JP2005314686A - Method for producing polyester resin, polyester resin, and toner composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyester resin, by which the polyester resin can efficiently be produced, even when a catalyst except tin compounds is used. <P>SOLUTION: This method for producing the polyester resin, comprising polycondensing a polyol component with a polycarboxylic acid component, is characterized by using the 1,2-propylene glycol ester of the polycarboxylic acid as at least one part of the polycarboxylic acid component, and releasing the 1,2-propylene glycol. The polycondensation in the presence of a titanium-containing catalyst is preferable. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a polyester resin, a polyester resin, and a toner composition using the same for electrophotography, electrostatic recording, electrostatic printing and the like.

As a method for producing a polyester resin, a method obtained by dehydrating and condensing a polycarboxylic acid and a polyol in the presence of an esterification catalyst, and a method using dealcoholization of a lower alkyl ester of a polycarboxylic acid are mainly used. As the catalyst, a tin compound is often used, but an alternative is demanded from the viewpoint of environmental problems.
As a method for producing a polyester resin without using a tin compound, for example, a titanium compound having a specific structure, which has excellent reaction activity, good hydrolysis resistance, and is suitable as a catalyst for the production of a binder resin for toner, is used. A method for use as a catalyst is disclosed (see Patent Document 1).
JP 2003-201342 A

However, even in the method using the titanium compound proposed in the above publication, which is said to be excellent in reaction activity, as a catalyst, even if the reaction rate, which is a low reaction rate as a sequential reaction, reaches 90%, depending on the monomer composition It takes about 20 hours, and when the reaction rate is further increased and the reaction is allowed to reach the softening point at which the toner can be used as a binder resin for toner, it takes a considerable amount of time, which is insufficient for industrial production. .
An object of this invention is to find the method of manufacturing a polyester resin efficiently, even when using catalysts other than a tin compound.

The inventor has intensively studied to solve these problems, and has reached the present invention.
That is, the present invention includes the following (I) to (IV).
(I) In a process for producing a polyester resin in which a polyol component and a polycarboxylic acid component are polycondensed, 1,2-propylene glycol ester of polycarboxylic acid is used as at least a part of the polycarboxylic acid component, (II) A polyester resin having a number average molecular weight of 1,000 to 20,000 obtained by the method of (I).
(III) A polyester resin comprising a polyol constituent unit and a polycarboxylic acid constituent unit, the polyol constituent unit containing 10 to 100 mol% of a propylene oxide adduct of bisphenol A, and the polycarboxylic acid constituent unit A polyester resin containing 60 mol% or more of aromatic polycarboxylic acid units and a tin content of 10 ppm or less.
(IV) A toner composition comprising the polyester resin of (II) or (III), a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.

  According to the production method of the present invention, when an esterification catalyst other than an organotin compound is used, even a polyester resin having a composition that requires a long time for the reaction can be combined in a relatively short time. The polyester resin obtained by the production method of the present invention is useful as a binder resin for electrostatic image toners.

The present invention is described in detail below.
In the method for producing a polyester resin of the present invention, a polyol component and a polycarboxylic acid component are polycondensed.
The polycarboxylic acid component contains 1,2-propylene glycol ester of polycarboxylic acid (hereinafter, 1,2-propylene glycol may be abbreviated as PG) as an essential component.
Among the polycarboxylic acids constituting the PG ester, aliphatic (including alicyclic) dicarboxylic acids include alkane dicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, repartic acid, And alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid).
Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid).

Among the carboxylic acids, trivalent to hexavalent or higher aliphatic (including alicyclic) polycarboxylic acids include aliphatic tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid) and unsaturated carboxylic acids. Vinyl polymer [number average molecular weight (hereinafter referred to as Mn, by gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid copolymer and the like) and the like.
Among the carboxylic acids, the aromatic polycarboxylic acids having 3 to 6 valences or more include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and vinyls of unsaturated carboxylic acids. Polymer [Mn: 450-10000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, styrene / fumaric acid copolymer, etc.) and the like.

  Among the carboxylic acids constituting these PG esters, preferred are alkane dicarboxylic acids having 2 to 50 carbon atoms, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and 9 carbon atoms. To 20 aromatic polycarboxylic acids, more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and these Particularly preferred are terephthalic acid, isophthalic acid, trimellitic acid, and a combination thereof, and most preferred is terephthalic acid.

