JP5584106B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to a binder resin for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner containing the binder resin.

  Patent Document 1 discloses a toner that is granulated in an aqueous medium with the object of providing a toner that has excellent smearing properties, good low-temperature fixability, and a high-quality image. A first resin that is a polyester-based resin, and a second resin that is present outside the first resin and has a glass transition temperature (° C.) higher than the glass transition temperature (° C.) of the first resin. And a crystalline polyester resin, and a resin using adipic acid as the first resin is described.

  Patent Document 2 contains at least a crystalline polyester resin and a colorant for the purpose of obtaining a high-density image while maintaining low-temperature fixability even under high-temperature and high-humidity conditions, and suppressing fogging, An electrostatic charge developing toner having a dielectric loss ratio ε ″ at 30 ° C. and 90% RH of 0.1 Hz and 500 V of 0.1 or less, wherein the aliphatic polyester has 8 to 12 carbon atoms as crystalline polyester A resin using a carboxylic acid component containing a dicarboxylic acid compound is described.

JP 2010-170151 A JP 2009-75342 A

  An object of the present invention is to provide a binder resin for toner and an electrophotographic toner containing the binder resin, which are excellent in low-temperature fixability of toner, storage stability of printed matter, and curling of printed matter. is there.

The present invention
[1] An amorphous substance having a number average molecular weight of 1000 to 2400, obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing 5 to 25 mol of an adipic acid compound with respect to 100 mol of the alcohol component Polyester and an alcohol component containing 70 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms are subjected to polycondensation. In addition, the present invention relates to a toner binder resin comprising the crystalline polyester obtained as described above, and [2] an electrophotographic toner comprising the toner binder resin described in [1].

  The electrophotographic toner containing the binder resin of the present invention exhibits excellent effects in low-temperature fixability of the toner, storage stability of the printed matter, and suppression of curling of the printed matter.

  Crystalline polyester obtained by condensation polymerization of an alcohol component containing 70 to 100 mol% of an aliphatic diol having 2 to 12 carbon atoms and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms Since the melting point is low, the printed materials are easily fused together, and the storability of the printed materials is low. Moreover, it does not show excellent low-temperature fixability as expected.

  This is because the crystalline polyester has a low affinity with the amorphous polyester, the crystalline polyester re-aggregates after melt-kneading the crystalline polyester and the amorphous polyester, and the crystalline polyester has a crystal grain size. This is probably due to the fact that

  Therefore, the present inventors are an amorphous polyester obtained by polycondensing an alcohol component and a carboxylic acid component containing 5 to 25 mol of an adipic acid compound with respect to 100 mol of the alcohol component, It has been found that by using a low molecular weight amorphous polyester having a number average molecular weight of 1000 to 2400 in combination with the crystalline polyester, the storability of the printed matter can be improved and curling of the printed matter can be suppressed.

  The use of a low molecular weight amorphous polyester can improve the dispersibility of the crystalline polyester, but at the same time inhibits the crystallinity of the crystalline polyester. If the crystalline polyester is not sufficiently crystallized, the glass transition point of the amorphous polyester is lowered, and the storage stability of the printed matter is lowered. In particular, since the crystalline polyester has a low melting point, the storability of the printed matter is remarkably lowered.

  In contrast, by using a certain amount of adipic acid for the carboxylic acid component of the amorphous polyester, the printed matter can be stored even at the temperature above the glass transition point of the amorphous polyester, even if the crystalline polyester is used. Became possible. This is presumed to be because the decrease in the glass transition point of the amorphous polyester was suppressed because the crystallization of the crystalline polyester was promoted with the adipic acid site finely dispersed in the amorphous polyester as the nucleus. Is done.

  Furthermore, the use of the amorphous polyester according to the present invention can suppress the curling of the printed matter. In general, when the amount of water in the paper is large, curling tends to curl when the water in the paper evaporates in the toner fixing process. Further, curling is more likely to occur when the volume becomes smaller after fixing in a solidified state after fixing than when fixing in a state where the toner is in a molten state. Crystalline polyester generally has a large volume change in the above two states, and thus easily causes curling. However, the toner using the binder resin of the present invention generates little curling. This is presumably due to the fact that the crystalline polyester crystals produced after printing and fixing are very small and finely dispersed.

  The binder resin of the present invention contains a crystalline polyester and an amorphous polyester each obtained by using a specific raw material monomer.

  Here, the crystallinity of a resin such as polyester is the crystallinity defined by the ratio of the softening point to the highest endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the “softening point / the highest endothermic peak temperature”. Expressed by an index. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, “crystalline polyester” means a polyester having a crystallinity index of 0.6 to 1.4, preferably 0.9 to 1.2, more preferably 1.0 to 1.2, and “amorphous polyester” means a crystallinity index. Refers to polyesters with a value greater than 1.4 or less than 0.6.

  The “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the conditions of the measurement methods described in the examples. If the maximum peak temperature is within 20 ° C of the softening point, the maximum peak temperature is the melting point of the crystalline resin (crystalline polyester), and the peak with a difference of more than 20 ° C from the softening point is amorphous polyester glass. The peak is attributed to the transition.

  The crystallinity of the resin can be adjusted by the types and ratios of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

  The carboxylic acid component of the amorphous polyester contains an adipic acid compound from the viewpoint of low-temperature fixability of the toner, storage stability of the printed matter, and curling of the printed matter.

  In the present invention, carboxylic acids, acid anhydrides thereof, derivatives thereof such as alkyl (C1-3) esters, and the like are collectively referred to as carboxylic acid compounds. Further, when the carboxylic acid compound is an alkyl ester, the carbon number described as the carbon number of the carboxylic acid compound does not include the carbon number of the alkyl group of the alkyl ester. Therefore, in the case of an adipic acid compound, adipic acid and its alkyl ester are included.

