JP5497850B2 - Polyester resin - Google Patents

Description

  The present invention relates to a polycondensation resin used for various applications such as films, sheets, fibers, toner materials for electrophotography and the like, and a method for producing the same.

  Polycondensation resins such as polyester and polyamide are used in various applications such as films, sheets, and fibers by utilizing their chemical and physical properties. Depending on the use of the resulting resin, polycondensation reaction Various types of promoters that promote the catalyst and promoters that enhance the activity of the catalyst have been studied.

  For example, as a catalyst used in the production of a polycondensation resin used for a toner binder resin, a tin compound such as dibutyltin oxide is considered in consideration of not only catalytic activity but also influence on toner performance such as charging property. However, in recent years, from the viewpoint of safety and the like, there is a tendency that a titanium compound is preferably used as a catalyst rather than a tin compound having a Sn—C bond such as dibutyltin oxide (see Patent Document 1). .

JP 2003-201342 A

  However, when a specific titanium compound is used as a catalyst, there is a problem that the reaction time becomes extremely long and the resin is colored. Further, when a resin obtained by using a titanium compound described later is used as a binder resin for a toner, there is a problem that the image quality is deteriorated.

  An object of the present invention is a polycondensation resin obtained by using a co-catalyst for polycondensation reaction that enhances the catalytic activity of the titanium compound and is effective for shortening the reaction time. An object of the present invention is to provide a polycondensation resin having a charging property that prevents fogging even when used as a resin, and a method for producing the same.

The present invention
[1] Formula (A):
Ti (Z) ₄ (A)
(Z is an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or an optionally substituted carbon. (It is an acyloxy group of the number 2 to 28)
A polycondensation resin obtained by polycondensing a raw material monomer in the presence of a pyrogallol compound having a benzene ring in which three hydrogen atoms adjacent to each other and substituted with a hydroxyl group are represented by: The amount of the titanium compound represented by the formula (A) is 0.01 to 2.0 parts by weight, and the amount of the pyrogallol compound is 0.001 to 1.0 parts by weight with respect to 100 parts by weight of the raw material monomer of the condensation polymerization resin. A polycondensation resin in which the weight ratio of the pyrogallol compound to the titanium compound represented by the formula (A) (pyrogallol compound / titanium compound) is 0.01 to 0.5, and [2] Formula (A):
Ti (Z) ₄ (A)
(Z is an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or an optionally substituted carbon. (It is an acyloxy group of the number 2 to 28)
In the presence of a pyrogallol compound having a benzene ring in which three hydrogen atoms adjacent to each other and a hydroxyl group are substituted with each other, a raw material monomer is subjected to polycondensation polymerization in the presence of the titanium compound represented by The amount of the titanium compound represented by the formula (A) is 0.01 to 2.0 parts by weight and the amount of the pyrogallol compound is 0.001 to 1.0 parts by weight with respect to 100 parts by weight of the raw material monomer of the condensation polymerization resin. The weight ratio of the pyrogallol compound to the titanium compound represented by the formula (A) (pyrogallol compound / titanium compound) is 0.01 to 0.5, and the titanium compound represented by the formula (A) and the pyrogallol compound are reduced. The present invention relates to a method for producing a condensation polymerization resin, which is added to a reaction system before the start of a polymerization reaction.

  The polycondensation resin of the present invention is a resin in which the catalytic activity of the titanium compound is enhanced by the combined use of a specific titanium compound and a pyrogallol compound, and the reaction time is shortened. Even when used as a binder resin, high-quality images are maintained and fogging is prevented.

  The polycondensation resin of the present invention is obtained by polycondensing a raw material monomer in the presence of a specific titanium compound and a pyrogallol compound having a benzene ring in which three hydrogen atoms adjacent to each other are substituted with a hydroxyl group. The titanium compound described below is not as high in catalytic activity as conventionally used dibutyltin oxide and has a long reaction time, but is excellent in sustainability and is capable of resin synthesis. Therefore, the resin tends to be colored or turbid due to the decomposition of the monomer component due to an extremely long reaction time. When an image is formed with a toner obtained using such a colored resin, the image quality (color) is inferior, and is particularly noticeable with yellow toner that is easily affected by the color of the resin. However, when a condensation polymerization resin obtained using a titanium compound described later is used as a binder resin for a toner, there is a problem that fog is likely to occur, but by coexisting with the pyrogallol compound, a low molecular weight component or An increase in volatile organic components can also be prevented. In addition, a condensation polymerization resin having a small heat history can be obtained as the reaction time is shortened. Although the reason is unknown, it is presumed that the coexistence of the pyrogallol compound suppresses a decrease in the catalytic activity of the titanium compound and maintains a high catalytic activity.

