KR20110081571A - Polyester resin and toner including the same - Google Patents
Polyester resin and toner including the same Download PDFInfo
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- KR20110081571A KR20110081571A KR1020100001791A KR20100001791A KR20110081571A KR 20110081571 A KR20110081571 A KR 20110081571A KR 1020100001791 A KR1020100001791 A KR 1020100001791A KR 20100001791 A KR20100001791 A KR 20100001791A KR 20110081571 A KR20110081571 A KR 20110081571A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
- G03G9/08708—Copolymers of styrene
- G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08775—Natural macromolecular compounds or derivatives thereof
Abstract
Description
The present invention relates to a polyester resin and a toner comprising the same, and more particularly, to a toner used in an electrophotographic copying process or an electrostatic printing process and a polyester resin included as a binder in the toner.
In general, an electrophotographic copying process or an electrostatic printing process involves (1) an electrostatically charged material, for example an electrostatically charged image corresponding to an image to be recorded on the surface of an organic photoconductor (OPC) drum. charged image) or electronically conductive phase (hereinafter referred to as " latent image "), and (2) electrostatic latent images formed on the surface of the drum by electrostatic attachment of charged toner to the drum. Developing and visualizing, (3) transferring the developed toner image to a recording medium such as paper or recording film, and (4) fixing the transferred image to the recording medium with a thermocompression roller or the like. Process.
Such an image-forming process is widely used in the field of copiers and printers because it is possible to obtain printed matter at high speed, has excellent control stability of the phase formed on the surface of the electrostatic rock material, and facilitates operation of the image-forming apparatus.
In the above development step, the toner used for dry development is classified into one component toner, two component toner, and the like. The two-component toner, together with a binder resin, a colorant, a charge control agent and other additives, includes a magnetic material for developing and transferring an electrostatic latent image formed on a drum, and melting, kneading, dispersing, finely pulverizing and It is produced in the form of particles by classification. The binder resin, which is a main component of the toner, should not only have excellent dispersibility, fixability, non-offsetability, storage stability, and other electrical properties of the colorant during melting and kneading, but also excellent transparency and a small amount of colorant. It should be possible to form a clear image without blur. In addition, the binder resin has a wide color reproducible width, can improve the image density of a copy or printed matter, and is environmentally friendly.
As the binder resin, a polystyrene resin, a styrene acrylic resin, an epoxy resin, a polyamide resin, and the like have conventionally been used, and in recent years, the use of polyester resins having excellent fixability and transparency has increased. However, at present, raw materials of numerous products including toners are manufactured from fossil resources such as petroleum, and a response to reducing the use of fossil resources is very important in preventing exhaustion of fossil resources. In particular, most of the toner resins, which account for more than 70% of the toner components, are mostly made from petroleum resources, and there are concerns about the depletion of petroleum resources, warming by consuming large amounts of petroleum resources, and the release of carbon dioxide into the atmosphere. have. As a toner resin, when a resin derived from a plant that grows carbon dioxide in the air and grows is used, the carbon dioxide generated is circulated in the environment, and there is a possibility of solving the problem of warming and depletion of petroleum resources at the same time. In particular, the attention is paid to the biomass raw material content (biomass) in the plant-derived environmentally cyclic polymer.
Biomass refers to a biological organism including plants, cells and animals that eat and live by photosynthesis of plants and microorganisms that receive solar energy. In addition, biomass resources include starch-based resources including cereals and potatoes, cellulose-based resources including agricultural products such as herbs, wood and rice straw, rice hulls, and environmentally cyclic resources derived from sugar-based plants such as sugar cane and sugar beets. Of course, it has a variety of properties, including animal manure, carcass and protein-based resources, including microbial cells. Organic wastes such as paper and food waste derived from these resources are also included.
Such biomass can be utilized as a biological resource that can be an energy source or a material of various synthetic materials by combining biological technology and chemical technology. The biggest advantage of this biomass is that it is renewable. Unlike other fossil fuels, carbon dioxide is not depleted and released into the atmosphere through combustion, which is obtained in the atmosphere through the growth of plants and microorganisms in the past few years, so there is no increase in atmospheric carbon dioxide. Thus, it will be able to replace existing products derived from petrochemicals.
In order to solve the above-mentioned problems, various techniques using a biomass raw material as a toner resin have been proposed. For example, Japanese Laid-Open Patent Publication Nos. 2009-75544, 2008-250171, 2001-166537, 1997-274335, 1997-308765, and 194-200250 use polylactic acid resin as it is or In some cases, since the concentration of the ester bond is higher than that of the general polyester resin, the application to the thermoplastic resin at the time of fixing is lowered. In addition, since the toner becomes considerably hard, there is a problem in that there is a lack of pulverization and inferior productivity, and a lot of fine powder is generated in response to the mechanical impact caused by stirring in the developing machine, resulting in severe offset generation and image contamination.