  The content of the adipic acid compound is 5 to 25 mol, preferably 7 to 23 mol with respect to 100 mol of the alcohol component, from the viewpoint of low-temperature fixability of the toner, storage stability of the printed matter and curling of the printed matter. 10 to 20 mol is more preferable. If the content of the adipic acid compound is less than 5 moles with respect to 100 moles of the alcohol component, the storability of the printed matter is lowered. This is presumably because the crystallization of the crystalline polyester is hardly promoted. Further, even if the content of the adipic acid compound exceeds 25 mol, the storability of the printed matter is lowered, but this is presumed that the crystallinity is lowered because the crystal becomes too small.

  In addition, the content of the adipic acid compound in the carboxylic acid component is preferably 6 to 30 mol%, and preferably 9 to 28 mol%, from the viewpoint of low-temperature fixability of the toner, storage stability of the printed matter, and curling of the printed matter. More preferably, 10-20 mol% is further more preferable.

  In addition to the adipic acid compound, the carboxylic acid component may contain a dicarboxylic acid compound or a trivalent or higher polyvalent carboxylic acid compound.

  Dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, sebacic acid, azelaic acid and other aliphatic dicarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid Aromatic dicarboxylic acids such as cycloaliphatic dicarboxylic acids; and anhydrides of these acids, alkyl (C1-3) esters, and the like.

  The carboxylic acid component preferably contains an aromatic dicarboxylic acid compound from the viewpoint of improving the chargeability of the toner. In the carboxylic acid component, the content of the aromatic dicarboxylic acid compound is preferably 30 to 90 mol%, more preferably 40 to 90 mol%, and still more preferably 50 to 50 mol%, from the viewpoint of low-temperature fixability and chargeability improvement of the toner. 85 mol%.

  Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and other aromatic carboxylic acids, and these Derivatives such as acid anhydrides and alkyl (C1-3) esters are exemplified.

  Other carboxylic acid compounds include rosin modified with rosin, fumaric acid, maleic acid, acrylic acid, and the like.

  In the present invention, the carboxylic acid component is a trivalent or higher polyvalent carboxylic acid compound, preferably a trimellitic acid compound, more preferably from the viewpoint of adjusting the molecular weight of the resin and enhancing the carrier contamination resistance and storage stability of the toner. It preferably contains trimellitic anhydride. The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol%, and still more preferably 5 to 25 mol% in the carboxylic acid component.

  The alcohol component of amorphous polyester is a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, 2 from the viewpoint of low-temperature fixability of toner, storage stability of printed matter, and curling of printed matter. An aromatic diol such as an alkylene oxide adduct of bisphenol A represented by the following formula (I) including a polyoxyethylene adduct of 2-bis (4-hydroxyphenyl) propane, etc. is preferable, 100 mol% is preferable, 80-100 mol% is more preferable, 90-100 mol% is still more preferable.

(In the formula, R ¹ O and OR ¹ are oxyalkylene groups, R ¹ is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, and each is a positive number; The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)

  The polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and the polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane are used together from the viewpoint of storage stability of printed matter. The molar ratio (polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane / polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane) is preferably 50/50. ˜10 / 90 is preferable, and 40/6 to 10/90 is more preferable.

  Examples of other alcohol components include aliphatic diols having 2 to 12 carbon atoms; trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

  Examples of the aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, neopentyl glycol, 2,3-pentanediol, 2,4-pentanediol and the like. Among these, at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,3-butanediol, and neopentylglycol from the viewpoint of low-temperature fixability of the toner. Is preferred.

  The content of the aliphatic diol having 2 to 12 carbon atoms is preferably 0 to 70 mol%, more preferably 0 to 50 mol%, and more preferably 0 to 30 mol% in the alcohol component from the viewpoint of low-temperature fixability of the toner. Further preferred.

  A monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight of the resin.

  The molar ratio of the alcohol component and the carboxylic acid component (carboxylic acid component / alcohol component), which is the raw material monomer of the amorphous polyester, is preferably 0.70 to 1.10 from the viewpoint of storage stability of the printed matter and curling of the printed matter. More preferably, it is 0.70-1.00, More preferably, it is 0.73-0.90.

  In the present invention, the above amorphous polyester includes not only polyester but also modified resins thereof.

  Examples of the modified resin include urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and a hybrid resin having two or more kinds of resin components including a polyester component. .

  A hybrid resin having a polyester component and a vinyl resin component is prepared by a method of melt-kneading each resin in the presence of an initiator or the like, a method of dissolving and mixing each resin in a solvent, It may be produced by any method such as a method of polymerizing the raw material monomer mixture. Preferably, it is a resin obtained by the method of performing a polycondensation reaction and an addition polymerization reaction using the raw material monomer of the said polyester component, and the raw material monomer of a vinyl resin component (Unexamined-Japanese-Patent No. 7-98518).

  Raw material monomers for vinyl resin components include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate Vinyl esters such as vinyl propionate; alkyl (carbon number 1 to 18) esters of (meth) acrylic acid; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether And vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone and the like. Styrene, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate are preferable, and the alkyl ester of styrene and / or (meth) acrylic acid is preferably contained in an amount of 50% by weight or more in the vinyl resin component. More preferably, it is 80 to 100% by weight.

  In addition, when polymerizing the raw material monomer of a vinyl-type resin component, you may use a polymerization initiator, a crosslinking agent, etc. as needed.

  The weight ratio of the raw material monomer of the polyester component to the raw material monomer of the vinyl resin component (polyester component raw material monomer / vinyl resin component raw material monomer) is preferably 55/45 to from the viewpoint of forming a continuous phase with the polyester component. It is 95/5, More preferably, it is 60 / 40-95 / 5, More preferably, it is 70 / 30-90 / 10.