  Examples of the pyrogallol compound include pyrogallol, gallic acid, gallic ester, benzophenone derivatives such as 2,3,4-trihydroxybenzophenone, 2,2 ′, 3,4-tetrahydroxybenzophenone, epigallocatechin, and epigallocatechin gallate. Among these, from the viewpoint of the transparency of the obtained resin, among them, the formula (I):

Wherein R ^{1 to} R ³ each independently represent a hydrogen atom or —COOR ⁴ (R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group or an alkenyl group). )
The compound represented by these is preferable. In the formula, the hydrocarbon group of R ⁴ preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms from the viewpoint of reaction activity. Among the compounds represented by the formula (I), a compound in which R ¹ and R ³ are hydrogen atoms and R ² is a hydrogen atom or —COOR ⁴ is more preferable. Specific examples include pyrogallol (R ^{1 to} R ³ : hydrogen atom), gallic acid (R ¹ and R ³ : hydrogen atom, R ² : —COOH), ethyl gallate (R ¹ and R ³ : hydrogen atom, R ² : —COOC ₂ H ₅ ), propyl gallate (R ¹ and R ³ : hydrogen atom, R ² : —COOC ₃ H ₇ ), butyl gallate (R ¹ and R ³ : hydrogen atom, R ² : —COOC) ₄ H ₉ ), octyl gallate (R ¹ and R ³ : hydrogen atom, R ² : —COOC ₈ H ₁₇ ), lauryl gallate (R ¹ and R ³ : hydrogen atom, R ² : —COOC ₁₂ H ₂₅ ) From the viewpoint of resin transparency, gallic acid and gallic acid ester are preferred.

A titanium compound used as a catalyst for polycondensation reaction together with the pyrogallol compound has the formula (A):
Ti (Z) ₄ (A)
(In the formula, Z has an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or a substituent. It is also an acyloxy group having 2 to 28 carbon atoms)
From the viewpoint of colorability and fogging, Z is preferably an alkoxy group having 2 to 28 carbon atoms which may have a substituent.

  In the formula (A), the number of carbon atoms of the group represented by Z is preferably 8 to 22 and more preferably 16 to 20 from the viewpoints of colorability and fog.

  Further, the groups represented by Z may be the same or different, but from the viewpoint of reaction activity and hydrolysis resistance, it is preferable that all four types are the same group.

  In the formula (A), the group represented by Z may have a substituent such as a hydroxyl group or a halogen, but is preferably unsubstituted or substituted with a hydroxyl group as a substituent. More preferred.

Specific examples of the titanium compound represented by the formula (A) include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetra Stearyl titanate [Ti (C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxy octyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like.

  Typical examples of the condensation polymerization reaction include a polyester unit having an ester bond (-COO-) by dehydration condensation of a carboxyl group and a hydroxyl group, and an amide bond (-CONH-) by dehydration condensation of a carboxyl group and an amino group. The reaction of forming a polycondensation resin unit such as a polyamide unit and a polyester polyamide unit having both an ester bond and an amide bond can be mentioned, and in the formation of a polycondensation resin unit having an ester bond, the effect of the present invention is more effective. Prominently demonstrated. In the present invention, not only the reaction between different raw material monomers, but also the reaction of producing polylactic acid by dehydration condensation from a monomer having different functional groups in one molecule, for example, lactic acid having a hydroxyl group and a carboxyl group. Included in the polymerization reaction.

  As the raw material monomer for the polyester unit, an alcohol component and a carboxylic acid component are usually used.

  Examples of the alcohol component include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, which are represented by the formula (II):

Wherein R ⁵ O is an alkyleneoxy group, R ⁵ is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average number of moles of alkylene oxide added, and the sum of x and y Is 1 to 16, preferably 1.5 to 5)
Aromatic diols such as alkylene oxide adducts of bisphenol represented by: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Aliphatic diols such as hexanediol, 1,4-butenediol, 1,3-butanediol and neopentyl glycol, and trihydric or higher polyhydric alcohols such as glycerin.

  Examples of carboxylic acid components include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc. Aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; And anhydrides of these acids, alkyl (1 to 3 carbon atoms) esters; rosins; rosins modified with fumaric acid, maleic acid, acrylic acid, and the like. Such acids, anhydrides of these acids, and alkyl esters of these acids are collectively referred to herein as carboxylic acid compounds. In the present invention, an aromatic dicarboxylic acid compound is preferred from the viewpoint of chargeability. 70 mol% or more is preferable in a carboxylic acid component, and, as for content of an aromatic dicarboxylic acid compound, 90 mol% or more is more preferable.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoints of molecular weight adjustment and offset resistance improvement.