  Moreover, as carboxylic acid, what contains 60 mol% or more of aromatic polycarboxylic acids is preferable. The content of the aromatic polycarboxylic acid is more preferably 70 mol% or more, particularly preferably 80 mol% or more. When it is contained in an amount of 60 mol% or more, it is preferable in terms of improving toner performance such as heat resistant storage stability and durability.

In the present invention, the polycarboxylic acid PG ester can be produced by an ordinary method. For example, the reaction temperature of the polycarboxylic acid or its anhydride or its lower alkyl ester (alkyl group having 1 to 4 carbon atoms) and PG in an inert gas (nitrogen gas or the like) atmosphere is preferably 150 to It can be obtained by reacting at 280 ° C., more preferably 160 to 260 ° C., particularly preferably 170 to 240 ° C. and a pressure of 0.2 to 0.8 MPa. At this time, an esterification catalyst may be used as necessary. Examples of the esterification catalyst include those described below.
The reaction ratio between the alcohol component and the carboxylic acid component is preferably 8/1 to 2/1, more preferably 6/1 to 2.5 / 1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. Especially preferably, it is 5/1 to 3/1.
The PG ester may be a structure in which one or more carboxyl groups of the polycarboxylic acid are esterified with PG, but PG polyester having a structure in which all the carboxyl groups are esterified with PG is preferable. The PG ester substitution rate (hereinafter also simply referred to as substitution rate) of the polycarboxylic acid is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more.
A substitution rate of 50% or more is preferable in that the esterification reaction time is shortened.
The substitution rate can be determined from ¹ H-NMR, for example.

As the polycarboxylic acid component, in addition to the PG ester of polycarboxylic acid, other polycarboxylic acids may be used.
Examples of the other polycarboxylic acid include those similar to the polycarboxylic acid constituting the PG ester. Preferred are alkane dicarboxylic acids having 2 to 50 carbon atoms, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and aromatic polycarboxylic acids having 9 to 20 carbon atoms or anhydrides thereof. Or a lower alkyl ester thereof (alkyl group having 1 to 4 carbon atoms), more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, Mellitic acid, pyromellitic acid, or an anhydride thereof, or a lower ester thereof and a combination thereof, particularly preferably fumaric acid, adipic acid, terephthalic acid, trimellitic acid, or an anhydride thereof, or a lower alkyl ester thereof And combinations thereof.
The content of the PG ester of polycarboxylic acid in the polycarboxylic acid component is preferably 50 mol% or more. More preferably, it is 70 mol% or more, Most preferably, it is 80 mol% or more.

  Among the polyol components used in the production method of the present invention, the dihydric alcohol (diol) includes an aliphatic diol having 2 to 36 carbon atoms (such as ethylene glycol, propylene glycol, and dodecanediol); a polyalkylene having 4 to 36 carbon atoms. Ether glycol (diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc.); C 2-4 alkylene oxide (hereinafter abbreviated as AO) of aliphatic diols having 2 to 6 and 7 to 36 carbon atoms [ethylene oxide] (Hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) and butylene oxide, etc.] Adducts (addition mole number: 2-30); C6-C36 alicyclic diol (1,4-cyclohexanedi) Methanol, hydrogenated bisphe AO adducts having 2 to 4 carbon atoms (addition moles 2 to 30) of the above alicyclic diols; bisphenols (such as bisphenol A, bisphenol F and bisphenol S) having 2 to 4 carbon atoms. AO adduct (addition mole number 2-30) etc. are mentioned.

