is less than 00, the glass transition point (Tg) of the vinyl-based copolymer constituting the toner resin composition may be lowered, and the storage stability may be lowered. Number average molecular weight is 50
If it exceeds 10,000, the low temperature fixability may be deteriorated.

The ternary block copolymer having a hydroxyl group at a terminal can be obtained by living polymerization. The olefin, which is one component of the ternary block copolymer, is preferably a diene-based monomer as a start monomer, and examples thereof include butadiene and isoprene.

The above-mentioned synthesized ternary block copolymer is
Double bonds remain as 1,4 and 1,2 bonds, but compounds obtained by hydrogenating these bonds can also be used. As described above, the polyolefin block portion can have various structures and is not particularly limited, but the polyolefin block portion is more preferably 1,4-butadiene hydrogenated type.

In addition, the terminal of the terpolymer block copolymer
Hydroxyl groups make it easy to control the amount of charge on the toner and easy to synthesize.
This is preferable.

In the toner resin composition, the content of the ternary block copolymer is such that the vinyl copolymer 10
0.1 to 5 parts by weight is preferable with respect to 0 parts by weight. When the content of the ternary block copolymer is less than 0.1 part by weight,
Offset resistance may decrease, and in a system containing a low-melting point crystalline compound, the dispersibility of the low-melting point crystalline compound in the resin composition may decrease, and storage stability may decrease. . When the content of the ternary block copolymer is more than 5 parts by weight, the storage stability and the low-temperature fixability also decrease due to the influence of the polyolefin block portion in the ternary block copolymer. Sometimes.

The ternary block copolymers may be used alone or in combination of two or more.

Next, the second invention will be described. The resin composition for a toner of the second invention contains a styrene-based monomer and a (meth) acrylic acid ester-based monomer as constituent units, and has a vinyl-based copolymer having an acid value of 1 to 40 KOHmg / g. the a toner resin composition as a main component, in the toner resin composition, a styrene having a terminal hydroxyl group - containing styrene triblock copolymer - olefin.

The above vinyl-based copolymer contains the same styrene-based monomer and (meth) acrylic acid ester-based monomer as constituent units as in the first invention. The vinyl copolymer preferably contains a low molecular weight polymer component and a high molecular weight polymer component, as in the first invention.

The acid value of the vinyl copolymer used in the second invention is limited to 1 to 40 KOHmg / g. When the acid value of the vinyl-based copolymer is 1 KOHmg / g, the effect of improving dispersibility due to grafting of a styrene-olefin-styrene ternary block copolymer having a hydroxyl group at the terminal is hardly exhibited, and exceeds 40 KOHmg / g. In some cases, the cohesive force between the vinyl copolymer and the vinyl copolymer is increased, and the low temperature fixability is not improved.

The acid value of the vinyl copolymer is 1 to 40K.
In order to obtain OH mg / g, it is preferable to use an acid-based monomer as a monomer constituting the vinyl-based copolymer, in addition to the styrene-based monomer and the (meth) acrylic acid ester-based monomer. preferable.

The above-mentioned acid-based monomer is not particularly limited, and examples thereof include vinyl-based monomers having groups such as carboxylic acid, sulfonic acid, sulfinic acid, phosphonic acid and boric acid. Above all, it is preferable to use a vinyl-based monomer having a carboxylic acid group from the viewpoints of the cohesive force of an acid and the ease of copolymerization.

Examples of the vinyl monomer having a carboxylic acid group include carboxylated styrene derivatives such as p-vinylbenzoic acid and 3-vinylsalicylic acid; (meth)
(Meth) acrylic acid derivatives such as acrylic acid, α-ethylacrylic acid, crotonic acid; fumaric acid, maleic acid,
Examples thereof include unsaturated dicarboxylic acids such as citraconic acid and itaconic acid.

The styrene having hydroxyl group at a terminal - olefin - as styrene triblock copolymer, the first
The same thing as the invention is used.

