JPH04492B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a new polyester resin that is strong, has excellent abrasion resistance, is flexible, has a low fixing temperature, and is resistant to blocking. [Conventional techniques and problems] As a conventional method for producing polyester resin,
A method for producing a linear polyester by reacting a dicarboxylic acid with a diol having an etherified diphenol as a backbone, and a method for producing a non-linear polyester by using an etherified polyhydroxyl compound as a third component in addition to these two components. A method of producing a non-linear polyester using a polycarboxylic acid having three or more basic acids as the third component is known. Polyester resins produced by these methods have some good performance. However, linear polyester resins exhibit good solubility in unsaturated monomers but lack toughness and abrasion resistance, so their performance as cured polyesters is still insufficient. Although it can be used as a binder for toner used in electrophotography, it cannot be used in high-speed copying where a heat roller is used for the fixing method because an offset phenomenon occurs. On the other hand, in the case of nonlinear polyester resins that use an etherified polyhydroxy compound as the third component, toughness and abrasion resistance are improved while maintaining some degree of solubility in unsaturated monomers, but glass transition Since the point does not become high, there is a high risk of solidification especially when used in powder form, and there is a drawback that it is difficult to use as a binder for glass fiber mats or a binder for electrophotographic nonners. In addition, when using a polycarboxylic acid of tribasic acid or more as a third component, if the amount used is small, the effect will be weak, and if the amount used is increased, it will be effective, but on the contrary, it will become hard and brittle and have a high softening point. Not only does this result in a polyester resin, but it also becomes insoluble in unsaturated monomers and cannot be used in cured polyester. In addition, it is dangerous in terms of production as it may solidify in the reaction tank during production. In addition, when polyester resin is used in powder coatings, powder adhesives, and electrophotographic toner binders,
Polyester resin will be used in powder form,
In this case, from the viewpoint of energy saving, it is necessary to fix the adhesive to the adherend at a low temperature, but it must not cause blocking during storage. [Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive research to obtain a resin that satisfies all of these points. That is, the present invention provides (a) the following general formula (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, X and Y are positive integers, and the average value of the sum is 2 to 16.); (a) Divalent carboxylic acid or its acid anhydride or its lower alkyl ester; (b) Trimethic acid or its acid anhydride or its lower alkyl ester; and (c) α-olefin having 22 to 62 carbon atoms and maleic anhydride. A polycarboxylic acid, its acid anhydride, or its lower alkyl ester, which is a copolymer with an average molecular weight of 8,000 to 20,000 obtained by a copolymerization reaction with an acid, or/and the following formula (X is an alkenylene group having 5 to 30 carbon atoms and having one or more side chains having 3 or more carbon atoms) A carboxylic acid component consisting of a tetracarboxylic acid, its acid anhydride, or its lower alkyl ester represented by ( Provided is a method for producing a novel polyester resin, in which b) is 5 to 30 mol % of the total carboxylic acid components, and (c) is condensation polymerized with a carboxylic acid component that is 0.1 to 20 mol % of the total carboxylic acid components. It is something. Examples of the diol component (a) in the present invention include polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2,2-bis(4- hydroxyphenyl) propane, polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)
Propane, polyoxypropylene (2.0)-polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (6)-2,2-bis(4-hydroxyphenyl)
Examples include propane. The description in parentheses after the polyoxyalkylene of the diol component above means the average number of moles of alkylene oxide added, and the same applies to the following description. Among the carboxylic acid components (b) in the present invention, the divalent carboxylic acids (a) include fumaric acid, maleic acid, phthalic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, and n-dodecylsuccinic acid. , isododecylsuccinic acid, n-octylsuccinic acid, isooctylsuccinic acid, n-octenylsuccinic acid, n-butylsuccinic acid, and other alkyl or alkenylsuccinic acids. By using fumaric acid, phthalic acid, etc. and alkyl or alkenyl succinic acid together as the divalent carboxylic acid mentioned above, it is possible to lower the minimum fixing temperature without lowering the offset generation temperature, but if there is too little, the effect is weak, and when too much is used, the minimum fixing temperature can be lowered. and the Tg decreases, making it difficult to control the reaction. Therefore, its content is preferably 5 to 30 mol% in the carboxylic acid component. In addition, (b) trimethic acid is a preferable acid component that improves the offset phenomenon, but if it is small, the effect is weak, and if it is large, it is difficult to control the reaction and it is not only difficult to obtain a polyester resin with stable performance, but also the resin deteriorates. Undesirable phenomena such as hardness and difficulty in crushing occur, such as an increase in the minimum fixing temperature, occur. Therefore, the amount of trimetic acid in the carboxylic acid component is preferably 5 to 30 mol%. Furthermore, the relatively low molecular weight copolymer having an average molecular weight of 8,000 to 20,000 obtained by the copolymerization reaction of (c) an α-olefin having 22 to 62 carbon atoms and maleic anhydride has a copolymerization ratio of α. - The molar ratio of olefin/maleic anhydride is preferably 1/4 to 4/1,
The softening point (ring and ball softening point according to ASTM-E28-51T) is preferably 60°C to 120°C. Examples of α-olefins used include n-dococene-(1), n-pentacocene-(1), n-dotriacontene-(1), n-tetracontene-
(1), n-pentatetracontene-(1), n-pentacontene-(1), n-hexacontene-