Among the polyhydric alcohols, alcohols having 3 to 8 or more valences include 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (glycerin, triethylolethane, trimethylolpropane, pentaerythritol and Sorbitol, etc.); AO adduct having 2 to 4 carbon atoms of the above aliphatic polyhydric alcohol (addition mole number 2 to 30); AO adduct having 2 to 4 carbon atoms (addition) of trisphenols (trisphenol PA, etc.) Mole number 2-30); C2-C4 AO adduct (addition mole number 2-30) etc. of novolak resin (phenol novolak, cresol novolak, etc .: average polymerization degree 3-60) etc. are mentioned.
Among these polyhydric alcohols, preferably, a polyalkylene ether glycol having 4 to 36 carbon atoms, an alicyclic diol, an AO adduct having 2 to 4 carbon atoms of an alicyclic diol having 6 to 36 carbon atoms, and bisphenol. C2-4 AO adducts and novolak resin C2-4 AO adducts, more preferably bisphenol C2-3 AO (EO and PO) adducts, and novolacs It is an AO (EO and PO) adduct having 2 to 3 carbon atoms of the resin.
Further, from the viewpoint of toner performance such as charging environmental stability, the content of the PO adduct of bisphenol A in the polyol component is preferably 10 to 100 mol%. More preferably, it is 60-100 mol%, Most preferably, it is 80-100 mol%.
When the polyol constituent unit of the polyester resin to be produced is only PG, it can be produced using only the PG ester of polycarboxylic acid without using any polyol component. This method is also the present invention. include.

In the present invention, the polyester resin can be produced in the same manner as in an ordinary polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 260 ° C, particularly preferably 170 to 240 ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction.
It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio between the alcohol component and the carboxylic acid component is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. .3, particularly preferably 1.3 / 1 to 1 / 1.2.

At this time, it is preferable to use an esterification catalyst. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts (eg, titanium alkoxide, potassium oxalate titanate, and titanium terephthalate), zirconium-containing catalysts (eg, zirconyl acetate), And zinc acetate. In addition, a catalyst described in International Publication No. WO03 / 073171 can also be used.
Among these catalysts, a catalyst other than a tin-containing catalyst is preferable from the viewpoint of environmental conservation, and a titanium-containing catalyst is more preferable.
The amount of the catalyst added is desirably determined as appropriate so as to maximize the reaction rate. The addition amount is 10 ppm to 1.9%, preferably 100 ppm to 1.7%. The amount added is preferably 10 ppm or more, so that the reaction rate is increased.

The number average molecular weight (hereinafter referred to as Mn) of the tetrahydrofuran (THF) -soluble component of the polyester resin obtained by the production method of the present invention is preferably 1000 to 20000 because it can exhibit the properties as a resin. More preferably, it is 1200-15000.
The polyester resin obtained by the production method of the present invention can be suitably used as a binder resin for toner because a resin having a relatively high softening point is efficiently obtained and the resin strength is high.

When used as a binder resin for toner, the Mn of tetrahydrofuran (THF) soluble component is preferably 1000 to 10,000. The lower limit is more preferably 1200, particularly preferably 1400, and the upper limit is more preferably 9500, particularly preferably 9000. When Mn is 1000 or more, the resin strength is good, and when it is 10000 or less, the low-temperature fixability of the toner and the resin grindability are good.
In addition, when used as a binder resin for toner, the peak top molecular weight (hereinafter referred to as Mp) of the THF-soluble component is preferably 1200 to 2000 from the viewpoint of the balance between resin strength, low-temperature fixability, and resin grindability. It is 50000, More preferably, it is 1500-40000.

In the above and below, the Mn and Mp of the THF-soluble component of the polyester resin are measured using GPC under the following conditions.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection volume: 100 μl
Detector: Refractive index detector Reference substance: Standard polystyrene The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The molecular weight of the polyester resin particles for toner was measured by taking one arbitrary particle in the toner polyester resin and dissolving it in THF as a sample solution. This measurement was performed on 10 particles.

For the first time by the production method of the present invention, the unit of the PO adduct of bisphenol A in the polyol constituent unit, which has been difficult to produce in the past, is 10 to 100 mol% (further 60 to 100 mol%, especially 80 to 100 mol%). Thus, a polyester resin having an aromatic polycarboxylic acid unit in the polycarboxylic acid constituent unit of 60 mol% or more (particularly 80 mol% or more) and a tin content of 10 ppm or less can be produced. Such a resin is suitable as a toner binder resin because it is excellent in low-temperature fixability and hot offset resistance and has a small environmental load.
In the present invention, the tin content is determined by the fluorescent X-ray method.

When used as a binder resin for toner, the glass transition point (Tg) of the polyester resin obtained by the production method of the present invention is preferably 40 to 90 ° C., more preferably 45 to 85, from the viewpoint of heat resistant storage stability and low temperature fixability. ° C, particularly preferably 50 to 80 ° C.
In addition, in the above and below, Tg is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20, SSC / 580.