  The number average molecular weight of the amorphous polyester is 1000 to 2400, preferably 1100 to 2000, and more preferably 1200 to 1800, from the viewpoints of low-temperature fixability of the toner, storage stability of the printed matter, and curling of the printed matter. The weight average molecular weight is preferably from 3000 to 7000, more preferably from 3500 to 6000, and even more preferably from 3500 to 5500, from the viewpoints of low-temperature fixability of toner, storage stability of printed matter, and curling of printed matter. The number average molecular weight and the weight average molecular weight of the amorphous polyester are both values obtained by measuring the tetrahydrofuran soluble content. If the number average molecular weight of the amorphous polyester is less than 1000, the storability of the printed matter is deteriorated, which is presumed to be due to a decrease in the glass transition point. On the other hand, if it exceeds 2,400, the low-temperature fixability of the toner and curling suppression of the printed matter are reduced. This is presumably because the crystalline polyester is difficult to finely disperse because the miscibility with the crystalline polyester is reduced. The

  The softening point of the amorphous polyester is preferably 68 to 120 ° C., more preferably 68 to 100, from the viewpoint of low-temperature fixability of the toner, dispersibility of the crystalline polyester, storage stability of the printed matter, and curling of the printed matter. ° C, more preferably 68-90 ° C, still more preferably 68-85 ° C.

  The present invention uses an amorphous polyester having a low softening point and an amorphous polyester having a high softening point from the viewpoints of low-temperature fixability and hot offset property of toner, storage stability of printed matter, and curling of printed matter. It is preferable.

  An amorphous polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing 5 to 25 moles of an adipic acid compound with respect to 100 moles of the alcohol component, the number average molecular weight being 1000 to 2400 It is preferable to use the amorphous polyester as the amorphous polyester having a low softening point. As the preferable carboxylic acid component and alcohol component of the polyester having a high softening point, the same polyester as the polyester having a low softening point can be used.

  The softening point of the amorphous polyester having a low softening point is preferably 68 to 120 ° C, more preferably 68 to 100 ° C, still more preferably 68 to 88 ° C, and the softening point of the amorphous polyester having a high softening point is 120 It exceeds 160 degreeC and 160 degreeC is preferable, 125-160 degreeC is more preferable, 125-155 degreeC is more preferable. The difference in softening point between the low softening point amorphous polyester and the high softening point amorphous polyester is preferably 10 to 90 ° C, more preferably 20 to 80 ° C. The weight ratio of the low softening point amorphous polyester to the high softening point amorphous polyester (low softening point amorphous polyester / high softening point amorphous polyester) is preferably 90/10 to 50/50 85/15 to 70/30 are more preferable.

  The acid value of the amorphous polyester is preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g, and further preferably 15 to 35 mgKOH / g, from the viewpoint of low-temperature fixability of the toner. The hydroxyl value is preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g, and even more preferably 15 to 35 mgKOH / g, from the viewpoint of low-temperature fixability of the toner.

  The glass transition point of the amorphous polyester is preferably 35 to 45 ° C., more preferably 37 to 43 ° C. from the viewpoints of low-temperature fixability of the toner, storage stability of the printed matter, and curling of the printed matter.

  The softening point, number average molecular weight, weight average molecular weight, acid value, hydroxyl group and glass transition point can be adjusted by adjusting the raw material monomer composition, polymerization initiator, molecular weight, catalyst amount, etc., or by selecting reaction conditions. .

  In the production of amorphous polyester, the condensation polymerization reaction between the alcohol component and the carboxylic acid component can be performed in the presence of an esterification catalyst, such as a tin compound or a titanium compound, which will be described later, in an inert gas atmosphere. It is preferable to carry out with. The final ultimate temperature after the temperature rise in the production of the amorphous polyester is preferably 180 to 250 ° C, more preferably 190 to 230 ° C.

As the esterification catalyst for amorphous polyester, from the viewpoint of curling suppression of the printed matter, the formula (IIa) or (IIb):
Ti (X) _m (OH) _n (IIa)
O = Ti (X) _p (OY) _q (IIb)
(In the formula, X is a residue obtained by removing a hydrogen atom from one hydroxyl group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and the other hydroxyl group of the polyalkanolamine is a hydroxyl group directly bonded to the same titanium atom. May be polycondensed in the molecule to form a ring structure, or a hydroxyl group directly bonded to another titanium atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization is 2 to 5. Y is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds, and m is 1 to 4, preferably 2 to 4. Integer, n is an integer from 0 to 3, preferably 0 to 2, the sum of m and n is 4. p is an integer from 1 to 2, q is an integer from 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different.)
The at least 1 type of titanium containing catalyst represented by these is preferable.

  X is preferably a monoalkanolamine (particularly ethanolamine) residue, a dialkanolamine (particularly diethanolamine) residue, or a trialkanolamine (particularly triethanolamine) residue. The monoalkanolamine is preferably ethanolamine, the dialkanolamine is preferably diethanolamine, and the trialkanolamine is preferably triethanolamine, and more preferably triethanolamine from the viewpoint of curling of printed matter.

  In Y, the alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and n-hexyl group. N-octyl group, β-methoxyethyl group, β-ethoxyethyl group and the like.

  Y is preferably a hydrogen atom and an alkyl group having 1 to 4 carbon atoms that does not contain an ether bond, and more preferably a hydrogen atom, an ethyl group, or an isopropyl group, from the viewpoint of curling suppression of printed matter.