  Furthermore, examples of the raw material monomer for forming an amide bond in the polyester polyamide unit and the polyamide unit include various known polyamines, aminocarboxylic acids, aminoalcohols, etc., preferably hexamethylenediamine and ε-caprolactam.

  The above raw material monomers also include those normally classified as ring-opening polymerization monomers, but these are hydrolyzed by condensation due to the presence of water or the like produced by the condensation polymerization reaction of other monomers. Therefore, it is considered to be included in the raw material monomer of the condensation polymerization resin in a broad sense.

  The abundance of the pyrogallol compound in the condensation polymerization reaction is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, and 0.02 to 0.3 part by weight with respect to 100 parts by weight of the raw material monomer subjected to the condensation polymerization reaction. Is more preferable. Here, the abundance of the pyrogallol compound means the total amount of the pyrogallol compound subjected to the condensation polymerization reaction.

  On the other hand, the existing amount of the titanium compound represented by the formula (A) is preferably 0.01 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the raw material monomer subjected to the condensation polymerization reaction. 0.2 to 1.0 part by weight is more preferable. Here, the abundance of the titanium compound represented by the formula (A) means the total amount of the titanium compound represented by the formula (A) subjected to the condensation polymerization reaction.

  The weight ratio of the pyrogallol compound to the titanium compound represented by formula (A) (pyrogallol compound / titanium compound) is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and even more preferably 0.05 to 0.2.

  The condensation polymerization reaction is preferably performed at a temperature of 180 to 250 ° C. in an inert gas atmosphere in the presence of the titanium compound and the pyrogallol compound represented by the formula (A). The titanium compound and pyrogallol compound represented by the formula (A) may be mixed and added to the reaction system, or may be added separately. Moreover, you may mix and add with a carboxylic acid component and an alcohol component. The timing of adding the titanium compound and pyrogallol compound represented by the formula (A) to the reaction system may be either before the start of the reaction or during the reaction, but a higher effect is obtained for the promotion of the polycondensation reaction. From this point of view, the time is preferably before the reaction temperature is reached, and more preferably before the start of the reaction. In the present invention, “before starting the reaction” means a state in which water accompanying the condensation polymerization reaction is not generated.

  In the present invention, the polycondensation resin refers to a resin containing a polycondensation resin unit, not only a resin comprising a polycondensation resin unit such as polyester, polyester polyamide, and polyamide obtained by the polycondensation reaction, A hybrid resin having two or more kinds of resin components including a condensation polymerization resin unit, for example, a hybrid resin in which a condensation polymerization resin unit and an addition polymerization resin unit are partially chemically bonded is also included.

  Further, the condensation polymerization resin may be modified to such an extent that the properties are not substantially impaired. For example, the modified polyester may be grafted or blocked with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, etc. Polyester.

  The condensation polymerization resin of the present invention can be suitably used as a binder resin for an electrophotographic toner.

  The softening point of the binder resin is preferably 90 to 160 ° C., more preferably 95 to 155 ° C., and further preferably 98 to 150 ° C. from the viewpoints of toner fixability, storage stability and durability. From the same viewpoint, the glass transition point is preferably 45 to 85 ° C, more preferably 50 to 80 ° C. From the viewpoint of chargeability and environmental stability, the acid value is preferably 1 to 90 mgKOH / g, more preferably 5 to 90 mgKOH / g, further preferably 5 to 88 mgKOH / g, and the hydroxyl value is 1 to 80 mgKOH / g. Preferably, 8 to 60 mgKOH / g is more preferable, and 8 to 55 mgKOH / g is more preferable.

  To the electrophotographic toner containing the condensation polymerization resin of the present invention, a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, Although other resins such as polyurethane may be used in combination, the content of the condensation polymerization resin of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, and 90% by weight in the binder resin. The above is more preferable, and it is more preferable that it is substantially 100% by weight.

  The toner further includes a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, Additives such as a cleaning property improving agent may be appropriately contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  The toner for electrophotography may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, a raw material such as a binder resin, a colorant, and a charge control agent is uniformly mixed with a mixer such as a Henschel mixer, and then a hermetically sealed kneader, a single or twin screw extruder It can be produced by melt-kneading with an open roll kneader or the like, cooling, pulverizing and classifying. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable. An external additive such as hydrophobic silica may be added to the surface of the toner.