The THF insoluble content in the polyester resin is preferably 70% or less from the viewpoint of low-temperature fixability. The lower limit is more preferably 1%, particularly preferably 3%, and the upper limit is more preferably 40%, particularly preferably 30%. In the above and the following, “%” means “% by weight” unless otherwise specified.
The THF insoluble matter was determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling, the insoluble content is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The insoluble matter is calculated from the weight of the dried resin content on the glass filter and the weight ratio of the sample.

The polyester resin of the present invention may be used in combination of two or more. When used as a binder resin for a toner, the linear polyester resin (B) and the non-linear polyester are used in terms of compatibility between low-temperature fixability, hot offset resistance and grindability. It is preferable to consist of resin (C). (B) and (C) may use 2 or more types together, respectively.
The weight ratio of (B) to (C) is preferably 10/90 to 80/20, more preferably 20/80 to 75/25, and particularly preferably 25/75 to 70/30.
For the same reason, the Mn content of the THF soluble component in (C) is preferably 200 or more, more preferably 300 or more, greater than that of (B).

The linear polyester resin (B) is usually obtained by polycondensation of the diol and dicarboxylic acid. Moreover, the molecular terminal may be modified with an anhydride of the carboxylic acid (including trivalent or higher carboxylic acid).
The nonlinear polyester resin (C) is usually obtained by reacting the above tricarboxylic acid and / or trihydric polyhydric alcohol together with the above dicarboxylic acid and diol.
In the case of obtaining (C), the ratio of the polycarboxylic acid having a valence of 3 or more and the polyhydric alcohol having a valence of 3 or more is such that the sum of these moles is the sum of the moles of all alcohol components and carboxylic acid components. Preferably it is 0.1-40 mol%, More preferably, it is 1-25 mol%, Most preferably, it is 3-20 mol%.

The THF-insoluble matter in (B) is preferably 3% or less, more preferably 1% or less, and particularly preferably 0%. A smaller amount of (B) insoluble in THF is preferred from the viewpoint of improving low-temperature fixability.
The THF-insoluble content of (C) is preferably 5 to 70%. The lower limit is more preferably 10%, particularly preferably 15%, and the upper limit is more preferably 60%, particularly preferably 50%. Inclusion of the THF-insoluble content in the above range is preferable from the viewpoint of improving hot offset resistance.

    The toner composition of the present invention contains the polyester resin for toner of the present invention as a binder resin, a colorant, and, if necessary, one or more additives such as a release agent, a charge control agent, and a fluidizing agent. .

  As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Varanitoaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt or nickel or a compound such as magnetite, hematite, or ferrite) can be added to serve as a colorant. The content of the colorant is preferably 1 to 40 parts, more preferably 3 to 10 parts, relative to 100 parts of the polyester resin of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts. Above and below, parts mean parts by weight.

  The release agent preferably has a softening point of 50 to 170 ° C., and examples thereof include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl carbon number 1 to 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.

  Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, and the like.

  Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

  The composition ratio of the toner composition of the present invention is preferably 30 to 97%, more preferably 40 to 95%, particularly preferably 45 to 92% of the polyester resin of the present invention based on the toner weight; Preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; Of the additives, the release agent is preferably 0 to 30%, more preferably 0 0.5-20%, particularly preferably 1-10%; charge control agent is preferably 0-20%, more preferably 0.1-10%, particularly preferably 0.5-7.5%; fluidization The agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. The total content of the additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

The toner composition of the present invention may be obtained by any conventionally known method such as a kneading and pulverizing method, an emulsion phase inversion method, or a polymerization method. For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. By further classifying, the particle size (D50) can be preferably made into fine particles having a particle size of 5 to 20 μm, and then mixed with a fluidizing agent. The particle size (D50) is measured using a Coulter counter [for example, trade name: Multitizer III (manufactured by Coulter)].
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  The toner composition of the present invention is electrically mixed with carrier particles such as ferrite coated on the surface with iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin, etc.) as necessary. Used as a latent image developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. In addition, instead of the carrier particles, it can be rubbed with a member such as a charging blade to form an electric latent image.