  Specific examples of the titanium-containing catalyst represented by the formula (IIa) include titanium tetrakis (monoethanolamate), titanium monohydroxytris (triethanolamate), titanium dihydroxybis (triethanolamate), and titanium trihydroxy. Triethanolaminate, Titanium dihydroxybis (diethanolamate), Titanium dihydroxybis (monoethanolamate), Titanium dihydroxybis (monopropanolamate), Titanium dihydroxybis (N-methyldiethanolamate), Titanium dihydroxybis (N- Butyl diethanolamate), reaction products of tetrahydroxytitanium and N, N, N ′, N′-tetrahydroxyethylethylenediamine, these Daughterscope or intermolecular polycondensates, and the like.

  Specific examples of the titanium-containing catalyst represented by the formula (IIb) include titanyl bis (triethanolaminate), titanyl bis (diethanolamate), titanyl bis (monoethanolamate), titanyl hydroxyethanolamate, titanyl hydroxytria Examples thereof include ethanolaminate, titanyl ethoxytriethanolamate, titanyl isopropoxytriethanolaminate, and intramolecular or intermolecular polycondensates thereof.

  The alcohol component which is a raw material monomer of the crystalline polyester contains an aliphatic diol having 6 to 12 carbon atoms from the viewpoint of enhancing the crystallinity of the polyester.

  Examples of the aliphatic diol having 6 to 12 carbon atoms in the present invention include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, Examples include 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, and 1,4-butenediol. Among these, the alcohol component preferably contains an aliphatic diol having 6 to 12 carbon atoms from the viewpoint of low-temperature fixability of toner, storage stability of printed matter, and suppression of curling suppression of printed matter. More preferably, it contains an aliphatic diol having 6 to 8 carbon atoms, and from the viewpoint of crystallinity, it preferably contains an α, ω-linear alkanediol having 6 to 12 carbon atoms, More preferably, it contains 8 α, ω-linear alkanediol, and more preferably 1,6-hexanediol.

  The content of the aliphatic diol having 6 to 12 carbon atoms is 70 to 100 mol%, preferably 80 to 100 mol%, more preferably in the alcohol component from the viewpoint of further improving the crystallinity of the crystalline polyester. 90 to 100 mol%. The content of one kind of C6-12 α, ω-linear alkanediol in the alcohol component is preferably 70 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%. The content of 1,6-hexanediol in the alcohol component is preferably 70 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%.

  Examples of alcohol components other than aliphatic diols having 6 to 12 carbon atoms include carbon numbers such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,5-pentanediol. Includes aliphatic diols other than 6-12, polyoxypropylene adducts of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene adducts of 2,2-bis (4-hydroxyphenyl) propane, etc. Examples include aromatic diols such as alkylene oxide adducts of bisphenol A represented by the following formula (I); trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

(In the formula, R ¹ O and OR ¹ are oxyalkylene groups, R ¹ is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, and each is a positive number; The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)

  The carboxylic acid component of the crystalline polyester contains at least an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms from the viewpoint of low-temperature fixability of the toner, storage stability of the printed matter, and curling suppression of the printed matter.

  Examples of the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms include suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid and the like. Among these, from the viewpoint of low-temperature fixability of toner, storage stability of printed matter, and curling suppression of printed matter, the carboxylic acid component preferably contains an aliphatic dicarboxylic acid compound having 10 to 12 carbon atoms. It is more preferable to contain an acid.

  Content of a C8-C12 aliphatic dicarboxylic acid compound is 70-100 mol% in a carboxylic acid component, Preferably it is 90-100 mol%, More preferably, it is substantially 100 mol%. When the content is less than 70 mol% in the carboxylic acid component, the low-temperature fixability of the toner is lowered. From the viewpoint of low-temperature fixability of the toner, storage stability of the printed matter, and curling suppression of the printed matter, the content of sebacic acid is preferably 70 to 100 mol%, more preferably 90 to 100 mol% in the carboxylic acid component. Substantially more preferably 100 mol%.

  Examples of the carboxylic acid component other than the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms include an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound having 2 to 7 carbon atoms, and an aromatic polycarboxylic acid compound having 3 or more valences. Although it is mentioned, it is not particularly limited to these.

  Preferred examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, anhydrides of these acids, and alkyl (C1 to C3) esters thereof.

  Examples of the aliphatic dicarboxylic acid compound having 2 to 7 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid and the like; anhydrides of these acids and the like And alkyl (carbon number 1 to 3) esters of these acids.

  Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and other aromatic carboxylic acids, and these Derivatives such as acid anhydrides and alkyl (C1-3) esters are exemplified.

  A monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight of the resin.

  The softening point of the crystalline polyester is preferably 60 to 160 ° C, more preferably 60 to 120 ° C, and more preferably 60 to 100 ° C, from the viewpoint of low-temperature fixability of the toner, storage stability of the printed matter, and curling of the printed matter. More preferably, 60-90 degreeC is still more preferable.

  The melting point of the crystalline polyester is preferably 60 to 130 ° C., more preferably 60 to 100 ° C., and still more preferably 60 to 90 from the viewpoints of low-temperature fixability of toner, storage stability of printed matter, and curling of printed matter. ° C.

  The number average molecular weight of the crystalline polyester is preferably 1000 or more, more preferably 1500 or more, from the viewpoints of low-temperature fixability of the toner, storage stability of the printed matter, and curling of the printed matter. However, considering the productivity of the crystalline polyester, the number average molecular weight is preferably 6000 or less, more preferably 5000 or less, and further preferably 4500 or less. From the above viewpoint, the number average molecular weight of the crystalline polyester is preferably 1000 to 6000, more preferably 1000 to 5000, and further preferably 1500 to 4500.

  Further, from the same viewpoint as the number average molecular weight, the weight average molecular weight is preferably 3,000 or more, more preferably 5,000 or more, further preferably 8,000 or more, preferably 100,000 or less, more preferably 50,000 or less, and further preferably 30,000. Below, more preferably 20,000 or less. In view of the above, the weight average molecular weight of the crystalline polyester is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000, and still more preferably 8,000 to 20,000.