The volume median particle size (D ₅₀ ) of the toner is preferably 3 to 15 μm, more preferably 3 to 10 μm. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  The obtained toner can be used as a one-component developing toner or as a two-component developer by mixing with a carrier.

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a 1.96 MPa load is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Melting point of wax]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The maximum peak temperature of heat of fusion is taken as the melting point.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D _50).

Examples 1 to 18, Comparative Examples 1 to 7 and Reference Examples 1 and 2
(Resin production example 1)
Polyoxypropylene (2.1) -2,2-bis (4-hydroxyphenyl) propane (BPA-PO) 3318 g (50 mol), polyoxyethylene (2.1) -2,2-bis (4-hydroxyphenyl) propane ( BPA-EO) 3024g (50 moles), terephthalic acid 2988g (90 moles per 100 moles of total BPA-PO and BPA-EO), catalyst and co-catalyst shown in Table 1 with nitrogen inlet tube, dehydration tube, stirring In a 10-liter four-necked flask equipped with a vacuum vessel and a thermocouple, and the reaction rate (the amount of reaction water produced (mol) / theoretical product water amount (mol) × 100) reaches 93% at 235 ° C. in a nitrogen atmosphere And further reacted at 8 kPa until the softening point reached 100 ° C. to obtain a polyester.

(Toner Production Example 1)
100 parts by weight of the polyester obtained in Resin Production Example 1, 4 parts by weight of yellow pigment “Pariotol Yellow D1155” (CI Pigment Yellow 185, manufactured by BASF), 1 part by weight of negatively chargeable charge control agent “Bontron E-84” Parts (manufactured by Orient Chemical Industry Co., Ltd.) and 3 parts by weight of carnauba wax “carnauba wax C1” (manufactured by Kato Yoko Co., Ltd., melting point: 83 ° C.) were thoroughly mixed with a Henschel mixer, Using a co-rotating twin screw extruder having a barrel inner diameter of 43 mm, melt kneading was performed at a roll rotation speed of 200 r / min and a heating temperature of 80 ° C. in the roll. The feed rate of the mixture was 20 kg / hr and the average residence time was about 18 seconds. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain a powder having a volume median particle size (D ₅₀ ) of 8.0 μm.

  To 100 parts by weight of the obtained powder, 1 part by weight of hydrophobic silica “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) as an external additive was added and mixed with a Henschel mixer to obtain a toner. . The obtained toner is classified into A to F according to the type of the catalyst and the cocatalyst, and Table 1 shows the physical properties together with the properties.

Test example 1
Toner was mounted on a non-magnetic one-component developing device “Oki Microline 5400” (Oki Data Co., Ltd.), and 50 diagonal stripe patterns with a printing rate of 5.5% were printed. After printing, a solid image having a size of 5 cm × 5 cm and an image density of 1.3 was printed, and the L ^* value, a ^* value, and b ^* value were measured using a color difference meter “CR-321” (manufactured by Konica Minolta). ΔE was calculated from the following formula using the L ^* value, a ^* value, and b ^* value of a solid image obtained by performing the same printing test using the toner of Reference Example 2, and evaluated as colorability. . The results are shown in Table 1.

(In the formula, L ₁ ^* , a ₁ ^* and b ₁ ^* represent the measured values, and L ₂ ^* , a ₂ ^* and b ₂ ^* represent the measured values of the toner of Reference Example 2, respectively.)

Test example 2
Toner was mounted on a non-magnetic one-component developing device “Oki Microline 5400” (Oki Data Co., Ltd.), and 50 diagonal stripe patterns with a printing rate of 5.5% were printed. After printing, a white solid image (printing rate 0%) was printed, and average values of L ^* values, a ^* values, and b ^* values were calculated for any four points in the same manner as in Test Example 1. Using the L ^* value, a ^* value, and b ^* value of blank paper as the standard, ΔE was calculated in the same manner as in Test Example 1 and evaluated as fog. The results are shown in Table 1.

Example 19 and Comparative Example 8
(Resin production example 2)
4,500g of 1,4-butanediol, 5800g of fumaric acid (100 moles per 100 moles of 1,4-butanediol), catalyst and promoter shown in Table 2, with nitrogen inlet tube, dehydration tube, stirrer and thermocouple Place in a equipped 10-liter four-necked flask and react at 190 ° C in a nitrogen atmosphere until the reaction rate (the amount of reaction water produced (mol) / theoretical product water (mol) x 100) reaches 93%. A polyester was obtained. The results are shown in Table 2. The abbreviations for catalyst, promoter and classification are the same as in Table 1.