In addition, polylactic acid is difficult to control the molecular weight, it is difficult to achieve the physical properties necessary for the toner only with polylactic acid because only the carbon atoms are used and ester bonds are present. In addition, there is a fear that fixing failure occurs when forming a black and white image, not a configuration that can sufficiently cope with an image forming apparatus that has made the process speed faster when forming a black and white image. There is also a problem of inferior long-term storage stability in order to have good biodegradability. That is, if left for a long time in a high temperature, high humidity environment, the toner may be hydrolyzed and unusable. In addition, when the printed matters are left in an overlapped state under the above-described conditions, there is a fear that the printed matters may stick together depending on the softened toner.
On the other hand, as in the conventional method, it is thought to mix the polylactic acid and other resins to secure the physical and thermal properties necessary for the toner, but the polylactic acid is a polyester resin and styrene-acryl that are used for general purposes in the toner. Due to the extremely poor compatibility and dispersibility with the copolymer, it is quite difficult to produce toner. In addition, US Patent No. 2006-010136 discloses a toner resin using isosorbide and dimer acid, which are plant-derived environmentally cyclic polymerization raw materials. However, this is difficult to commercialize as an expensive raw material, there is a limit to increase the biomass content.
Generally, the polyester resin used as the binder resin for toner uses bisphenol-A or a derivative thereof as the alcohol component. However, since bisphenol-A is an environmentally undesirable compound, it does not contain bisphenol-A or its derivatives, and thus, good offset resistance, low temperature fixing property, sharp melt resistance, blocking resistance, charging property, grinding property, The development of the polyester resin which is excellent in the characteristics, such as storage stability and transparency, and forms a favorable image development even after leaving for a long time is tried.
Germanium-based catalysts, antimony-based catalysts, tin-based catalysts, and the like have been used in the production of toner polyester resins. However, since the catalysts are excessively used due to their low activity, they are not environmentally preferable, For example, the antimony-based catalyst has a problem in that transparency of the polyester resin is lowered due to gray colorability). Thus, tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, TiO 2 / SiO 2 A method of improving the reactivity and transparency of the resin has been attempted by using a titanium-based catalyst such as a coprecipitation agent and a TiO 2 / ZrO 2 coprecipitation agent.
An object of the present invention is to increase the biomass material content in the resin by using a biomass polymerization raw material, does not include bisphenol-A or its derivatives, and does not require the use of heavy metal catalysts such as tin and antimony during the polymerization. It is to provide a polyester resin for toner.
Another object of the present invention can be economically produced, has excellent offset resistance and storage stability, excellent fixability to an electrostatic lock material or recording medium, and high image density, and excellent durability and moisture resistance of the toner, It is to provide a toner having improved image stability.
In order to achieve the above object, one aspect of the present invention is a toner containing lactic acid (D or L-lactic acid) or a derivative thereof, lactide (D or L-lactide) and 1,4-cyclohexanedimethanol It provides a polyester resin.
One embodiment of the present invention is 5 to 70% by weight of a biomass resource-derived compound including lactic acid (D or L-lactic acid) or a lactide (D or L-lactide) derived therefrom based on the total polyester resin And 30 to 94% by weight of a petroleum-derived compound including the 1,4-cyclohexanedimethanol; And greater than 0 to less than 1% of a heat stabilizer.
According to one embodiment of the present invention, the petroleum resource-derived compound is composed of 2 to 70% by weight of an acid component and 24 to 92% by weight of an alcohol component including 1,4-cyclohexanedimethanol.
In one embodiment of the present invention, 1,4-cyclohexanedimethanol contains 0.5 to 28% by weight of the total polyester resin.
According to one embodiment of the present invention, the biomass resource-derived compound is 0.5 to 50% by weight of lactic acid (D or L-lactic acid) or a lactide (D or L-lactide) thereof, based on the total polyester resin. 0 to 10 weight percent diol, 0 to 5 weight percent fatty acid or fatty acid alkyl ester, and 0.5 to 10 weight percent glycerin component.
In one embodiment of the present invention, the polyester resin further includes a styrene resin or a styrene-acrylic resin. .
In one embodiment of the present invention, the softening temperature of the polyester resin is 125 to 190 ℃, the acid value of the resin is 1 to 30 KOHmg / g, Tg is 58 to 75 ℃ or less.
One aspect of the present invention provides a toner containing the polyester resin. .