A low melting point crystalline compound may be added to the toner resin composition of the present invention. The low melting point crystalline compound is preferably a compound having a melting point of 55 to 130 ° C. If the melting point is less than 55 ° C, the storage stability may decrease, and if the melting point is higher than 130 ° C,
The low temperature fixability may decrease.

As such a low melting point crystalline compound,
Examples thereof include low molecular weight crystalline compounds, waxes, crystalline polymers and the like.

Examples of the low molecular weight crystalline compound include, for example, 1-hexadecanol, 1-heptadecanol, stearyl alcohol, 1-nonadecanol, 1-eicosanol, 1-docosanol, 1-tricosanol, 1-tetracosa. Higher alcohols such as nor and ceryl alcohol; palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid and other higher fatty acids and their esters; linoleic acid amide, ricinoleic acid amide, eruca Examples thereof include fatty acid amides such as acid amide, oleic acid amide, eicosenoic acid amide, erucic acid amide, and palmitoleic acid amide.

Examples of the above waxes include animal waxes such as beeswax and whale wax; plant waxes such as carnauba wax, candelilla wax and wood wax; petroleum waxes such as paraffin wax and microcrystalline wax; Synthetic hydrocarbons such as Tropsch wax and low molecular weight polyethylene; and n-paraffins having 21 or more carbon atoms.

Examples of the crystalline polymer include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hexamethylene glycol and tetramethylene glycol. With polyols such as fumaric acid, maleic acid,
Polyesters obtained by polycondensation with polybasic acids such as itaconic acid, terephthalic acid, succinic acid, adipic acid and sebacic acid; polyethers such as polyethylene glycol and polypropylene glycol; behenyl acrylate, behenyl methacrylate, itacone Examples thereof include vinyl polymers containing a long-chain alkyl ester such as behenyl acid salt and stearyl itaconic acid as a main polymerization unit.

The amount of the low melting point crystalline compound added is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the vinyl copolymer. If the addition amount is less than 5 parts by weight, sufficient low-temperature fixability may not be obtained, and if it is more than 20 parts by weight, storage stability may decrease.

The toner resin composition of the present invention is, for example,
The vinyl-based copolymer, the ternary block copolymer,
And, it can be produced by mixing a low-melting-point crystalline compound as necessary and melt-kneading this with a roll mill, a kneader, an extruder or the like.

As a method for producing a resin composition for a toner other than the above, in the polymerization process of the vinyl copolymer,
Examples thereof include a method of adding a ternary block copolymer and, if necessary, a low-melting point crystalline compound at any stage before polymerization, during polymerization, and after polymerization. As the polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like can be adopted, but in particular, a ternary block copolymer or the like is added before polymerization from the viewpoint of ease of production, and a solution is obtained. The method of carrying out the polymerization is preferred.

The toner of the present invention can be produced, for example, using the above resin composition for toner as follows. 1) A colorant and other additives are mixed with the toner resin composition, and the mixture is melt-kneaded with a roll mill, a kneader, an extruder or the like. After cooling, finely pulverize with a pulverizer such as a jet mill, classify if necessary, and have a particle size of 5 to 20μ.
m toner particles.

2) The vinyl copolymer is mixed with a ternary block copolymer, a colorant, other additives and, if necessary, a low melting point crystalline compound, and this is mixed with a roll mill,
Melt and knead with a kneader or an extruder. After cooling, it is finely pulverized using a pulverizer such as a jet mill, and if necessary, classified to obtain toner particles having a particle size of 5 to 20 μm.

The other additives are additives that are added as necessary, and examples thereof include a charge control agent, a release agent, and magnetic fine particles.

Examples of the colorant include carbon black, chrome yellow, aniline blue, phthalocyanine blue, ultramarine blue, and nigrosine dye. Examples of the charge control agent include nigrosine dye, rhodamine dye, and azo metal complex. Examples of the releasing agent include polypropylene, polyethylene, ethylene-propylene copolymer and the like. Examples of the magnetic fine particles include fine powders of metals such as nickel, manganese, iron, cobalt and chromium, various ferrites and various alloys.