  The toner composition of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

A method for measuring the properties of the polyester resin for toner obtained in Examples and Comparative Examples is shown below.
1. Acid value and hydroxyl value Method defined in JIS K0070 (1992 edition).
When the sample had a solvent-insoluble component accompanying crosslinking, the sample after melt kneading was used as a sample by the following method.
Kneading device: Labo plast mill MODEL30R150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 30 minutes at 130 ° C. and 70 rpm Measurement of softening point Using a flow tester, the temperature was raised at a constant speed under the following conditions, and the temperature at which the outflow amount became 1/2 was taken as the softening point.
Device: Shimadzu Corporation flow tester CFT-500
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.
3. PG ester substitution rate The proton nuclear magnetic resonance spectrum was measured under the following conditions, and the PG ester substitution rate was calculated from the amount of remaining terephthalic acid dimethyl ester or terephthalic acid.
Device: JEOL XL-300
Number of integrations: 64 times Measurement solvent: Deuterated chloroform Internal standard: Tetramethylsilane Proton nuclear magnetic resonance spectrum measurement of 30 parts of deuterated chloroform added to 1 part of synthesized terephthalic acid diester and completely dissolved Went.
4). Tin content According to the fluorescent X-ray method.
Device: SXF-1200BF (manufactured by Shimadzu Corporation)

Production Example 1
[Synthesis of terephthalic acid diester A1]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 647 parts (24.0 moles) of PG, 688 parts (10.0 moles) of dimethyl terephthalate and 3 parts of tetraisopropoxide titanate as a catalyst. The reaction was carried out for 3 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Subsequently, while gradually raising the temperature to 230 ° C., the reaction was carried out for 5 hours while removing methanol and excess PG in a nitrogen stream, and then taken out. This is designated as terephthalic acid diester (A1). The substitution rate of A1 was 99.9%.

Production Example 2
[Synthesis of terephthalic acid diester A2]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1078 parts (40.0 mol) of PG, 589 parts (10.0 mol) of terephthalic acid, and 3 parts of tetraisopropoxide titanate as a catalyst were prepared. The reaction was carried out for 3 hours while distilling off water under pressure of 230 ° C. and 0.4 to 0.5 MPa. Subsequently, after cooling to 180 ° C., the temperature was gradually raised to 230 ° C., and the reaction was carried out for 5 hours while distilling off water and an excessive amount of PG in a nitrogen stream. This is designated as terephthalic acid diester (A2). The substitution rate of A2 was 97.0%.

Comparative production example 1
[Synthesis of terephthalic acid diester A3]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 800 parts (24.0 moles) of 1-octanol, 497 parts (10.0 moles) of dimethyl terephthalate and tetraisopropoxide titanate as a catalyst 3 parts were charged and reacted at 180 ° C. under a nitrogen stream for 3 hours while distilling off generated methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 5 hours while distilling off methanol and excess 1-octanol under a nitrogen stream, and then taken out. This is designated as terephthalic acid diester (A3). The octanol ester substitution rate of A1-3 (measured according to the above PG ester substitution rate) was 99.9%.

Example 1
[Synthesis of linear polyester B1]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 520 parts (10.0 mol) of terephthalic acid diester (A1), 353 parts (5.5 mol) of bisphenol A / PO2 mol adduct, bisphenol A -408 parts (5.5 mol) of PO3 mol adduct and 3 parts of tetraisopropoxide titanate as a condensation catalyst were charged and heated to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was carried out while distilling off PG under a reduced pressure of 5 to 20 mmHg. The reaction was followed while measuring the softening point of the polymer to be produced, taken out when the softening point reached 110 ° C., cooled to room temperature, pulverized and granulated. This is designated as linear polyester (B1). The time required to reach the softening point of B1 was 10 hours.
The linear polyester (B1) had a Tg of 60 ° C., an Mp of 12000, an Mw of 14000, a THF-insoluble content of 0%, and a tin content of 10 ppm or less.