Another aspect of the present invention is (a) 0.5 to 50% by weight of lactic acid (D or L-lactic acid) derived from biomass resources or a compound thereof, lactide (D or L-lactide), 0% by weight of aliphatic diol To 10 weight percent, 0 to 5 weight percent fatty acid or fatty acid alkyl ester, 0.5 to 10 weight percent glycerin component; And esterification reaction or transesterification in the presence of titanium-based catalyst, including 30 to 94% by weight of acid components derived from petroleum resources and alcohol components containing 1,4-cyclohexanemethanol as reactants. Carrying out the reaction; And
(b) polycondensing the reactants, wherein at least one of the reaction steps provides a method for producing a polyester resin for a toner, which is carried out in the presence of a thermal stabilizer of more than 0% and less than 1% by weight. .
The polyester resin according to the present invention contains an environmentally cyclic biomass polymerization raw material lactic acid (D or L-lactic acid) or a derivative thereof, lactide (D or L-lactide) and 1,4-cyclohexanedimethanol. do.
The polyester resin according to the present invention is a binder capable of producing environmentally friendly toner, and does not include bisphenol-A or its derivatives as an alcohol component, and does not use heavy metal catalysts such as tin or antimony, More preferred. In addition, the toner made of the polyester resin according to the present invention has not only an excellent storage stability, a fixing temperature range and an image density, but also an advantage that it can be manufactured inexpensively.
Hereinafter, the present invention will be described in more detail.
The polyester resin according to the present invention is a biomass polymerized raw material lactic acid (D or L-lactic acid) or a derivative compound thereof, such as lactide (D or L-lactide) and 1,4-cyclohexanedimethanol containing poly It provides an ester resin.
The biomass polymerization raw material component is 5 to 70% by weight, preferably 20 to 60% by weight, more preferably 30 to 50% by weight based on the total polyester resin polymerization raw material. If the content of the biomass polymerization raw material is less than 5% by weight, it can be seen that there is no meaning of using the biomass polymerization raw material, if it is more than 70% by weight, economic efficiency as a toner can not be secured, the basic physical resistance of the toner Fixability, storage stability, burn density, durability and moisture resistance are poor.
The biomass polymerization raw material component includes lactic acid (D or L-lactic acid) or a derivative thereof, lactide (D or L-lactide), which have acid and alcohol properties simultaneously, 0.5 to 50% by weight or less, preferably 10 to 40% by weight, more preferably 20 to 30% by weight.
The lactic acid (D or L-lactic acid) or lactide (D or L-lactide), which is a derivative thereof, is competitive with petroleum-derived polymerization raw materials, so that the lactic acid (D or L-lactic acid) is used as long as it does not affect toner properties, but the content thereof is high. When it is more than 50 weight%, ester content which is a polar group in resin becomes relatively large, and water content tends to increase in high temperature / high humidity conditions.
Therefore, under the high temperature / high humidity in-cartridge environment, the print initial image is good, but as the printing proceeds, the water content of the toner increases, the charging characteristic is lowered, and the image tends to be poor. In addition, there is a fear that the glass transition temperature (Tg) of the polyester resin is lowered, resulting in poor storage stability. The lactic acid (D or L-lactic acid) or its derivative, lactide (D or L-lactide), is preferably introduced at the beginning of the polymerization reaction and contained in the form of random polymer in the resin.
When introduced at the end of polymerization or introduced in the form of polymerized polylactic acid oligomer or polymer, it is blocked in resin and the toner becomes considerably hard due to the crystallinity peculiar to polylactic acid. In addition, there is also a problem that the characteristics of the thermoplastic resin at the time of fixing due to the high heat melting temperature characteristics are poor, and inferior to long-term storage stability because it has biodegradability.
The fatty acid or alkyl ester thereof may be used as the biomass polymerization raw material acid component. In particular, biodiesel, which is an environmentally friendly fuel rather than a fossil fuel derived from petroleum resources, is in the spotlight. The main component of biodiesel fuel is composed of 14 to 24 fatty acid methyl esters, and the content of each component is different depending on oil type (soybean oil, rapeseed oil, palm oil, etc.) used as raw materials. Among them, when the methyl ester component of saturated palmitic acid is high, it affects low temperature fluidity, which is disadvantageous for use as fuel for vehicles in winter.
In some biodiesel, some of these ingredients are excluded to satisfy winter cold flow and are treated as by-products. Applying the methyl palmitic acid ester component treated as a by-product as a toner resin ensures eco-friendly resource utilization and economics through the use of by-products, and improves melting characteristics of the toner to obtain good fixability. However, the type of fatty acid methyl ester is not limited to methyl palmitate, and all 14 to 24 fatty acid methyl esters used for biodiesel fuel can be used.
The fatty acid methyl ester component is used in an amount of 0 to 5% by weight or less based on the total resin polymerization raw material, and preferably 2 to 5% by weight. If the content thereof is more than 5% by weight, the glass transition temperature (Tg) of the polyester resin may be lowered, resulting in poor storage stability. Moreover, it becomes impossible to ensure the target degree of polymerization of a polyester resin with a monovalent acid component.