(Toner Production Example 2)
In Toner Production Example 1, a toner was produced in the same manner as described above except that 100 parts by weight of the polyester obtained in Resin Production Example 2 was used instead of 100 parts by weight of the polyester resin obtained in Resin Production Example 1. Sex and fog were evaluated. The results are shown in Table 2.

  From the above results, it can be seen that, in the polycondensation reaction, the use of a pyrogallol compound as a co-catalyst with the catalyst increases the catalytic activity and promotes the reaction from the result of the reaction time. That is, in Examples 1 to 19, the reaction time required to advance the reaction to the same extent is significantly shortened as compared with the comparative examples in the classified group. In addition, it can be seen that the resins obtained in the examples have a low degree of coloring and are effective in preventing fogging as a binder resin for toner.

  The polycondensation resin of the present invention is used in various applications such as films, sheets, fibers, and toner materials for electrophotography.

The following are mentioned as an aspect of this invention.
1. Formula (A):
Ti (Z) ₄ (A)
(Z is an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or an optionally substituted carbon. (It is an acyloxy group of the number 2 to 28)
A polycondensation resin obtained by polycondensing a raw material monomer in the presence of a pyrogallol compound having a benzene ring in which three hydrogen atoms adjacent to each other are substituted with a hydroxyl group.
2. The pyrogallol compound has the formula (I)
The condensation polymerization resin according to [1], represented by
3. The amount of the titanium compound represented by the formula (A) is 0.01 to 2.0 parts by weight and the amount of the pyrogallol compound is 0.001 to 1.0 parts by weight with respect to 100 parts by weight of the raw material monomer of the condensation polymerization resin. 1] or the condensation polymerization resin according to [2].
4). The condensation polymerization resin according to any one of [1] to [3] above, wherein the weight ratio of the pyrogallol compound to the titanium compound represented by the formula (A) (pyrogallol compound / titanium compound) is 0.01 to 0.5.
5. In the formula (A), the polycondensation resin according to any one of [1] to [4], wherein all Zs are the same group.
6). Formula (A):
Ti (Z) ₄ (A)
(Z is an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or an optionally substituted carbon. (It is an acyloxy group of the number 2 to 28)
In the presence of a pyrogallol compound having a benzene ring in which three hydrogen atoms adjacent to each other and a hydroxyl group are substituted with each other, a raw material monomer is subjected to polycondensation polymerization in the presence of the titanium compound represented by A method for producing a condensation polymerization resin, comprising adding the titanium compound represented by the formula (A) and the pyrogallol compound to a reaction system before the start of the condensation polymerization reaction.

Claims (4)

Formula (A):
Ti (Z) ₄ (A)
(Z is an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or an optionally substituted carbon. (It is an acyloxy group of the number 2 to 28)
A titanium compound represented in, a three presence of pyrogallol compound wherein the hydrogen atoms having a benzene ring substituted by a hydroxyl group, a polyester resin obtained by the raw material monomers by polycondensing the adjacent, the polyester The amount of the titanium compound represented by the formula (A) is 0.01 to 2.0 parts by weight, the amount of the pyrogallol compound is 0.001 to 1.0 parts by weight with respect to 100 parts by weight of the raw material monomer of the resin, and the pyrogallol compound A polyester resin in which the weight ratio of the titanium compound represented by formula (A) (pyrogallol compound / titanium compound) is 0.01 to 0.5. The pyrogallol compound has the formula (I):

(Wherein R ^{1 to} R ³ each independently represent a hydrogen atom or —COOR ⁴ (R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms))
The polyester resin of Claim 1 represented by these. The polyester resin according to claim 1 or 2, wherein in formula (A), all Zs are the same group. Formula (A):
Ti (Z) ₄ (A)
(Z is an optionally substituted alkoxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or an optionally substituted carbon. (It is an acyloxy group of the number 2 to 28)
A titanium compound represented in the presence of the pyrogallol compound is three hydrogen atoms adjacent to each other with a benzene ring substituted by a hydroxyl group, a raw material monomer to condensation polymerization, a process for making a polyester resin, wherein The amount of the titanium compound represented by the formula (A) is 0.01 to 2.0 parts by weight, the amount of the pyrogallol compound is 0.001 to 1.0 parts by weight with respect to 100 parts by weight of the raw material monomer of the polyester resin, and the pyrogallol The weight ratio of the compound and the titanium compound represented by the formula (A) (pyrogallol compound / titanium compound) is 0.01 to 0.5, and the polycondensation reaction of the titanium compound represented by the formula (A) and the pyrogallol compound is started. A method for producing a polyester resin, which is added to the reaction system before.