Example 2
[Synthesis of Linear Polyester B2]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 493 parts (10.0 mol) of terephthalic acid diester (A2), 359 parts (5.9 mol) of bisphenol A / PO2 mol adduct, bisphenol A -414 parts (5.9 moles) of PO3 mole adduct and 3 parts of tetraisopropoxide titanate as a condensation catalyst were charged and heated to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was carried out while distilling off PG under a reduced pressure of 5 to 20 mmHg. The reaction was followed while measuring the softening point of the polymer to be produced, taken out when the softening point reached 96 ° C., cooled to room temperature, pulverized and granulated. This is designated as linear polyester (B2). The time required to reach the softening point of B2 was 10 hours.
The linear polyester (B2) had a Tg of 58 ° C., an Mp of 7000, an Mw of 8000, a THF-insoluble content of 0%, and a tin content of 10 ppm or less.
[Synthesis of Non-Linear Polyester C2]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 351 parts (9.0 mol) of terephthalic acid diester (A1-2), 16 parts (1.0 mol) of fumaric acid, 3 mol of bisphenol A · PO3 694 parts (12.5 mol) of an adduct, 56 parts (0.5 mol) of an EO adduct of phenol novolac, and 3 parts of tetraisopropoxide titanate as a condensation catalyst were charged and the temperature was raised to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was carried out while distilling off PG under a reduced pressure of 5 to 20 mmHg. The reaction was followed while measuring the softening point of the polymer produced, and when the softening point reached 85 ° C, it was cooled to 180 ° C. Subsequently, 77 parts (1.2 mol) of trimellitic anhydride was added, and after 2 hours of reaction under normal pressure sealing, the reaction was performed at 220 ° C. under reduced pressure of 5 to 20 mmHg, and the softening point was removed when the temperature reached 160 ° C. After cooling to room temperature, it was pulverized into particles. This is designated as nonlinear polyester (C2). The time required to reach the softening point of C2 was 12 hours.
The nonlinear polyester (C2) had a Tg of 58 ° C., an Mp of 6000, a THF-insoluble content of 30%, and a tin content of 10 ppm or less.
[Creation of polyester resin for toner]
600 parts of linear polyester (B2) and 400 parts of non-linear polyester (C2) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature and then pulverized by a pulverizer to form particles to obtain a polyester resin for toner (D2).

Comparative Example 1
[Synthesis of linear polyester B'3]
Addition of 306 parts (10.0 mol) of terephthalic acid, 353 parts (5.5 mol) of bisphenol A / PO2 mol adduct, 3 mol of bisphenol A / PO in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube 408 parts (5.5 mol) of the product and 3 parts of dibutyltin oxide as a condensation catalyst were charged and reacted at 230 ° C. under a nitrogen stream for 6 hours while distilling off the generated water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and the reaction was followed while measuring the softening point of the polymer produced. When the softening point reached 110 ° C., the reaction product was taken out, cooled to room temperature, pulverized and granulated. This is designated as linear polyester (B′-3). The time required to reach the softening point of B′-3 was 12 hours.
The linear polyester (B′3) had a Tg of 60 ° C., an Mp of 12000, an Mw of 14000, a THF-insoluble content of 0%, and a tin content of 1000 ppm.

Comparative Example 2
[Synthesis of Linear Polyester B′-4]
Addition of 306 parts (10.0 mol) of terephthalic acid, 353 parts (5.5 mol) of bisphenol A / PO2 mol adduct, 3 mol of bisphenol A / PO in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube 408 parts (5.5 mol) of the product and 3 parts of tetraisopropoxide titanate as a condensation catalyst were charged and reacted at 230 ° C. under a nitrogen stream for 6 hours while distilling off the generated water. Next, the reaction was followed by reaction under reduced pressure of 5 to 20 mmHg, and the reaction was followed while measuring the softening point of the produced polymer. The softening point at the time of reaction for 48 hours was 65 ° C., and the desired softening point (110 ° C. ) Was not reached, so the synthesis was stopped.

Comparative Example 3
[Synthesis of Linear Polyester B′-5]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 358 parts (10.0 mol) of dimethyl terephthalate, 353 parts (5.5 mol) of bisphenol A · PO2 mol adduct, bisphenol A · PO3 408 parts (5.5 mol) of a mole adduct and 3 parts of tetraisopropoxide titanate were charged as a condensation catalyst, and the mixture was reacted at 180 ° C. for 6 hours while distilling off the produced methanol. Subsequently, the reaction was conducted for 4 hours while distilling off the generated water under a nitrogen stream at 230 ° C., and further under a reduced pressure of 5 to 20 mmHg, and the reaction was followed while measuring the softening point of the produced polymer. The softening point at the point of time reaction was 65 ° C., and since the desired softening point (110 ° C.) was not reached, synthesis was stopped.