As the biomass polymerization raw material alcohol component, dianhydrohexitol (1,4-3,6-Dianhydrohexitol), which is a bioderived sugar derivative, may be used. This is a condensation reaction under condensation reaction under acid catalysts of D-sorbitol, D-mannitol, and D-iditol, respectively, derived from starch, respectively, and alcohol components such as isosorbide, isomannide, and isoidide, respectively, to polyester resin. When applied, it has the characteristic of increasing the glass transition temperature (Tg).
This can solve the problem of lowering the glass transition temperature (Tg) of the polyester resin by applying a large amount of biomass polymerization raw material (aliphatic). This component may be used in an amount of 0% to 30% by weight based on the total resin polymerization raw material.
Aliphatic diol may be used as the biomass polymerization raw material alcohol component. In addition, it is produced through a fermentation process using a sugar component as a raw material, it is applied as an aliphatic diol component of the toner resin, such as 1,3-propanediol and 1,4-butanediol. This component increases the speed of polymerization of polyester resin and increases productivity. It also serves to improve fixability by lowering the melt viscosity as a soft segment in the resin.
This component is used in an amount of 0 wt% to 10 wt% or less with respect to the total resin polymerization raw material, and preferably 0.1 to 5 wt%. If the content is more than 10% by weight, the economical efficiency as a toner is not produced as an expensive raw material, and the glass transition temperature (Tg) of the polyester resin may be lowered, resulting in poor storage stability.
In addition to the above components, glycerin, which is a byproduct of the production of biodiesel from biomass vegetable oils (palm oil, soybean oil, castor oil, seaweed seed oil, rapeseed oil), may be used as a polymerization raw alcohol component. The purity of Crude Glycerin is usually 70-80%, and in order to use it as a polymerization raw material, it is preferable to use it as a raw material of purity of 90% or more after purification by a conventional fractional distillation method. This component has the effect of giving cohesiveness to the resin and improving storage stability of the toner while raising the Tg of the resulting resin. The content of the polyhydric alcohol is 0.5 to 10% by weight or less, preferably 2 to 5% by weight based on the total alcohol component. If the content of such polyhydric alcohol is less than 0.5% by weight, the molecular weight distribution is small to narrow the fixing temperature range of the toner, and if it exceeds 10% by weight, it is difficult to control the gelation of the polyester resin during the production of the polyester resin, which is preferable. It is difficult to obtain.
As long as the polyester resin has the necessary physical properties as the binder for the toner in the remaining components except for the biomass polymerization raw material component, acid components and alcohol components derived from ordinary petroleum resources can be used. The acid component may include an aromatic dibasic acid component, a cycloaliphatic dibasic acid component, an aliphatic dibasic acid, an alkyl ester thereof and / or an acid anhydride thereof, and a trivalent or more polyacid component. The alcohol component also includes alicyclic diols and aliphatic diols.
In particular, the aromatic dibasic acid component includes aromatic dibasic acids, alkyl esters thereof, and acid anhydrides commonly used in the preparation of polyester resins. Typical examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid and 5-sulfoisophthalic acid sodium salt. Examples of the alkyl ester of the aromatic dibasic acid include dimethyl terephthalate, dimethyl isophthalate, and diethyl terephthalate. , Diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, dimethyl 5-sulfoisophthalate sodium salt, and the like.
The aromatic dibasic acid and alkyl esters thereof may be used alone or in combination of two or more thereof. Since the aromatic dibasic acid component contains a benzene ring having high hydrophobicity, it improves the moisture resistance of the toner, increases the glass transition temperature (hereinafter referred to as Tg) of the resulting resin, and consequently improves the storage stability of the toner. .
The amount of the aromatic dibasic acid component used is 20 to 70% by weight, preferably 25 to 50% by weight, more preferably 30 to 40% by weight based on the total resin polymerization raw materials. In addition, since the terephthalic acid component increases the toughness and Tg of the resin, and the isophthalic acid component increases the reactivity, the terephthalic acid component can be used by changing its use ratio as desired.
The cycloaliphatic dibasic acid component, aliphatic dibasic acid, alkyl esters thereof and / or acid anhydrides thereof, and trivalent or higher polyacid components, as long as the polyester resin has the necessary physical properties as a binder for a toner, except for these components. The content of the alicyclic diol and aliphatic diol components can be appropriately adjusted as necessary.
The alcohol component of the petroleum resource constituting the polyester resin according to the present invention includes an alicyclic diol. In the alicyclic diol component, the alicyclic group preferably has 5 to 20 carbon atoms, and as the alicyclic diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or spiroglycol More preferably 1,4-cyclohexanedimethanol is used. The amount of the 1,4-cyclohexanedimethanol used is 0.5 to 28% by weight, preferably 10 to 28% by weight, more preferably 10 to 20% by weight, based on the total polyester resin weight ratio.
