JP2004091794A - Composition and method for producing the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition having small dispersion and excellent dispersivity stability, and to provide a method for producing the composition. <P>SOLUTION: The method comprises heating a copolymer resin at 60-150°C, adding a pigment and a crosslinking agent and crosslinking the resin, wherein the copolymer resin is selected from an α, β unsaturated aliphatic carboxylic acid/α-olefin copolymer, an α, β unsaturated aliphatic carboxylic ester/α-olefin copolymer or an α, β unsaturated aliphatic carboxylic acid/α, β unsaturated aliphatic carboxylic ester/α-olefin copolymer. The composition is obtained by the method. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a composition, a method for producing the composition, an electrophotographic developer, a paint, a printing ink, and an ink for inkjet.

Conventionally, a polyfunctional (meth) acrylate such as diethylene glycol dimethacrylate and a polymerizable monomer such as lauryl acrylate are mixed with an aromatic hydrocarbon solvent such as an aliphatic hydrocarbon, toluene, benzene, or xylene in a polymerization initiator. There is known a method of producing a copolymer resin dispersion by performing a polymerization reaction in the presence (Patent Documents 1 and 2).
However, since the resin dispersion obtained by this production method uses an aromatic hydrocarbon solvent, the crosslinking of the contained resin is easy to proceed, and the resin generated during the progress of the polymerization reaction is gelled or stored. There were problems such as solidification of the resin. In addition, when the non-aqueous resin is used for paints and adhesives, it solidifies during storage, resulting in a decrease in adhesive strength. Therefore, in order to solve these problems, it is necessary to reduce the amount of polyfunctional acrylate or methacrylate such as polyhydric glycol diacrylate to 2% by weight or less. Certainly, the conventional problem can be solved by setting the content to 2% by weight or less, but as a result, the resin becomes soluble in an aromatic solvent. Less, resulting in poor adhesion. In particular, when used as an electrodeposition coating material, the pigment is not adsorbed on the resin, which is not desirable as a coating material.
Further, it has been pointed out that the aromatic solvent used in this method has high toxicity and flammability, and has not only a problem in environmental health, but also a problem of a great risk of fire.
The present inventors have developed a method for producing a dispersion comprising a non-aqueous resin in order to solve the above problems. In this method, a polyfunctional acrylic acid ester or methacrylic acid ester as described above is mixed with an unsaturated hydrocarbon or a halogenated aliphatic hydrocarbon as a main component in the presence of a polymerization initiator. This is a method in which a polar monomer such as carboxylic acid and a monomer that can be solvated with the solvent before and after polymerization such as lauryl acrylate are polymerized (Patent Document 3). However, in this method, the polyfunctional acrylate or methacrylate used as a cross-linking agent has a high cross-linking property, that is, a high cross-linking rate. In addition to the disadvantages that certain dispersion resins tend to vary, (2) the polymerization is not performed uniformly, only products having a wide particle size distribution can be obtained, and (3) the dispersion stability of the products is poor. Since polyfunctional acrylic acid or methacrylic acid monomer does not have a polar group, (4) the ability to disperse the colorant is low, and even if a monomer having a polar group is used in combination, the copolymerizability is very poor and uniform polymerization is performed. There is a problem that can not be.

JP-A-56-145911 JP-A-56-79112 JP-A-56-79112

課題 An object of the present invention is to provide a composition having a small dispersion and excellent dispersion stability, and a method for producing the composition.