(1), 3-butyldocosene-(1), 3-ethylhexacosene-(1), and the like. Inner olefins other than α-olefins, such as triaconten-(4) and hexacocene-(8), can also be contained, but since the toner tends to cause caking, they should only be contained up to 10% by weight of the olefins. I can do it. By using such a polycarboxylic acid, it is possible to improve offset resistance without raising the minimum fixing temperature in the fixing process, but if a large amount is used, toner caking is likely to occur and it is difficult to control the reaction. It becomes difficult. Therefore, its content in the carboxylic acid component is 0.1 to 20 mol%, more preferably 1 to 10 mol%.
It is mole%. When producing the polyester resin of the present invention, the ratio of the number of hydroxyl groups in the diol component to the number of carboxyl groups in the carboxylic acid component is determined.
It is good to set it to 1.2 to 0.8, preferably 1.1 to 0.9. Furthermore, the tetracarboxylic acid (c) represented by formula () used in the present invention includes (1) 4-neobentridenyl-1,2,6,7-
Heptanetetracarboxylic acid (2) 4-Neopentyl-1,2,6,7-heptene (4)-tetracarboxylic acid (3) 3-Methyl-4-heptenyl-1,2,5,
6-hexanetetracarboxylic acid (4) 3-methyl-3-heptyl-5-methyl-
1,2,6,7-heptene(4)-tetracarboxylic acid(5) 3-nonyl-4-methylidenyl-1,2,
5,6-hexanetetracarboxylic acid (6) 3-decylidenyl-1,2,5,6-hexanetetracarboxylic acid (7) 3-nonyl-1,2,6,7-heptene (4)-tetracarboxylic acid (8) 3-decenyl-1,2,5,6-hexanetetracarboxylic acid (9) 3-butyl-3-ethylenyl-1,2,5,
6-hexanetetracarboxylic acid (10) 3-methyl-4-butylidenyl-1,2,
6,7-heptanetetracarboxylic acid (11) 3-methyl-4-butyl-1,2,6,7
-heptene (4)-tetracarboxylic acid (12) 3-methyl-5-octyl-1,2,6,
Examples include 7-heptene(4)-tetracarboxylic acid. The structural formulas of these compounds are shown below. For convenience, all are shown in the form of acid anhydrides. By using these tetracarboxylic acids, the minimum fixing temperature can be lowered in the fixing process and offset resistance can be improved, but if used in a small amount, the effect is small, and if used in a large amount, the fixing Not only does this result in poor properties, but it also becomes difficult to control the degree of resin polymerization during production. Therefore, its content is 0.1 to 20 mol% in the carboxylic acid component,
More preferably, it is 1 to 10 mol%. Also, similar tetracarboxylic acids include aliphatic tetracarboxylic acids without side chains or aliphatic tetracarboxylic acids with very short side chains, such as 1,2,7,8-octanetetracarboxylic acid, 1,2,5 , 6-hexanetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 3-methyl-1,2,10,11-undecanetetracarboxylic acid, 4-ethyl-1,
Examples include 2,7,8-octene(4)-tetracarboxylic acid, but it is not as effective in low-temperature fixing properties as tetracarboxylic acid having one or more side chains with 3 or more carbon atoms, so the amount used should be increased. This is undesirable because toner caking tends to occur and it becomes difficult to control the reaction during production. Also, alicyclic polycarboxylic acids, aromatic tetravalent carboxylic acids, such as 3-methyl-
5-succinyl-4-cyclohexene-1,2-
Dicarboxylic acid, pyromellitic anhydride, benzophenonetetracarboxylic acid, cyclopentenetetracarboxylic acid, melfanic acid, etc. often undergo decomposition, sublimation, coloring, etc. during resin production, and also have poor low temperature fixing properties and offset resistance. It has little effect. The polyester resin used in the present invention can be produced by condensation polymerization of a polyhydric carboxylic acid component and a polyol component at a temperature of 180 to 250°C in an inert gas atmosphere. At this time, commonly used esterification catalysts such as zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate, etc. can be used to accelerate the reaction.
It can also be produced under reduced pressure for the same purpose. The polyester resin produced according to the present invention can be used for various purposes, and is useful as a binder, as well as for powder applications such as powder coatings, powder adhesives, and electrophotographic toners. It is convenient for applications such as industrial binders. The resin produced according to the present invention can be mixed with other chemical substances such as pigments, dyes, and magnetic powders depending on the purpose. Colorants used in combination with the resin produced according to the present invention include, for example, carbon black, acetylene black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, and solvent red. 49, Solvent Red 146,
Solvent blue 35, iron black, nigrosine, benzidine yellow, quinacridone, rhodamine B, phthalocyanine blue nigrosine dye, aniline blue, calco oil blue, chrome yellow,
Ultramarine blue, Dupont oil red,
Examples include quinoline yellow, methylene blue, chloride/malachite green oxalate, rose bengal, etc., and mixtures thereof. Examples of the magnetic material used in the present invention include alloys containing ferromagnetic elements such as ferrite and magnetite; The magnetic material is in the form of fine powder with an average particle size of 0.1 to 1μ and is contained in a resin containing 40 to 70% of the magnetic material.
It can be used by dispersing amounts of % by weight. Furthermore, when the resin produced by the production method according to the present invention is used in an electrophotographic toner binder, it acts as a binder that binds various components used to produce the toner, such as colorants, magnetic materials, etc. , an offset prevention agent, a charge control agent, etc., constitute the toner. In this case, the following compounds, for example, can be used as the charge control agent. R: a group selected from the group consisting of hydrogen, a lower alkyl group, a lower alkoxy group, and a halogen. R ¹ : A group selected from the group consisting of hydrogen, a lower alkyl group, a lower alkoxy group, and a halogen. R ² , R ³ : an azo group, an imino group bonded to a substituent selected from an aryl group, an arylalkenyl group, a substituted aryl group, and a substituted arylalkenyl group represented by the following general formulas (1) to (3) and the same or different groups selected from the group consisting of alkenyl groups. (In the formula, R ⁴ is hydrogen, lower dialkylamino group,
A group selected from the group consisting of a nitro group, a lower alkoxymorpholino group, a piperidino group, a halogen group, and a diurolidino group, where n is an integer of 0 to 3 and m is an integer of 1 to 4. ) (In the formula, R ₁ and R ₂ are hydrogen, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or