The 1,4-cyclohexanedimethanol component, in the high temperature region of 170 ° C or higher, increases the storage modulus among the viscoelastic properties of the polyester resin, enables high temperature offset, and has lipophilic properties, Improve the moisture resistance of the toner, which is lowered due to the introduction of hydrophilic dianhydrohexitol (isosorbide or isomannide) or biomass polymerized raw material lactic acid or its derivative lactide, thereby maintaining good toner image density. Can be.
In addition, the cyclic structure of the 1,4-cyclohexanedimethanol improves the hydrolysis resistance and thermal stability of the resin, suppresses the phenomenon of lowering the molecular weight during toner production, and exhibits a wide range of fixing region characteristics. When the content of the 1,4-cyclohexanedimethanol component is less than 0.5% by weight, the moisture content of the polyester resin is high, the moisture content of the toner is high, the viscoelastic properties are poor, and high temperature offset characteristics cannot be obtained. If it exceeds, the polyester resin may have crystallinity, resulting in poor transparency, and poor fixing area due to high softening point.
In the present invention, the alcohol component does not contain environmentally undesirable aromatic diols. Examples of the aromatic diol include bisphenol-A derivatives, specifically, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-(2.3) -2,2- Bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2-bis (4-hydroxy Phenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Ethylene- (3.0) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene- (6) -2,2-bis (4-hydroxyphenyl) propane are commonly used, but these are environmentally It is not desirable.
The polyester resin which concerns on this invention contains a conventional heat stabilizer (polymerization stabilizer) as an additive. Conventional compounds may be used as the heat stabilizer, and preferably phosphoric acid, trimethyl phosphate, and triethyl phosphate are not limited thereto.
The amount of the thermal stabilizer is preferably added at a concentration of 5 to 500 ppm relative to the total resin weight.
The polyester resin according to the present invention, like conventional polyester resins, is produced in two stages: esterification reaction or transesterification reaction and polycondensation reaction. In order to prepare a polyester resin according to the present invention, first, the acid component, alcohol component, lactic acid (D or L-lactic acid) or a derivative thereof, lactide (D or L-lactide), and a heat stabilizer are charged to a reactor. And heating to effect esterification or transesterification, followed by polycondensation. Thus, at least one of the reactions can be carried out in the presence of a heat stabilizer.
Here, it is preferable that the molar ratio of the total alcohol component usage amount (G) with respect to the total acid component usage amount (A) is 1.1-1.8.
The esterification reaction or transesterification reaction is a conventional titanium catalyst, for example, tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, ethyl acetoacetic ester Titanate, isostearyl titanate, titanium dioxide, TiO 2 / SiO 2 coprecipitation, TiO 2 / ZrO 2 coprecipitation, and the like.
On the other hand, heavy metal antimony-based and tin-based catalysts are preferably not used from an environmental point of view. The esterification reaction or transesterification reaction can be carried out, for example, at a reaction temperature of 230 to 260 ° C. under a nitrogen stream, while the water or alcohol produced from the reactants is removed in a conventional manner during the reaction.
When the esterification reaction or transesterification reaction is completed, a polycondensation reaction is performed. The polycondensation reaction may also be carried out under conventional polycondensation reaction conditions of a polyester resin, for example, at a temperature of 240 to 270 ° C., preferably at a temperature of 250 ° C. or lower, (a) the first of the polycondensation reaction As a step, the reaction is carried out by low speed agitation at low vacuum, and (b) the reaction is carried out by high speed agitation of the reactant at high vacuum, and (c) finally the reaction is reacted at low speed while the reactor is kept at atmospheric pressure. Polyester resin can be manufactured.
In this polycondensation reaction, by-products such as glycol are distilled off, and in the case of high vacuum at the first stage of the polycondensation reaction, the pressure is 100 mmHg or less, preferably 30 mmHg or less, and the high vacuum produces a low boiling point compound produced in the polycondensation reaction. It gives the effect of removing from a reaction system.
The Tg of the polyester resin according to the present invention is preferably 58 to 75 ° C. or less. If the Tg is less than 58 ° C., the toner crushability and storage stability may be lowered. If the Tg exceeds 75 ° C., the thermoplastic resin of the resin There is a possibility of poor fixability due to lack of characteristics.
The softening temperature of the said polyester resin is 125-190 degreeC, and it is more preferable if it is 140-170 degreeC. If the softening temperature is lower than 125 ° C., the Tg is lowered and the storage stability is lowered. Therefore, the toner particles may be agglomerated during storage, and there is a fear that an offset occurs at a high temperature. If the softening temperature exceeds 190 ° C., the low temperature fixability of the toner may deteriorate and offset may occur.