Comparative Example 4
[Synthesis of Linear Polyester B′-6]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 719 parts (10.0 mol) of terephthalic acid diester (A1-3), 353 parts (5.5 mol) of bisphenol A · PO2 mol adduct, 408 parts (5.5 moles) of bisphenol A · PO3 mole adduct and 3 parts of tetraisopropoxide titanate as a condensation catalyst were charged and heated to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was conducted while distilling off 1-octanol under reduced pressure of 5 to 20 mmHg. The reaction was followed while measuring the softening point of the polymer to be produced, but the softening point at the time of reaction for 48 hours was 65 ° C., and the synthesis was stopped because the desired softening point (110 ° C.) was not reached.

Comparative Example 5
[Synthesis of Linear Polyester B′-7]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 468 parts (10.0 moles) of terephthalic acid diethylene glycol ester, 353 parts (5.5 moles) of bisphenol A · PO2 mole adduct, bisphenol A · PO3 408 parts (5.5 moles) of a mole adduct and 3 parts of tetraisopropoxide titanate were charged as a condensation catalyst, and the temperature was raised to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was conducted while distilling off ethylene glycol under a reduced pressure of 5 to 20 mmHg. The reaction was followed while measuring the softening point of the polymer to be produced, but the softening point after the reaction for 48 hours was 65 ° C., and the synthesis was stopped because the desired softening point (110 ° C.) was not reached. .

Comparative Example 6
[Synthesis of Linear Polyester B′-8]
Addition of 290 parts (10.0 mol) of terephthalic acid, 359 parts (5.9 mol) of bisphenol A · PO2 mol adduct, 3 mol of bisphenol A · PO in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube 414 parts (5.9 moles) of the product and 3 parts of dibutyltin oxide as a condensation catalyst were allowed to react at 230 ° C. for 6 hours while distilling off the water produced under a nitrogen stream. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, the reaction was followed while measuring the softening point of the polymer to be produced, taken out when the softening point reached 96 ° C., cooled to room temperature, pulverized and granulated. This is designated as linear polyester (B′-8). The time required to reach the softening point of B′-8 was 10 hours.
The linear polyester (B′-8) had a Tg of 58 ° C., an Mp of 7000, an Mw of 8000, a THF-insoluble content of 0%, and a tin content of 1000 ppm.
[Synthesis of Nonlinear Polyester C′-8]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 206 parts (9.0 moles) of terephthalic acid, 16 parts (1.0 moles) of fumaric acid, 694 parts of adducts of bisphenol A and PO3 moles (12 parts) 0.5 mol), 56 parts (0.5 mol) of phenol novolak EO adduct and 3 parts of dibutyltin oxide as a condensation catalyst were allowed to react at 230 ° C. for 6 hours while distilling off the produced water under a nitrogen stream. It was. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and the reaction was followed while measuring the softening point of the produced polymer. Next, 77 parts (1.2 mol) of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. under reduced pressure of 5 to 20 mmHg, and taken out when the softening point reached 160 ° C. After cooling to room temperature, it was pulverized into particles. This is designated as nonlinear polyester (C′8). The time required to reach the softening point of C′-9 was 12 hours.
The nonlinear polyester (C′8) had a Tg of 58 ° C., an Mp of 6000, a THF-insoluble content of 30%, and a tin content of 1000 ppm.
[Creation of polyester resin for toner]
600 parts of linear polyester (B′8) and 400 parts of nonlinear polyester (C′8) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a polyester resin for toner (D′ 4).