  In the present invention, the number average molecular weight and the weight average molecular weight of the crystalline polyester are both values obtained by measuring the chloroform-soluble content. The number average molecular weight and the weight average molecular weight can be increased by increasing the reaction temperature of polycondensation, increasing the amount of catalyst, using a cocatalyst together, or lengthening the reaction time.

  The raw material molar ratio of the alcohol component and the carboxylic acid component (carboxylic acid component / alcohol component), which is the raw material monomer of the crystalline polyester, is mainly composed of carboxy groups at the ends of the polyester, and suppresses curling of the printed matter. From this viewpoint, it is preferably 1.03 to 1.20, more preferably 1.03 to 1.15, further preferably 1.04 to 1.12, and still more preferably 1.05 to 1.10. When the molar ratio (carboxylic acid component / alcohol component) is 1.03 or more, the hydroxyl group terminal ratio decreases, and the storability of the printed matter and the curling of the printed matter are improved. When the molar ratio (carboxylic acid component / alcohol component) is 1.20 or less, the storage stability of the printed matter and the curling of the printed matter are improved without increasing the amount of the low molecular weight component of the crystalline polyester.

  The temperature condition in the production of the crystalline polyester is preferably 130 to 250 ° C, and the final temperature after the temperature rise is preferably 180 to 250 ° C, more preferably 190 to 230 ° C.

  In the production of crystalline polyester, from the viewpoint of low-temperature fixability of toner, storability of printed matter and curling of printed matter, 130 to 160 ° C, preferably 130 to 150 ° C, when discharging theoretical reaction water. When the reaction rate is 100%, the condensation polymerization reaction is carried out until the reaction rate of the condensation polymerization reaction determined from the amount of discharged reaction water is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more. It is preferable to make it.

  Considering a relatively low temperature of 130 to 160 ° C., the reaction rate is preferably 80% or less, more preferably 40 to 80%, further preferably 50 to 80%, and even more preferably 60 to 80%. The polycondensation reaction is preferably performed within the above temperature range.

  That is, in the process of conducting the condensation polymerization reaction by raising the temperature of the mixture of the alcohol component and the carboxylic acid component, the condensation polymerization reaction is carried out at a relatively low temperature range of 130 to 160 ° C. until the reaction rate becomes 40% or more. By proceeding, the amount of the low molecular weight component of the crystalline polyester can be reduced, and the storage stability of the printed matter and the curling of the printed matter can be improved. This is presumably because the low molecular weight component is reduced because the monomer component reacts sufficiently compared with the case of reacting at a high temperature in a short time.

  It is not always necessary to maintain the temperature range of 130 to 160 ° C. until the reaction rate of the condensation polymerization reaches 40% or more, and may be temporarily outside the range as long as the effect of the present invention is not impaired. In addition, it is preferable that the reaction rate is in a temperature range of 130 to 160 ° C. at any point where the reaction rate is 40% or more.

  Specifically, the reaction rate is preferably set to 40% or more by maintaining the reaction in the above temperature range for 3 to 12 hours, more preferably 3 to 10 hours, and further preferably 3 to 8 hours. .

  Further, the catalyst has a reaction rate of the condensation polymerization reaction (the reaction rate of the condensation polymerization reaction calculated from the amount of discharged reaction water when the reaction rate is 100% when the theoretical reaction water amount is discharged. The same applies hereinafter). From the viewpoint of storage stability of printed matter and curling of the printed matter, addition to the reaction system at the time when the content becomes more than% is preferable. The catalyst may be deactivated by the reaction water. If the catalyst used from the early stage of the reaction is deactivated, the action of the catalyst added in the later stage of the reaction may be hindered or the crystallinity of the crystalline polyester may be lowered. Therefore, it is preferable to suppress the amount of catalyst used at the beginning of the reaction.

  The amount of catalyst to be added when the reaction rate of the condensation polymerization reaction is 70% or more, preferably 70 to 90% of the condensation polymerization reaction, is preferably 50% by weight or more, more preferably 70% by weight or more of the total amount of the catalyst. Preferably it is 80 weight% or more.

  Further, the condensation polymerization reaction rate is 90% or more and the degree of vacuum is 12 kPa or less, preferably the pressure reduction time is 1 hour or more, more preferably 1 to 10 hours, and further preferably 1 to 5 hours. This is preferable from the viewpoint of storage stability and curling of printed matter.

  The end point of the polycondensation reaction is when the crystalline polyester is taken out from the reaction tank when it is finished in the reaction tank not using the stirrer, and when it is finished in the reaction tank using the stirrer, the stirring is substantially performed. It ’s time to stop. The end point of the condensation polymerization reaction depends on the required resin performance, but it is usually preferable that the reaction rate of the condensation polymerization reaction is 90% or more.

  As the esterification catalyst for the crystalline polyester, a tin (II) compound having no Sn—C bond is preferable from the viewpoint of improving the storage stability of the toner.

  Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferably, a tin (II) compound having a Sn—O bond is more preferable.

Examples of tin (II) compounds having Sn-O bonds include tin (II) oxalate, tin (II) acetate, tin (II) octoate, tin (II) 2-ethylhexanoate, and tin (II) laurate. , Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), stearoxy tin (II) ), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as oleyloxytin (II); tin (II) oxide; tin (II) sulfate, Sn—X (X represents a halogen atom) Examples of the tin (II) compound having a bond include tin (II) halides such as tin (II) chloride and tin (II) bromide. Among these, from the viewpoint of catalytic ability, (R ² COO) ₂ Sn (wherein R ² represents an alkyl or alkenyl group having 5 to 19 carbon atoms), fatty acid tin (II), (R ³ O) ₂ Sn (where R ³ is carbon 6 ~ 20 alkyl or alkenyl groups Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by the be), (R ² COO), more preferably the fatty acid tin represented by ₂ Sn (II) and tin oxide (II) Further preferred are tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide.