In addition, the acid value of the polyester resin is preferably 30 KOH mg / g or less, more preferably 1 to 30 KOH mg / g, most preferably 1 to 20 KOH mg / g. If the acid value exceeds 30 KOH mg / g, there is a risk of poor storage stability during storage and transportation of the polyester and in the developer.
The polyester resin according to the present invention is used as a main component of the toner binder resin, but if necessary, other resins such as styrene resin or styrene-acrylic resin may be used in combination.
The content of the binder resin in the components of the toner according to the present invention is preferably 30 to 95% by weight, more preferably 35 to 90% by weight. If the binder resin content is less than 30% by weight, the offset resistance of the toner tends to be lowered. If the binder resin content is more than 95% by weight, the charging stability of the toner may deteriorate.
The polyester resin which concerns on this invention can also be used together with the coloring agent component of a toner. Examples of such colorants and pigments include carbon black, nigrosine dyes, lamp blacks, Sudan black SM, navel yellow, mineral fast yellow, littol red, permanent orange 4R, and the like.
In addition, the polyester resin according to the present invention can be used in combination with conventional additives such as magnetic materials such as wax, charge control agent, magnetic powder, and other components of the toner. Examples of the wax include polyethylene, polypropylene, and ethylene-polypropylene copolymers. Examples of the charge control agent include nigrosine, alkyl-containing azine dyes, basic dyes, monoazo dyes and metal complexes thereof, salicylic acid, and the like. Metal complexes, alkyl salicylic acid and metal complexes thereof, naphthoic acid and metal complexes thereof, and the like, and examples of the magnetic powders include ferrite and magnetite.
The toner containing the polyester resin according to the present invention can be produced by a conventional method. For example, the binder resin, the colorant, and other additives are kneaded at a temperature higher than the softening temperature of the binder resin by using a kneader such as a single screw extruder, a twin screw extruder, a mixer, and the mixture is pulverized to form a particle. Toner can be produced. The average particle size of the produced toner particles is usually 5 to 10 mu m, preferably 7 to 9 mu m, and it is more preferable that fine particles having a particle size of 5 mu m or less are present in less than 3% by weight of the whole.
The toner containing the polyester resin according to the present invention may be used as a toner binder of a chemically produced toner (CPT) in addition to the conventional grinding method. The toner is prepared by dispersing a solution obtained by dissolving a polymerized resin in a solvent in an aqueous medium in the presence of a dispersant such as a surfactant or a water-soluble resin and a dispersion stabilizer such as inorganic fine particles and resin fine particles, and removing the solvent according to heating, reduced pressure, or the like. It is also possible to obtain a uniform toner by dissolving resin suspension, emulsion or the like.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples. The performance evaluation method used in the following Examples and Comparative Examples is as follows.
(1) Polymerization product: When the polymerization reaction under the same polycondensation reaction conditions resulted in a rapid rise in viscosity, the reaction was not allowed to come out of the reactor (gelation), and it was defined as a failure, and the polymerization time was too slow during the polycondensation reaction. When this time exceeds 300 minutes, it is defined as unreacted. Other normal reactions are defined as good.
(2) Bio content (%): The content of the biomass polymerization raw material component in the resin was quantitatively analyzed using a 600 Mhz nuclear magnetic resonance (NMR) spectrometer.
(3) Resin transparency: After the completion of the polymerization of the polyester resin, the hot melt discharged product was received in a plate shape of about 1 cm and solidified at room temperature, and then evaluated visually after annealing for 2 hours in an oven at 80 degrees according to the following criteria. (Double-circle): resin is amorphous and transparent, (circle): resin hazes with some crystallinity, x: resin is crystalline and opaque.
(4) Tg (glass transition temperature, ° C): After using a differential scanning calorimeter (TA Instruments), the sample was melt-quenched and then measured by raising the temperature to 10 ° C / min. The baseline near the endothermic curve and the mid value of each tangent line are Tg.
(5) Acid value (KOHmg / g): The resin was dissolved in dichloromethane, cooled, and titrated with 0.1N KOH methanol solution.
(6) Softening temperature (° C.): 1.5 g, using a flow tester (CFT-500D, manufactured by Shimadzu Laboratories), under conditions of a 1.0Φ × 10 mm (height) nozzle, a 10 kgf load, and a rate of temperature rise of 6 ° C./min. The temperature at which half of the sample flowed out was referred to as softening temperature (° C).
(7) Crushability: The toner production produced per hour was evaluated by pulverizing and classifying the melt-extruded flakes (Flake) in a toner production by a Hosogawa jet mill pulverizer and a classifier (100AFG, 50ATP, 50ZPS) as follows. .
◎: 0.4 kg / 1 hour or more, ○: 0.2 to 0.4 kg / 1 hour, X: 0 to 0.2 kg / 1 hour.