[Formula] (R ₃ and R ₄ represent hydrogen or an alkyl group having 1 to 6 carbon atoms). or the following compound R ₁ = hydrogen or hydroxyl group or alkenyl group or alkyl group R ₂ =

[Formula] or

【Formula】Also teeth

[Formula] R ₃ to _{R 6} = hydrogen, alkyl group, allyl group, aralkyl group, or alkenyl group The content of this compound is 0.1 to 15% by weight in the resin, preferably 0.8 to 5% by weight. . If the content is less than 0.1% by weight, the stability of the charge will be lost, and if the content is 15% by weight, the charge will be saturated, and there will be no effect even if it is added more than that, and on the contrary, it will not be effective when adding other electrophotographic materials. Adversely affects physical properties. The above compounds will be specifically shown below, but the invention is not limited to these examples. Pyrazoline derivatives represented by the following general formula [] may also be used. General formula [] In the formula, Ar ₁ , Ar ₂ and Ar ₃ represent a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle, and at least one of Ar ₁ , Ar ₂ and Ar ₃ is It is an electron donating group, and n represents 0 or 1. Preferred pyrazoline derivatives are those represented by the following general formula []. General formula [] In the formula, Ar ₃ represents a substituted/unsubstituted aromatic heterocyclic group or a substituted/unsubstituted aromatic heterocyclic group, R ₁ ,
R ₂ , R ₃ and R ₄ are substituted/unsubstituted alkyl groups, substituted/unsubstituted aryl groups, or may form a ring together with a nitrogen atom, and R ₁ , R ₂ , R ₃
and R ₄ may be the same or different, and n represents 0 or 1. In addition, the above general formula []