To the toner thus obtained, a fluidizing agent may be added later in order to enhance the fluidity as a powder. Examples of the fluidizing agent include hydrophobic silica powder, acrylic resin powder, fluorine resin powder, and higher fatty acid metal salt powder.

[0052]

In the resin composition for a toner of the present invention, a vinyl-based copolymer having a styrene-based monomer and a (meth) acrylic acid ester-based monomer as a constitutional unit is a main component, and a terminal is further added.
Styrene having a hydroxyl group - olefin - by containing a styrenic triblock copolymer, by a hydroxyl group of a polystyrene block portion and a distal end of triblock copolymer having, improved compatibility with the resin matrix However, the effect of the polyolefin block portion improves the offset resistance.

[0053] In the toner resin composition of the second invention, the hydroxide base and an acid number of ends triblock copolymer has partially grafting the monomer component 1~40KOHmg / g As a result, the compatibility with the resin matrix is further improved, and the offset resistance is improved by the effect of the polyolefin block portion.

In the resin composition for toner of the present invention, the low-temperature fixing property is improved by adding the low-melting point crystalline compound, but the ternary block copolymer can improve the dispersibility of the low-melting point crystalline compound. It has the effect of further improving.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION Examples and comparative examples of the present invention will be described below. (Example 1) Toluene 600 was placed in a 3 L (liter) separable flask.
g of styrene having a weight average molecular weight of 2,000,000-n-
Butyl acrylate-methyl methacrylate copolymer 1
20 g, and styrene / hydrogenated isoprene / styrene terpolymer having a hydroxyl group at the terminal (Mw =
54,000, styrene content 30% by weight) 15 g were added and dissolved. After replacing the gas phase with nitrogen gas, the system was heated to the reflux temperature of toluene. While stirring under reflux of toluene, 760 g of styrene, 100 g of methyl methacrylate, 1 n-butyl acrylate
Solution polymerization was carried out while dropping 40 g and a mixture in which 55 g of azobisisobutyronitrile as a polymerization initiator was dissolved over 2.5 hours. After completion of the dropping, the mixture was aged for 30 minutes while stirring at the reflux temperature of toluene, and then toluene was removed under reduced pressure while raising the oil bath temperature to 160 ° C. to obtain a resin. After cooling this resin, it was pulverized to obtain the resin composition for toner of the present invention.

100 parts by weight of this toner resin composition, 5 parts by weight of carbon black ("MA-100" manufactured by Mitsubishi Chemical Co., Ltd.), 1 part by weight of Spiron Black TRH and 3 parts of PP wax ("Viscor 550P" manufactured by Sanyo Kasei Co., Ltd.) 3 Parts by weight are melt-blended, cooled, coarsely pulverized, and then finely pulverized with a jet mill (“Labojet” manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a toner powder having an average particle size of about 8 to 12 μm. Pneumatic Mfg. Co., Ltd. “MDS
-2 ") to produce a toner having an average particle size of 10 μm. To 300 g of this toner, 0.9 g of hydrophobic silica powder finely pulverized with a coffee mill was added and blended with a mixer to prepare a developer.