(8) Storage stability: The prepared toner was placed in a 100g glass bottle and sealed, and after 48 hours at 50 ° C, the degree of aggregation between the toners was visually evaluated as follows.
◎: no aggregation and good storage stability, ○: fine aggregation but good storage stability, X: severe aggregation and poor storage stability.
(9) Minimum fixing temperature and offset temperature: The minimum temperature of the heat roller which coats the manufactured toner on white paper, passes the heat roller coated with silicone oil at a speed of 200 mm / sec, and maintains a fixing efficiency of 90% or more. The minimum fixing temperature, the maximum temperature is defined as the offset temperature, and the heat roller temperature was adjusted from 50 ° C to 230 ° C to measure the minimum fixing temperature and the offset temperature. The offset temperature minus the minimum fixing temperature is defined as the fixing temperature range.
(10) Toner Image Density Evaluation: 100 when printed on up to 5,000 sheets on an OHP film or paper using a black and white printer having a Teflon-coated heat roller, free of temperature change, and having a printing speed of 40 pages / minute. The image flow and image density (solid area image) of each sheet of 2000 sheets and 5000 sheets were measured with a Macbeth reflectometer RD918 and evaluated according to the following criteria.
(Double-circle): The image density of an image is 1.4 or more, (circle): The image density of an image is 1.2 or more, and x: The image density of an image is 1.2 or less.
The polymerization raw materials used in the following Examples and Comparative Examples are as follows.
-TPA: terephthalic acid
-IPA: isophthalic acid
DMS: dimethyl 5-sulfoisophthalate, sodium salt
-TMA: trimellitic acid
EG: ethylene glycol
1,2-PG: 1,2-propylene glycol
CHDM: 1,4-cyclohexanedimethanol
1,3-PDO: 1,3-Propane diol (aliphatic diol)
Isosorbide: 1,4-3,6-Dianhydrosorbitol
Glycerin: Glycerin
Lactide: L-Lactide
C16: methyl palmitic acid ester
C18: methyl stearic acid ester
BPA-PO: polyoxypropylene- (2,3) -2,2-bis (4-hydroxyphenyl) propane
Catalyst: Titanium dioxide and silicon dioxide copolymer
Stabilizer: Trimethyl phosphate
Example 1-6 and Comparative Example 1-6
A. Preparation of Polyester Resin
In a 2L reactor equipped with a stirrer and an outlet condenser, the reactants (proportions of acid and alcohol components, G / A = 1.2 to 1.5) and TiO 2 / SiO 2 coprecipitation as a catalyst and components as shown in Table 1 below 100 ppm (based on weight ratio to total polyester resin) were packed together. The temperature of the reactor was gradually raised to 250 ° C. under a nitrogen stream, and the esterification reaction was carried out while water, a byproduct, was flowed out of the reactor.
After the generation and outflow of the water was complete, the reaction was transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser and a vacuum system. After adding a heat stabilizer (trimethyl phosphate), the reaction temperature was raised to 250 ° C., and the excess diol component was allowed to flow out while reacting under low vacuum while reducing the reaction pressure to 50 mmHg over 30 minutes.
Next, the reaction pressure was gradually reduced to 0.1 mmHg, and under high vacuum, the reaction was terminated until a predetermined stirring torque was indicated, and then the reaction was terminated. Softening temperature, Tg and acid value of the prepared polyester resin was measured and shown in Table 1.
B. Preparation of Toner
50 parts by weight of the prepared polyester resin, 45 parts by weight of magnetic material and a colorant, 2 parts by weight of an azo dye-based metal complex as a charge control agent, and 3 parts by weight of polyethylene wax were mixed using a mixer and melted and kneaded in an extruder.
Then, it was pulverized with a jet mill grinder, classified with a wind classifier, and then coated with 1 part by weight of silica and 0.2 part by weight of titanium dioxide to prepare toner particles having a volume average particle diameter of 8 to 9 탆. The pulverization, storage stability, minimum fixing temperature, offset generation temperature and toner image concentration (100 sheets, 2000 sheets and 5000 sheets) of the prepared toner particles are shown in Table 1 together.
Comparative Example 7
A. Preparation of Polyester Resin
In a 2 L reactor equipped with a stirrer and an outlet condenser, the reactants of TPA, EG, CHDM, isosorbide components and contents in the components shown in Table 1 below, and TiO 2 / SiO 2 coprecipitation agents as catalysts were used for the entire polyester resin. Filling with 50 ppm by weight. The temperature of the reactor was gradually raised to 250 ° C. under a nitrogen stream, and the esterification reaction was carried out while water, a byproduct, was flowed out of the reactor.
After the generation and outflow of the water was complete, the reaction was transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser and a vacuum system. After adding a heat stabilizer (trimethyl phosphate), the reaction temperature was raised to 240 ° C., and the excess diol component was allowed to flow out while reacting under low vacuum while reducing the reaction pressure to 50 mmHg over 30 minutes.