According to the present invention, the following inventions are provided.
(1) In the presence of a non-aqueous solvent, an α, β unsaturated aliphatic carboxylic acid and an α-olefin copolymer, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer, or α, β A copolymer resin selected from an unsaturated aliphatic carboxylic acid, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer is heated to 60 to 150 ° C., a crosslinking agent is added, and the resin is crosslinked. The composition characterized by being obtained by doing.
(2) The composition according to (1), wherein the α, β unsaturated aliphatic carboxylic acid ester component in the copolymer is obtained by solvating a non-aqueous solvent.
(3) The composition according to (1), wherein the crosslinking agent is selected from a crosslinking agent containing a metal or a metal compound, or an organic amine.
(4) In the presence of a non-aqueous solvent, an α, β unsaturated aliphatic carboxylic acid and an α-olefin copolymer, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer, or α, β A copolymer resin selected from an unsaturated aliphatic carboxylic acid, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer is heated to 60 to 150 ° C., a crosslinking agent is added, and the resin is crosslinked. A method for producing a composition, comprising:
(5) The method for producing a composition according to (4), wherein the α, β unsaturated aliphatic carboxylic acid ester component in the copolymer is obtained by solvating with a non-aqueous solvent. .
(6) The method for producing a composition according to (4), wherein the crosslinking agent is selected from a crosslinking agent containing a metal or a metal compound, or an organic amine.

The composition according to the present invention can provide an electrophotographic developer, a paint, a printing ink, and an ink for ink jet by using a coloring agent.
Electrophotographic liquid developers and electrophotographic dry developers are excellent in image density, resolution, electrodeposition properties, and durability. Further, the occurrence of offset in heat roller fixing is small.
In addition, paints, printing inks, and inks for ink jet provide high image density and good results in resolution, fixability, gloss, ink dischargeability, and light fastness.

In the present invention, α-olefin / α, β-unsaturated carboxylic acid copolymer, α-olefin / α, β-unsaturated aliphatic carboxylic acid ester copolymer, α-olefin / α, β-unsaturated aliphatic carboxylic acid / α, It crosslinks β-unsaturated aliphatic carboxylic acid esters. The following are shown as specific examples of these. Ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / lauryl methacrylate, methacrylic acid copolymer, propylene / styrene divinylbenzene / 2-ethylhexyl acrylate / maleic acid copolymer Polymers, ethylene / glycidyl methacrylate / methacrylic acid copolymer, butene / acrylic acid / ethylene glycol dimethacrylate polymer, and the like.
These can use a random, block, or graft copolymer.
In these copolymers, α-olefin is 30 to 95% by weight, preferably 50 to 80% by weight of the whole copolymer, α, β unsaturated aliphatic carboxylic acid is 30 to 0.1% by weight, It is preferably 15 to 1% by weight, and the α, β unsaturated aliphatic carboxylic acid ester is 70 to 3% by weight, preferably 50 to 10% by weight.

In the present invention, crosslinking is performed in the presence of a non-aqueous solvent.
As the non-aqueous solvent, kerosene, ligroin, n-hexane, n-octane, i-dodecane, toluene, xylene, silicone oil, fatty acid ester, low molecular weight olefin compound, fluorinated oil and the like are used. As commercial products, Exoper G, Isopar H, Isopar L, and Isopar M are used.

At the time of crosslinking, the copolymer is mixed with the above non-aqueous solvent and heated to 60 to 150 ° C., preferably 90 to 120 ° C., to maintain the polymer in a dissolved, molten or dispersed state.

金属 As the crosslinking agent, a metal or metal compound crosslinking agent, an organic compound, and an organic amine can be used. Examples of the metal or metal compound crosslinking agent include beryllium hydroxide, magnesium hydroxide, barium hydroxide, zinc, calcium, strontium, zinc oxide, titanium oxide, and calcium carbonate. As the organic amine, n-hexylamine , Hexamethylenediamine, triethylamine, pyridine, triethanolamine, metaxylenediamine and the like, and the organic amine can be used in combination with a metal crosslinking agent. The carboxyl groups in the copolymer are crosslinked by the crosslinking agent.

By heating the copolymer in a non-aqueous solvent at the time of crosslinking, the components contained in these copolymers are solvated with non-aqueous solvents such as kerosene, toluene, silicone oil, and fluorine oil, which are non-aqueous solvents. .
The component of the copolymer to be solvated is an α, β unsaturated carboxylic acid ester, and as a result of solvation, contributes to the dispersion stability of the obtained resin solvent and the fixability of the colorant.
Monomers solvated in non-aqueous solvents include lauryl methacrylate, 2-ethylhexyl, methyl methacrylate, methacryl-modified silicone monomers, and acryl-modified fluorine monomers.