[Formula] Group or

[Formula] Examples of the group include dimethylamino group, diethylamino group, methyl-ethylamino group,

[Formula] Group or

Examples of the group include electron-donating groups such as morpholino, piperidino, piperazino, and pyrrolidino groups, and examples of Ar ₃ include substituted and unsubstituted phenyl groups, naphthyl groups, anthranyl groups, Examples include pyridyl group and quinolyl group. Specific examples of the pyrazoline derivatives represented by the general formulas [] and [] include those having the following structural formulas. Piperazine derivatives represented by the following general formula [] can also be used. General formula [] In the formula, Ar represents a substituted/unsubstituted aromatic carbocyclic group or a substituted/unsubstituted aromatic heterocyclic group, and preferably has an electron-donating substituent. R represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or an aryl group. Examples of Ar include a substituted or unsubstituted phenyl group, naphthyl group, anthranyl group, pyridyl group, or quinolyl group, and preferably an electron-donating substituent, such as
dimethylamino group, diethylamino group, methyl-
More preferred are an ethylamino group, a morpholino group, a piperidino group, a piperazino group, a pyrrolidino group, and the like. R represents a hydrogen atom, an unsubstituted/substituted lower alkyl group (eg, methyl group, ethyl group, butyl group, propyl group), or an aryl group (eg, phenyl group). Specific examples of the piperazine derivative represented by the general formula [] include those having the following structural formula. Also, compounds represented by the following general formula may be used. (In the formula, R represents a substituted or unsubstituted aromatic ring or heterocycle.) Representative specific examples of the compound represented by the above general formula include the following. Furthermore, a compound of the following general formula (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group or an aralkyl group, and may be the same or different.) Or a compound of the following general formula (In the above formula, R ₃ , R ₄ and R ₅ represent an alkyl group or an aralkyl group, and may be the same or different.) may also be used. Typical specific examples of the compound represented by the general formula () include the following. Further, as the compound represented by the general formula (), the following compounds are exemplified. Alternatively, the following compounds may also be used. However, R ₁ to R ₄ : H, C _o H _2o +1 (n=1 to 3) or