(Example 2) Styrene having a hydroxyl group at the terminal instead of styrene having a hydroxyl group at the terminal-hydrogenated isoprene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) Example 1 except that 15 g of hydrogenated 1,4-butadiene-styrene ternary block copolymer (Mw = 54,000, styrene content 35% by weight) and 100 g of polyethylene wax having a melting point of 80 ° C. were added. A resin composition was synthesized in the same manner as in. A toner having an average particle diameter of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Example 3 A resin composition was synthesized in the same manner as in Example 1 except that 150 g of polyethylene wax having a melting point of 100 ° C. was further charged into a 3 L separable flask. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Example 4 Instead of 120 g of styrene-n-butyl acrylate-methyl methacrylate copolymer having a weight average molecular weight of 2,000,000, 250 g of styrene-n-butyl acrylate-methyl methacrylate copolymer having a weight average molecular weight of 1.7 million.
Was added, and a resin composition was synthesized in the same manner as in Example 1 except that 40 g of azobisisobutyronitrile was used as a polymerization initiator. A toner having an average particle size of 10 μm was prepared from this resin composition in the same manner as in Example 1,
A developer was prepared in the same manner as in Example 1.

Example 5 Instead of 15 g of a styrene-hydrogenated isoprene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) having a hydroxyl group at the terminal, it has a hydroxyl group at the terminal. A resin composition was synthesized in the same manner as in Example 1 except that 15 g of styrene-hydrogenated isoprene-styrene ternary block copolymer (Mw = 61,000, styrene content 65% by weight) was used. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Example 6 Instead of 15 g of a styrene-hydrogenated isoprene-styrene ternary block copolymer having a hydroxyl group at the terminal (Mw = 54,000, styrene content 30% by weight), a hydroxyl group at the terminal is present. A resin composition was synthesized in the same manner as in Example 1 except that 25 g of styrene-hydrogenated isoprene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) was used. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Example 7 A styrene-n-butyl acrylate-methyl methacrylate copolymer having a weight average molecular weight of 1.7 million was used instead of 120 g of a styrene-n-butyl acrylate-methyl methacrylate copolymer having a weight average molecular weight of 2 million. United 25
A resin composition was synthesized in the same manner as in Example 2 except that 0 g was used and the amount of azobisisobutyronitrile used was 40 g. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Example 8 A styrene-hydrogenated 1,4-butadiene-styrene ternary block copolymer having a hydroxyl group at the end (Mw = 54.0)
0, styrene content 35% by weight) 15 g instead of 15 g of a styrene-hydrogenated isoprene-styrene ternary block copolymer having terminal hydroxyl groups (Mw = 61,000, styrene content 65% by weight). A resin composition was synthesized in the same manner as in Example 2 except for the above. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

(Example 9) Styrene-hydrogenated 1,4-butadiene-styrene ternary block copolymer having a hydroxyl group at the end (Mw = 54.0)
0, styrene content 35% by weight) 15 g instead of 15 g of styrene-hydrogenated 1,4-butadiene-styrene terpolymer block copolymer (Mw = 54.0)
A resin composition was synthesized in the same manner as in Example 2 except that 25 g of 0, styrene content 35% by weight) was used.
From this resin composition, an average particle size of 1 was obtained in the same manner as in Example 1.
After producing a toner of 0 μm, a developer was prepared in the same manner as in Example 1.

(Comparative Example 1) A resin composition was synthesized in the same manner as in Example 1 except that no styrene-hydrogenated isoprene-styrene ternary block copolymer having a hydroxyl group at the terminal was used. From this resin composition, an average particle size of 10 was obtained in the same manner as in Example 1.
After producing a toner of μm, a developer was prepared in the same manner as in Example 1.

(Comparative Example 2) A resin composition was prepared in the same manner as in Example 2 except that no styrene-hydrogenated 1,4-butadiene-styrene ternary block copolymer having a hydroxyl group at the terminal was used. Was synthesized, and a toner having an average particle diameter of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Comparative Example 3 Instead of 15 g of a styrene-hydrogenated isoprene-styrene ternary block copolymer having a hydroxyl group at the terminal (Mw = 54,000, styrene content 30% by weight), a hydroxyl group at the terminal is present. Example 1 except that 15 g of styrene-hydrogenated isoprene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) was used.
A resin composition was synthesized in the same manner as in 1., and a toner having an average particle diameter of 10 μm was produced from the resin composition in the same manner as in Example 1 and then a developer was prepared in the same manner as in Example 1.