  As another catalyst used for the production of amorphous polyester and crystalline polyester, a titanium compound having a Ti-O bond is preferable, specifically, an alkoxy group having 1 to 28 carbon atoms, 2 to 2 carbon atoms in total. Compounds having 28 alkenyloxy groups or acyloxy groups having 1 to 28 total carbon atoms are more preferred.

Specific examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium di Ethylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₂ H ₅ O) ₂ ], titanium dihydroxyoctyl bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (OHC ₈ H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C ₆ H ₁₄ O ₃ N) (C ₃ H ₇ O) ₃ ], titanium monopropyl tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O)] and the like, among these, titanium diisopropyl Preferred are rate bistriethanolamate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate, which are also available as commercial products from Matsumoto Trading Co., Ltd., for example.

Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl 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 dihydroxyoctyl 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. Among these, tetrastearyl titanate, tetra Myristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.

  One or two or more esterification catalysts can be used in combination.

  The amount of the esterification catalyst used is preferably 0.01 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, and still more preferably 0.2 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.

  In the present invention, a pyrogallol compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group can be used as a co-catalyst together with an esterification catalyst.

  Examples of pyrogallol compounds include pyrogallol, gallic acid, gallic acid esters, 2,3,4-trihydroxybenzophenone, benzophenone derivatives such as 2,2 ', 3,4-tetrahydroxybenzophenone, epigallocatechin, epigallocatechin gallate, etc. Catechin derivatives and the like.

  The weight ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably from 0.01 to 0.5, more preferably from 0.03 to 0.3, and even more preferably from 0.05 to 0.2, from the viewpoint of storage stability of the toner.

  In the binder resin of the present invention, the weight ratio of the crystalline polyester to the amorphous polyester (amorphous polyester / crystalline polyester) is 95/5 to 50/50 from the viewpoint of improving the low-temperature fixability of the toner. Preferably, 95/5 to 60/40 is more preferable, and 93/7 to 70/30 is more preferable.

  In the binder resin of the present invention, known binder resins other than crystalline polyester and amorphous polyester, for example, vinyl resins such as styrene-acrylic resins, epoxy resins, and the like, within a range not impairing the effects of the present invention. Other resins such as polycarbonate and polyurethane may be used in combination, but the total content of the crystalline polyester and the amorphous polyester is preferably 70% by weight or more, more preferably 80% by weight or more in the binder resin. Preferably, 90% by weight or more is more preferable, and substantially 100% by weight is further preferable.

  The toner of the present invention preferably contains an amide compound from the viewpoint of improving the storage stability of the toner.

  Examples of the amide compound include polyamides, fatty acid amides, aromatic amide compounds, etc. Among these, fatty acid amides are preferable from the viewpoint of affinity with the catalyst, and fatty acid amides are from the viewpoint of compatibility with polyester. Therefore, an alkylene bis fatty acid amide is preferable. Suitable fatty acid amides in the present invention include stearic acid amide, oleic acid amide, methacrylic acid amide, nicotinic acid amide phenylacetic acid amide, n-butyric acid amide, isobutyric acid amide, propionamide, ethylene bis stearic acid amide, hexamethylene bis Lauric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide, N, N-ethylene bis octadamide, etc. are mentioned, and from the viewpoint of high thermal stability, stearic acid amide and ethylene bis stearic acid amide are More preferred.

  The content of the amide compound is preferably 0.1 to 5 parts by weight and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the binder resin.

  The toner of the present invention further includes a colorant, a release agent, a charge control agent, a charge control resin, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an oxidation Additives such as an inhibitor, an anti-aging agent, and a cleaning property improver 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.

  Release agents include polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant waxes such as oils; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax, which are used alone or in combination of two or more Can be mixed and used.

  The melting point of the release agent is preferably 60 to 160 ° C., more preferably 60 to 150 ° C., from the viewpoints of low-temperature fixability and offset resistance of the toner.

  The content of the release agent is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and more preferably 1.5 to 7 parts by weight from the viewpoint of dispersibility in the binder resin with respect to 100 parts by weight of the binder resin. Part by weight is more preferred.

  The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.

  Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-07”, “Bontron N-09” ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.), etc .; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 ”(Orient Chemical) Manufactured by Kogyo Co., Ltd.), cetyltrimethylammonium bromide, “COPY CHARGE PX VP435” (manufactured by Hoechst), etc .; polyamine resin such as “AFP-B” (manufactured by Orient Chemical Co., Ltd.), etc .; , “PLZ-8001” (manufactured by Shikoku Kasei Co., Ltd.) and the like.

  In addition, as a negatively chargeable charge control agent, metal-containing azo dyes such as “Varifirst Black 3804”, “Bontron S-31” (above, manufactured by Orient Chemical Industries), “T-77” (Hodogaya Chemical) Manufactured by Kogyo Co., Ltd.), Bontron S-32, Bontron S-34, Bontron S-36 (above, Orient Chemical Co., Ltd.), Eisenspiron Black TRH (Hodogaya Chemical Co., Ltd.) A metal compound of a benzylic acid compound, such as “LR-147”, “LR-297” (manufactured by Nippon Carlit Co., Ltd.); a metal compound of a salicylic acid compound, such as “Bontron E-81”, “Bontron E- 84, “Bontron E-88”, “E-304” (manufactured by Orient Chemical Co., Ltd.), “TN-105” (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dye; quaternary ammonium salt such as “ COPY CHARGE NX VP434 "(Hoechst), nitroimidazole derivative; organometallic compound , For example, "TN105" (commercially available from Hodogaya Chemical Co., Ltd.), and the like.