In the case of producing a colorant, a resin comprising the above copolymer is added to a non-aqueous solvent, mixed and stirred, and after further dispersing the pigment, a crosslinking agent is added and heated to obtain a colorant containing the pigment in the resin. Can be If a crosslinking agent is not used, the bonding force between the pigment and the resin is weak, the pigment and the resin are easily separated, not only the fixability and dispersibility are deteriorated, but also the life of the developer is shortened. The type of the crosslinking agent is the same as in the case of producing the non-aqueous resin dispersion.
Pigments are used to specify the color of the colorant.
Examples of the pigment include carbon black, phthalocyanine blue, disazo yellow, carmine 6B, and quinacridone.
This coloring agent can be used for an electrophotographic developer, a paint, a printing ink, and an ink jet ink.

Electrophotographic developers include dry and wet developers.
In the dry developer for electrophotography, carbon black is added to a resin dispersion liquid composed of a non-aqueous solvent, followed by stirring and mixing. Next, a crosslinking agent is added, and the mixture is heated to 60 to 150 ° C. for crosslinking. After producing the coloring agent thus obtained, the solvent is removed by heating. The solid mass obtained is made into a powder with a crusher to produce a toner. The particle size of the toner is generally from 0.1 to 5 μm.
In a wet developer for electrophotography, carbon black is added to a resin dispersion liquid containing a non-aqueous solvent, followed by stirring and mixing. Next, a crosslinking agent is added, and the mixture is heated to 60 to 150 ° C. for crosslinking. The coloring agent thus obtained is used.

(4) In order to produce a paint, a pigment is added to a resin dispersion composed of a non-aqueous solvent, and after stirring and mixing, a crosslinking agent is added and the mixture is heated to 60 to 150 ° C. to perform crosslinking. Next, carbon is added to the obtained product, a solvent is further added, and the mixture is mixed and stirred to obtain a paint. Due to the crosslinking, the adhesiveness and glossiness of the coating film were good.

For use as a printing ink, the wet developer of the present invention can be used as it is.
For use as an inkjet ink, the wet developer of the present invention can be used as it is.

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
200 parts by weight of kerosene was placed in a 1-liter four-necked flask and heated to 100 ° C. in an oil bath. 100 parts by weight of an ethylene / methacrylic acid (90/10) copolymer was added therein and dissolved with stirring for 1 hour. Into this, 10 parts by weight of zinc hydroxide was added, and the mixture was stirred and reacted at 100 ° C. for 40 hours. Next, the obtained product was cooled with stirring to obtain a resin dispersion.

Example 2
A resin dispersion was similarly obtained using an ethylene / lauryl methacrylate / methacrylic acid (60/30/10) copolymer instead of the copolymer of Example 1.

Example 3
A resin dispersion was similarly obtained using an ethylene / methyl methacrylate / acrylic acid (60/30/10) copolymer instead of the copolymer of Example 1.

Example 4
A resin dispersion was obtained in the same manner as in Example 3 except that toluene was used as the non-aqueous solvent instead of kerosene.

Example 5
In place of zinc hydroxide as a crosslinking agent used in Example 1, 1.0 part by weight of metaxylenediamine and 2.0 parts by weight of magnesium hydroxide were added, and a resin dispersion was obtained in the same manner.

Example 6
Kerosene was added to the copolymer of Example 1, and 20 parts by weight of carbon black was further added and mixed and stirred for 4 hours to disperse carbon in the black resin dispersion. Next, 10 parts by weight of zinc hydroxide was added, and crosslinking was performed at 100 ° C. for 6 hours to obtain a colorant. Thereafter, the non-aqueous solvent was removed to obtain a powder, and a dry toner having an average particle diameter of 10 μm was prepared.