Comparative Example 7
[Synthesis of linear polyester B'9]
Addition of 290 parts (10.0 mol) of terephthalic acid, 359 parts (5.9 mol) of bisphenol A · PO2 mol adduct, 3 mol of bisphenol A · PO in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube 414 parts (5.9 moles) of the product and 3 parts of tetraisopropoxide titanate as a condensation catalyst were added and reacted at 230 ° C. under a nitrogen stream for 6 hours while distilling off the generated water. Next, the reaction was followed while measuring the softening point of the polymer produced under a reduced pressure of 5 to 20 mmHg. The softening point reached only 65 ° C. even when the reaction was performed for 48 hours. The synthesis was stopped because the desired softening point (85 ° C.) was not reached.
[Synthesis of Nonlinear Polyester C′-9]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 206 parts (9.0 moles) of terephthalic acid, 16 parts (1.0 moles) of fumaric acid, 694 parts of adducts of bisphenol A and PO3 moles (12 parts) 0.5 mol), 56 parts (0.5 mol) of phenol novolak EO adduct and 3 parts of tetraisopropoxide titanate as a condensation catalyst, while distilling off the water produced at 230 ° C. in a nitrogen stream The reaction was performed for 6 hours. Subsequently, the reaction was conducted under a reduced pressure of 5 to 20 mmHg, and the reaction was followed while measuring the softening point of the produced polymer. When the reaction was performed for 48 hours, the softening point reached only 65 ° C. The synthesis was stopped because the desired softening point (85 ° C.) was not reached.

Example [1] / Comparative Example [1]
To 100 parts of each of the polyester resin B1 of the present invention and the comparative polyester resin B′3, 8 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 5 parts of carnauba wax were added to form toner.
First, after pre-mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.] 8 μm toner particles were obtained. Next, 100 parts of the toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and the toner composition (1) of the present invention and the comparative toner composition (2). Got.
The evaluation results evaluated by the following evaluation methods are shown in Table 1.

Example [2] / Comparative Example [2]
For each 100 parts of the polyester resin D2 of the present invention and the comparative polyester resin D′ 4, 8 parts of carbon black MA-100 [Mitsubishi Chemical Corporation], 5 parts of carnauba wax, charge control agent T-77 [retained] 1 part of Tsuchiya Chemical Co., Ltd.] was added to make a toner by the following method.
First, after pre-mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.] 8 μm toner particles were obtained. Next, 100 parts of the toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and the toner composition (3) of the present invention and the comparative toner composition (4). Got.
Table 2 shows the evaluation results evaluated by the following evaluation methods.

[Evaluation methods]
[1] Minimum fixing temperature (MFT)
An unfixed image developed using a commercial copying machine (AR5030; manufactured by Sharp) was evaluated using a fixing machine of a commercial copying machine (AR5030; manufactured by Sharp). The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was set as the minimum fixing temperature.
[2] Hot offset generation temperature (HOT)
The fixing was evaluated in the same manner as the MFT, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.
[3] Gloss development temperature (Gross)
In the same manner as the MFT, the developed unfixed image was subjected to fixing evaluation using a fixing device of a commercially available color printer (LBP2160; manufactured by Canon). The fixing roll temperature at which the 60 ° gloss of the fixed image was 10% or more was defined as the gloss development temperature.

  If the manufacturing method of the polyester of this invention is used, polyester can be synthesize | combined, without using the tin compound which may cause an environmental problem. Further, even if the synthesized resin is used for toner, particularly for color toner, it has the same performance as a resin synthesized using a conventional tin catalyst.

Claims (9)

In a process for producing a polyester resin in which a polyol component and a polycarboxylic acid component are polycondensed, 1,2-propylene glycol ester of polycarboxylic acid is used as at least part of the polycarboxylic acid component, and 1,2-propylene glycol is eliminated. A process for producing a polyester resin, characterized in that The process for producing a polyester resin according to claim 1, wherein the polycondensation is carried out in the presence of a titanium-containing catalyst. The method for producing a polyester resin according to claim 1 or 2, wherein the polyol component comprises a propylene oxide adduct of 10 to 100 mol% of bisphenol A. The method for producing a polyester resin according to any one of claims 1 to 3, wherein the polycarboxylic acid constituting the 1,2-propylene glycol ester of the polycarboxylic acid comprises 60 mol% or more of an aromatic polycarboxylic acid. A polyester resin obtained by the production method according to claim 1 and having a number average molecular weight of 1,000 to 20,000. A polyester resin comprising a polyol constituent unit and a polycarboxylic acid constituent unit, wherein the polyol constituent unit contains 10 to 100 mol% of a propylene oxide adduct unit of bisphenol A, and the polycarboxylic acid constituent unit contains an aromatic polymer. A polyester resin containing 60 mol% or more of carboxylic acid units and a tin content of 10 ppm or less. The polyester resin according to claim 5 or 6, which is used for a toner binder resin. A toner composition comprising the polyester resin according to claim 7, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent. The toner composition according to claim 8, which is for a color toner.