Next, the reaction pressure was gradually reduced to 0.1 mmHg, and the reaction was carried out under high vacuum for 30 minutes, and then the weight ratio of Sn (Oct) 2 to the total polyester resin Sn (Oct) 2 as a reactant and a catalyst of the lactide component and content shown in Table 1 below. 50 ppm was added thereto, the reaction was performed at atmospheric pressure for 80 minutes, and the reaction pressure was reduced to 0.1 mmHg over 10 minutes to remove the unreacted residual lactide component under high vacuum, and then the reaction was terminated. Softening temperature, Tg and acid value of the prepared polyester resin was measured and shown in Table 1.
B. Preparation of Toner
It carried out similarly to the manufacturing method of toner of Example 1-6 and Comparative Example 1-6.
TABLE 1
Comparative Example 1 is a conventional toner binder using an aromatic diol, a bisphenol-A derivative, which has a good storage stability, crushability, and storage stability due to high Tg, but does not contain any biomass content in the overall resin, which is environmentally friendly. I can't do this. In addition, without the heat stabilizer, a difference in the softening temperature of the resin and the softening temperature of the toner after extrusion occurred by 10 ° C., and the softening temperature was lowered more severely due to thermal decomposition during toner production.
Comparative Example 2 is a non-BPA-based toner binder using 1,4-cyclohexanedimethanol instead of bisphenol-A or derivatives thereof. Although good crushability, storage stability and image density were obtained, bisphenol-A or derivatives thereof were used. Although not used, it is environmentally friendly, but it does not use lactide and isosorbide or isomannide, and uses excessive amount of 1,4-cyclohexanedimethanol. The temperature could not be obtained a good fixing area, and the bio mss content in the total resin is less than 5% by weight can be said to be less environmentally friendly.
In Comparative Example 3, the lactide content is more than 50% by weight, the ester content as a polar group in the resin is relatively increased, and the water content is likely to increase in high temperature / high humidity conditions. As a result, the charging characteristics were deteriorated and the image was poor, and the glass transition temperature (Tg) of the polyester resin was lowered, resulting in poor crushability, storage stability, fixing area, and the like.
Comparative Examples 4 to 7 contained 5 to 70% by weight of the non-petroleum biomass polymerization raw material component relative to the total resin polymerization raw material, while in Comparative Example 4, when the content of isosorbide exceeds 30% by weight, the polymerization of the resin The reaction rate was poor, so that the target degree of polymerization could not be obtained within the desired reaction time. As a result, the glass transition temperature (Tg) of the polyester resin was lowered, resulting in poor storage stability and fixing area.
When the thermal stabilizer content in Comparative Example 5 exceeds 500ppm in the resin polymerization raw material, the polymerization reaction rate of the resin was poor to obtain the target degree of polymerization within the desired reaction time, and when the fatty acid methyl ester content exceeded 5 wt% polyester The glass transition temperature (Tg) of the resin was lowered, so that the pulverization of the resin was impossible due to fusion problems caused by frictional heat, and thus toner was not manufactured.
When the glycerin content in Comparative Example 6 is used in excess of 10% by weight, the polymerization rate is so fast that the resin gels and the resin is not easily pulverized, and thus toner production is impossible, and when the 1,3-propanediol content exceeds 10% by weight, The problem that the glass transition temperature (Tg) of ester resin falls also occurred.
In Comparative Example 7, after obtaining a predetermined degree of polymerization (softening temperature of 120 to 140 ° C) as a polymerization raw material of the polyester resin, addition polymerization was carried out with lactide at the end of the polymerization, or in the form of a polylactic acid oligomer or polymer that has already been polymerized. If the polymer is further polymerized with the polymerization raw material of the polyester resin, the poly lactic acid in the resin is blocked and the toner becomes considerably hardened due to the crystallinity peculiar to the polylactic acid. There is also a problem that the characteristics of the thermoplastic resin at the time of fixing are lowered and the biodegradability is inferior to long-term storage stability due to the temperature characteristics. Therefore, the lactic acid (D or L-lactic acid) or its derivative, lactide (D or L-lactide), is introduced at the beginning of the polymerization reaction and is preferably included in the form of random polymer in the resin.
Claims (9)
(b) polycondensing the reactants, wherein at least one of the reaction steps is carried out in the presence of more than 0% by weight and less than 1% by weight of a heat stabilizer.
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KR1020100001791A KR20110081571A (en) | 2010-01-08 | 2010-01-08 | Polyester resin and toner including the same |
PCT/KR2011/000060 WO2011083970A2 (en) | 2010-01-08 | 2011-01-06 | Polyester resin and toner comprising the same |
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