(Comparative Example 4) Styrene-hydrogenated 1,4-butadiene-styrene ternary block copolymer (Mw = 54.0) having a hydroxyl group at the terminal.
0, styrene content 35% by weight) 15 g instead of 15 g of styrene-hydrogenated isoprene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) having no hydroxyl group at the end. Except that I used it
A resin composition was synthesized in the same manner as in Example 2, and a toner having an average particle diameter of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

With respect to the resin compositions for toner obtained in the above Examples and Comparative Examples, and the toner and the developer using the same, the performance evaluation of the following items was performed, and the evaluation results are shown in Table 1.

(1) Measurement of glass transition point (Tg) Using a "DSC220C" manufactured by Seiko Denshi Kogyo Co., Ltd., a resin composition for a toner is shown in FIG. After obtaining the curve shown, the intersection of the tangents was taken as the glass transition temperature (Tg).

(2) Measurement of softening point (Tf) Flow tester "CFT-500" manufactured by Shimadzu Corporation
“A”, the measurement temperature is 60 ° C. by the temperature raising method under the measurement conditions of nozzle diameter 1 mm, thickness 0.1 mm, and load 20 kgf.
˜200 ° C., temperature rising rate 6 ° C.-min, preheat 300 seconds, and the flow curve shown in FIG. 2 was obtained for the resin composition for toner. The temperature corresponding to 1/2 h in the figure was defined as the softening point (Tf).

(3) Measurement of Molecular Weight From the molecular weight distribution of the resin composition for toner obtained by gel permeation chromatography (GPC), the molecular weights of two peaks indicating the copolymer component are based on the molecular weight distribution as shown in FIG. The weight average molecular weight (Mw) of each was calculated by dividing the line by a line perpendicular to the valley of the peak. Here, the GPC is "HTR-C" manufactured by Japan Millipo Limited, and "KF-800P" (1) and "KF-806M" (2) manufactured by Showa Denko KK for the column.
Book) and "KF-802.5" (1 book) were connected in series and used. The measurement conditions were a temperature of 40 ° C., a sample concentration of 0.2 wt% THF solution (passed through a 0.45 μm filter), and an injection amount of 100 μl was injected. Standard polystyrene was used as a calibration sample.

(4) Measurement of dispersed particle diameter The dispersed state of the added low melting point crystalline compound was observed with a TEM (transmission electron microscope). As a dispersed state, TEM
The particle diameter of the more confirmed low melting point crystalline compound was measured, and the average value was taken.

(5) Preservation test 20 g of the toner is put in a 200 ml sample bottle and stored at 50 ° C.
After leaving it in the constant temperature bath for 48 hours, use a powder tester "PT-E type" manufactured by Hosokawa Micron Co., Ltd.
Sieving under the condition of 10 m for 10 seconds, and the remaining amount of the sieve having an opening of 250 μm was 1 g or less, it was determined to be acceptable.

(6) Measurement of Fixing Temperature 6.5 parts by weight of toner was mixed with 93.5 parts by weight of iron powder carrier having a particle size of about 50 to 80 μm to prepare a mixture, and a copy was obtained using this mixture. . The electrophotographic copying machine used is a modified version of "U-BIX4160AF" manufactured by Konica. The fixing temperature is such that the copy obtained by changing the set temperature of the heat roller of the electrophotographic copying machine is rubbed with a pad,
The rate of change in the density of the copied image, that is, the set temperature when the fixing rate was 85% was used.

(7) Measurement of non-offset width The set temperature of the heat roller of the electrophotographic copying machine was variously changed to a temperature range in which no offset occurred.

[0077]

[Table 1]

Example 10 Styrene 760 g, methyl methacrylate 100 g, n
-Styrene 8 instead of 140 g butyl acrylate
00g, n-butyl acrylate 90g, acrylic acid 1
A toner having an average particle size of 10 μm was prepared in the same manner as in Example 1 except that 0 g was used, and then a developer was prepared in the same manner as in Example 1.