  The content of the charge control agent is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the binder resin, from the viewpoint of the charge rising property of the toner. More preferably, 0.5 to 3 parts by weight is even more preferable, and 1 to 2 parts by weight is even more preferable.

  The toner of the present invention 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 hermetic kneader, a single-screw 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.

The volume median particle size (D ₅₀ ) of the toner of the present invention 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.

  In the toner of the present invention, it is preferable to use inorganic fine particles as an external additive in order to improve transferability. Specifically, at least one selected from the group consisting of silica, alumina, titania, zirconia, tin oxide, and zinc oxide is preferable. Among these, silica is preferable, and from the viewpoint of preventing embedding, the specific gravity is More preferably, small silica is contained.

  The content of the external additive is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and still more preferably 0.3 to 100 parts by weight of toner particles before being processed with the external additive. ~ 3 parts by weight.

  The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed 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.

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan and cool it from room temperature to 0 ° C at a rate of 10 ° C / min. Then, it was left still for 1 minute. Thereafter, the measurement was carried out at a heating rate of 50 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C of the softening point, the peak temperature is taken as the melting point.

[Glass transition point of resin]
Using a differential scanning calorimeter (Q-20, Japan, Q-20), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and decrease the temperature from that temperature. The sample cooled to 0 ° C at 10 ° C / min is heated at a heating rate of 10 ° C / min, and the maximum slope from the peak rising portion to the peak apex is reached. The temperature at the intersection with the indicated tangent.

[Acid value of the resin]
Measured by the method of JIS K0070. However, only the measurement solvent is 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)).

[Hydroxyl value of the resin]
Measured by the method of JIS K0070.

[Weight average molecular weight and number average molecular weight of the resin]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method according to the following method to determine the weight average molecular weight and the number average molecular weight.
(1) Preparation of sample solution The sample is dissolved in chloroform (crystalline polyester) or tetrahydrofuran (amorphous polyester) at 25 ° C. so that the concentration is 0.5 g / 100 ml. Next, this solution is filtered using a fluororesin filter (manufactured by ADVANTEC, DISMIC-25JP) having a pore size of 0.2 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Molecular weight measurement Chloroform (crystalline polyester) or tetrahydrofuran (amorphous polyester) as an eluent was flowed at a flow rate of 1 ml per minute using the following measuring apparatus and analytical column, and the column was placed in a constant temperature bath at 40 ° C. To stabilize. Measurement is performed by injecting 100 μl of the sample solution. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. At this time, several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A- 5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), F- 20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) prepared as standard samples are used.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[Melting point of release agent]
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 electrolytic solution is added, and further dispersed for 1 minute by an ultrasonic disperser.
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).

Amorphous polyester production example 1 [resins AA to AL]
BPA-PO, BPA-EO, 40 g of terephthalic acid and titanium dihydroxybis (triethanolamate) and 1 g of gallic acid were added in the amounts shown in Tables 1 and 2 and reacted at 230 ° C. for 10 hours. After the reaction, the temperature was lowered to 190 ° C., adipic acid was added, and the mixture was reacted at normal pressure for 2 hours. Furthermore, trimellitic anhydride was added and reacted until the softening points shown in Tables 1 and 2 were reached, thereby obtaining an amorphous polyester.

Production Example 2 of Amorphous Polyester [Resin AM]
An amorphous polyester was obtained in the same manner as in Production Example 1, except that 40 g of tin (II) 2-ethylhexanoate was used instead of titanium dihydroxybis (triethanolaminate).

Production Example 3 of Amorphous Polyester [Resin B]
BPA-PO, BPA-EO, 40 g of terephthalic acid and titanium dihydroxybis (triethanolaminate) and 2 g of gallic acid were added in the amounts shown in Table 2 and reacted at 230 ° C. for 10 hours. After the reaction, the temperature was lowered to 190 ° C., adipic acid and trimellitic anhydride were added, reacted for 1 hour, then heated to 210 ° C., and further reacted for 1 hour. Then, it was made to react at 30 Kpa until it reached the softening point shown in Table 2, and amorphous polyester was obtained.

Production Example of Crystalline Polyester [Resin A-1, C-1]
A 10-L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was charged with the raw material monomer in the blending amount shown in Table 3, heated to 140 ° C. and reacted for 6 hours (reaction The reaction was carried out while raising the temperature up to 200 ° C. at a rate of 10 ° C./hour. After reacting to a reaction rate of 80% at 200 ° C., 20 g of tin (II) 2-ethylhexanoate was added, and the reaction was further carried out at 200 ° C. for 2 hours. The reaction was further performed at 8 kPa for 2 hours to obtain a crystalline polyester.

Production Example of Crystalline Polyester [Resin B-1]
Into a 10-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 40 g of tin (II) ethyl 2-ethylhexanoate was added together with the raw material monomer of the blending amount shown in Table 3, and 200 ° C. The reaction was continued while heating up to 4 hours. Furthermore, after reacting to a reaction rate of 90% at 200 ° C., the reaction was carried out at 8 kPa for 1 hour to obtain a crystalline polyester.