Example 7
100 g of isoparaffin (Isoper M, manufactured by Exxon Chemical), 50 g of ethylene / stearyl methacrylate / methacrylic acid (70/20/10) copolymer, and 10 g of carbon black (manufactured by Mitsubishi Chemical, carbon MA100) in a 300 ml content attritor. Was added and dispersed by stirring at 90 ° C. for 2 hours. Next, 5 g of zinc hydroxide was added, and the mixture was kneaded, stirred, and dispersed at 100 ° C. for 1 hour to obtain a colorant composition.

Comparative Examples 1 to 7
The processing was carried out under the same conditions except that the crosslinking agent used in Examples 1 to 7 was not used.

Example 8
100 g of the resin of Example 1, 10 g of carbon black (manufactured by Mitsubishi Chemical, MA-100) and 100 g of isoparaffin (Isoper L, manufactured by Exxon Chemical) were placed in a 1-liter attritor, dispersed at 80 ° C. for 6 hours, and electrophotographically developed. A preparation was made. Using this developer, copying was performed by a wet copying machine (Recopy FT-400i). The offset was reproduced at an image density of 1.28, a resolution of 6.3 lines / mm, a fixing property of 78%, and a fixing temperature of 90 to 160 ° C. Did not.
The durability of the developer was 25,000 sheets.

も Examples 2 to 5 and Comparative Examples 2 to 5 were evaluated in the same manner as in Example 1, and the following results were obtained. Table 1 shows the results.

The colorant of Example 6 was evaluated as a dry toner by Ricopy FT4060, and the colorant of Example 7 was evaluated as a liquid toner by Ricopy FT400i. The following results were obtained. Table 2 also shows the results of Comparative Examples 6 and 7.

Example 9
To 100 g of the resin of Example 4, 10 g of carbon black (Carbon MA100 manufactured by Mitsubishi Chemical Corporation) and 100 g of toluene were added and dispersed by an attritor to obtain a paint. The particle size of the paint was 0.2 μm, and the adhesion and gloss of the coating film were good.

Example 10
When the liquid toner of Example 7 was used for an inkjet ink, the image density was 1.44, the ejection property was 25 μm dots, and the light fastness was one year or more.
On the other hand, the result of the conventional ink-jet ink (ink for Mach Jet manufactured by Seiko Epson Corporation) was 1.22 in image density, 80 μm dots in ejection property, and 1 month or less in light fastness.

Example 11
When Example 7 was similarly used as a printing ink, a printed matter having high fixability, gloss, and image density was obtained.

Claims (6)

In the presence of a non-aqueous solvent, an α, β unsaturated aliphatic carboxylic acid and an α-olefin copolymer, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer, or an α, β unsaturated fatty A copolymer resin selected from an aromatic carboxylic acid, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer is heated to 60 to 150 ° C., and a pigment and a crosslinking agent are added to crosslink the resin. The composition characterized by being obtained by this. 。 The composition according to claim 1, wherein the α, β unsaturated aliphatic carboxylic acid ester component in the copolymer is obtained by solvating with a non-aqueous solvent. The composition according to claim 1, wherein the crosslinking agent is selected from a crosslinking agent containing a metal or a metal compound, or an organic amine. In the presence of a non-aqueous solvent, an α, β unsaturated aliphatic carboxylic acid and an α-olefin copolymer, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer, or an α, β unsaturated fatty A copolymer resin selected from an aromatic carboxylic acid, an α, β unsaturated aliphatic carboxylic acid ester and an α-olefin copolymer is heated to 60 to 150 ° C., a pigment and a crosslinking agent are added, and the resin is crosslinked. A method for producing a composition, comprising: 5. The method for producing a composition according to claim 4, wherein the α, β unsaturated aliphatic carboxylic acid ester component in the copolymer is obtained by solvating with a non-aqueous solvent. 5. The method according to claim 4, wherein the crosslinking agent is selected from a crosslinking agent containing a metal or a metal compound, or an organic amine.