Example 11 Instead of 15 g of a styrene-hydrogenated isoprene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) having a hydroxyl group at the terminal, it has a hydroxyl group at the terminal. Except that 15 g of styrene-hydrogenated 1,4-butadiene-styrene ternary block copolymer (Mw = 54,000, styrene content 30% by weight) and 100 g of polyethylene wax having a melting point of 80 ° C. were added. A resin composition was synthesized in the same manner as in Example 10. A toner having an average particle diameter of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

(Example 12) 800 g of styrene, 100 g of methyl methacrylate, n
-Butyl acrylate 90g and acrylic acid 10g
A resin composition was synthesized in the same manner as in Example 1 except that 780 g of styrene, 60 g of methyl methacrylate, 120 g of n-butyl acrylate, and 40 g of methacrylic acid were used instead of. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Comparative Example 5 A resin composition was prepared in the same manner as in Example 10 except that no styrene-hydrogenated 1,4-isoprene-styrene ternary block copolymer having a hydroxyl group at the terminal was used. Was synthesized. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

Comparative Example 6 A resin composition was prepared in the same manner as in Example 11 except that no styrene-hydrogenated 1,4-butadiene-styrene ternary block copolymer having a hydroxyl group at the end was used. Was synthesized. A toner having an average particle size of 10 μm was produced from this resin composition in the same manner as in Example 1, and then a developer was prepared in the same manner as in Example 1.

With respect to the resin compositions for toner obtained in Examples 10 to 12 and Comparative Examples 5 and 6, and the toner and the developer using the same, the same items (1) to (7) as in Example 1 were used. In addition, (8) was further evaluated, and the evaluation results are shown in Table 2.

(8) Acid Value In the above Examples 10 to 12 and Comparative Examples 5 and 6, polymers not containing only the ternary block copolymer were synthesized, 2.0 g of this polymer was precisely weighed, and methyl ethyl ketone was added. 30m
dissolve in 1. The solution was titrated with a 1 / 50N potassium hydroxide-isopropyl alcohol solution (KOH-IPA solution) using a 1% phenolphthalein solution as an indicator, and calculated by the following formula. Acid value (KOHmg-g) = | (1/50) * F * 56.11 * (AB) | -M where F: 1-50 NKOH-IPA solution titer A: KOH required for titration of solution -IPA solution B: KOH-IPA solution amount required for titration in blank test (only methyl ethyl ketone) M: Sample weight

[0085]

[Table 2]

[0086]

EFFECT OF THE INVENTION The resin composition for toner and the toner of the present invention have the above-mentioned constitutions and are excellent in offset resistance, low temperature fixing property, storage stability and pulverizability, and fixing strength.

[Brief description of drawings]

FIG. 1 is a graph showing a DSC curve.

FIG. 2 is a graph showing a flow curve.

FIG. 3 is a graph showing a GPC curve.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (4)

(57) [Claims] 1. A resin composition for a toner, which comprises, as a main component, a vinyl-based copolymer containing a styrene-based monomer and a (meth) acrylic acid ester-based monomer as constituent units,
To the toner resin composition, a styrene having a hydroxyl group at the terminal - olefin - toner resin composition characterized by containing a styrenic triblock copolymer. 2. A styrene-based monomer and a (meth) acrylic acid ester-based monomer are contained as constitutional units and have an acid value of 1
A toner resin composition as a main component a vinyl-based copolymer is a ~40KOHmg / g, in the toner resin composition, a styrene having a hydroxyl group at the terminal - olefin - styrene triblock copolymer A resin composition for a toner, which comprises a polymer. 3. The toner resin composition according to claim 1 or 2, further comprising a low melting point crystalline compound having a melting point of 55 to 130 ° C. 4. A toner comprising the resin composition for toner according to any one of claims 1 to 3 .