[Formula], R ₅ , R ₆ :C _o H _2o +1 (n=1 to 3) or

〔Example〕

Examples will be described in detail below, but the present invention is not limited to these examples. Example 1 Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 525g, polyoxyethylene(2)-2,2-bis(4-hydroxyphenyl)propane 487.5g, fumaric acid
Put 172.5 g of isooctyl succinic acid, 138 g of isooctyl succinic acid, and 0.1 g of hydroquinone into a 4-neck glass flask, attach a thermometer, a stainless steel stirring bar, a flowing-down condenser, and a nitrogen inlet tube, and place them in an electric heating mantle in a nitrogen stream. The reaction was carried out at 200°C with stirring. When water stopped flowing out, the acid value was measured and found to be 1.0 mgKOH/g. Furthermore, 115.2 g of trimellitic anhydride, 50% by weight of α-olefin having an average carbon number of 32, and maleic anhydride.
50% by weight of copolymer A (average molecular weight 8000, softening point
60℃) was added and reacted for about 8 hours until the acid value reached
The reaction was terminated when 25 mgKOH/g was reached. The resulting resin was a pale yellow solid with a softening point of 122°C at the end of the process. Even when this resin was pulverized and left at 45°C for one month, no blocking occurred. To 100 parts of the resin, 8 parts of carbon black (Raben 3500 manufactured by Columbia Carbon Co., Ltd.) and 2 parts of a chromium-containing charge control agent (Bontron S34 manufactured by Orient Chemical Co., Ltd.) were milled in a ball mill and then kneaded with three rolls. After cooling, the mixture was coarsely crushed and finely pulverized using a jet mill, and a toner having an average particle size of 12 μm was produced using an air classifier. 100 parts of this toner and 1200g of iron powder (manufactured by Nippon Iron Powder)
EFV200/300) was uniformly mixed in a blender to prepare a developer. Clear images with no spot stains were obtained using a commercially available copying machine. The temperature of the definition roller of the commercial copying machine was modified to be variable.100
Images were taken at various temperatures ranging from .degree. C. to 240.degree. The results are shown in Table-1. Fixability evaluated using Sellotape peel test
No peeling of the fixed toner was observed even at 120°C. Example 2 Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 1000g, terephthalic acid 237.1g, n-dodecylsuccinic acid 286g
g, 0.5 g of stannous oxide, and 0.1 g of hydroquinone were placed in the same apparatus as in Example 1, and heated in a nitrogen stream.
The reaction was carried out at 230°C. When water stopped flowing out, the acid value was measured and found to be 1.5 mgKOH/g. Additionally, 54.9g of trimethic anhydride and average carbon number 45
Copolymer B of 30% by weight of α-olefin and 70% by weight of maleic anhydride (average molecular weight 10,000, softening point 75
℃）29g was added and reacted for about 8 hours until the softening point reached 125℃.
The reaction was terminated when the temperature reached . The resulting resin was a pale yellow solid with an acid value of 16 mgKOH/g. Even when this resin was crushed and left at 45°C for one month, no blocking occurred. In the same manner as in Example 1, the offset occurrence temperature and minimum fixing temperature were measured. The results are shown in Table 1. Examples 3 to 5, Comparative Examples 1 to 5 Next, Table 1 shows several examples and comparative examples using polyester resins synthesized by a method similar to Example 1.
Shown below.

【table】

【table】

[Table] Example 6 Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 525g, polyoxyethylene(2)-2,2-bis(4-hydroxyphenyl)propane 488g, fumaric acid 139
g, trimethic acid 126 g, 3-isodecenyl-1,
Put 60 g of 2,5,6-hexanetetracarboxylic acid, 170 g of isodecenylsuccinic acid, and 1.5 g of hydroquinone into a 2-piece glass four-necked flask, and attach a thermometer, a stainless steel stirring bar, a flowing condenser, and a nitrogen introduction tube. The reaction was carried out in an electric heating cloak at 200°C under a nitrogen stream with stirring.
The degree of polymerization was monitored from the softening point according to ASTM E28-51T, and the reaction was terminated when the softening point reached 122°C. The resulting resin is a pale yellow solid;
Glass transition temperature measured by DSC (differential calorimeter) is 62℃
It was hot. Comparative Example 6 A resin was produced using the same equipment and procedure as in Example 6 except that 3-isodecenyl-1,2,5,6-hexanetetracarboxylic acid was removed, and the softening point was
The reaction was terminated when the temperature reached 122°C. The obtained resin was a pale yellow solid with a glass transition point of 62°C. Examples 7 to 12, Comparative Examples 7 to 10 Several examples and comparative examples using polyester resins synthesized by a method similar to Example 6 are shown in Table 2.

【table】

【table】

【table】

Claims (1)

[Claims] 1 (a) The following general formula (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, X and Y are positive integers, and the average value of the sum is 2 to 16.); (a) divalent carboxylic acid or its acid anhydride or its lower alkyl ester; (b) trimellitic acid or its acid anhydride or its lower alkyl ester; and (c) α-olefin having 22 to 62 carbon atoms and maleic anhydride. A polycarboxylic acid, its acid anhydride, or its lower alkyl ester, which is a copolymer with an average molecular weight of 8,000 to 20,000 obtained by a copolymerization reaction with an acid, or/and the following formula (X is an alkenylene group having 5 to 30 carbon atoms and having one or more side chains having 3 or more carbon atoms) A carboxylic acid component consisting of a tetracarboxylic acid, its acid anhydride, or its lower alkyl ester represented by ( Production of a new polyester resin characterized by condensation polymerization of b) with a carboxylic acid component of 5 to 30 mol% of the total carboxylic acid component and (c) of 0.1 to 20 mol% of the total carboxylic acid component Method.