Examples 1-10 and Comparative Examples 1-6
100 parts by weight of the binder resin shown in Table 4, 6 parts by weight of the colorant “Fastgen Super Magenta R” (CI Pigment Red 122, manufactured by Dainippon Ink & Chemicals, Inc.), the charge control agent “LR-147 1 part by weight (manufactured by Nippon Carlit Co., Ltd.), 2 parts by weight of ethylenebisstearic acid amide “Kao wax EB-P” (manufactured by Kao Corporation) and mold release agent “Carnauba Wax C1” (manufactured by Kato Yoko Co., Ltd., melting point: (80 ° C.) 4 parts by weight were thoroughly stirred with a Henschel mixer, and then melt-kneaded using a co-rotating twin screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The roll rotation speed was 200 r / min, the heating set temperature in the roll was 100 ° C., the kneaded product temperature was 160 ° C., the kneaded product feed rate was 10 kg / hour, and the average residence time was about 18 seconds. After cooling, toner particles having a volume median particle size (D ₅₀ ) of 6.5 μm were obtained with a jet mill.

  For 100 parts by weight of the obtained toner particles, 1.5 parts by weight of “Aerosil R-972” (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 16 nm) and “SI-Y” (hydrophobic) 1.0 part by weight of silica (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 40 nm) was added, and the mixture was mixed with a Henschel mixer at 3600 r / min for 5 minutes to perform external additive treatment to obtain a toner.

Test Example 1 [Evaluation of minimum fixing temperature]
The toner was mounted on the copier “AR-505” (manufactured by Sharp), and the image was printed on the recycled paper (recycled cut size G80A4W, manufactured by Toppan Forms) without fixing (printing area: 2cm × 12cm, adhesion amount) : 0.6 mg / cm ² ). The fixing machine of the copying machine was fixed on paper at 600 mm / sec while increasing the fixing temperature in steps of 5 ° C. from 90 ° C. to 240 ° C. offline.

  A sand eraser (Lion ER-502R Ink & Ballpen) with a bottom of 15mm x 7.5mm under a load of 500g is used to rub the image fixed through the fixing machine 5 times, and the reflection density meter "RD-915" ”(Trade name, manufactured by Macbeth Co., Ltd.), and the fixing roller temperature at which the ratio between the two (after rubbing / before rubbing) first exceeds 80% is defined as the minimum fixing temperature. Sex was evaluated. The results are shown in Table 4.

〔Evaluation criteria〕
A: The minimum fixing temperature is less than 110 ° C.
B: The minimum fixing temperature is 110 ° C. or higher and lower than 115 ° C.
C: The minimum fixing temperature is 115 ° C. or higher and lower than 120 ° C.
D: The minimum fixing temperature is 120 ° C. or higher and lower than 130 ° C.
E: The minimum fixing temperature is 130 ° C. or higher.

Test Example 2 [Preservation of printed matter]
Using the copying machine of Test Example 1, in the same manner as Test Example 1, an image was unfixed on the recycled cut G80A4W paper (19 cm × 26 cm, adhesion amount: 0.6 mg / cm ² ). Fixing was performed at the determined minimum fixing temperature + 20 ° C. to obtain a test paper (printed matter). The test paper was placed on the new paper (G80A4W) with the print side down, and 50 new papers (G80A4W) were further stacked thereon. In that state, after putting it in a constant temperature and humidity chamber of 50 ° C. and 60% humidity for 8 hours, it was taken out and checked at 25 ° C. The printed matter storability was evaluated according to the following evaluation criteria. The results are shown in Table 4.

<Evaluation criteria>
A: There is no fusion at all.
B: There is a slight fusion when peeling, but no image loss after peeling.
C: There is fusion at the time of peeling, and there are slight image defects after peeling.
D: There is fusion at the time of peeling, and the image defect after peeling is apparent.
E: It is completely fused and cannot be peeled off.

Test Example 3 [Evaluation of curling suppression of printed matter]
Place the test paper (printed material) of Test Example 2 on a parallel plate such as a desk with the printing surface facing up (25 ° C) and measure the distance (distance) from the desk at the end to four points. The away value of was calculated. The curl was evaluated according to the following evaluation criteria. The results are shown in Table 4.

〔Evaluation criteria〕
A: Maximum value of end curvature is 1 mm or less B: Maximum value of end curvature exceeds 1 mm, 3 mm or less C: Maximum value of end curvature exceeds 3 mm, 5 mm or less D: End The maximum value of warping exceeds 5mm and 10mm or less E: The maximum value of end warping exceeds 10mm

  From the above results, it can be seen that the toners of Examples 1 to 10 have better low-temperature fixability and printed matter storage stability than those of Comparative Examples 1 to 6, and curling is also suppressed.

  The binder resin for toner of the present invention is suitably used for a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

Claims (9)

An amorphous polyester having a number average molecular weight of 1000 to 2400, obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing 7 to 25 mol of an adipic acid compound with respect to 100 mol of the alcohol component; Obtained by polycondensation of an alcohol component containing 70 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms A binder resin for toner, comprising crystalline polyester.   The binder resin for toner according to claim 1, wherein the amorphous polyester has a glass transition point of 35 to 45 ° C.   The binder resin for toner according to claim 1 or 2, wherein the softening point of the amorphous polyester is 68 to 120 ° C.   The binder resin for toner according to claim 1, wherein a raw material molar ratio (carboxylic acid component / alcohol component) of the alcohol component and the carboxylic acid component of the crystalline polyester is 1.03 to 1.20. The amorphous polyester has the formula (IIa) or (IIb):
Ti (X) _m (OH) _n (IIa)
O = Ti (X) _p (OY) _q (IIb)
(In the formula, X is a residue obtained by removing a hydrogen atom from one hydroxyl group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and the other hydroxyl group of the polyalkanolamine is a hydroxyl group directly bonded to the same titanium atom. May be polycondensed in the molecule to form a ring structure, or a hydroxyl group directly bonded to another titanium atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization is 2 to 5. Y is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds, m is an integer of 1 to 4, and n is 0 to 0. The integer of 3 and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, respectively X in the above may be the same or different.)
In the presence of at least one titanium-containing catalyst is represented, an alcohol component and a carboxylic acid component is an amorphous polyester obtained by polycondensing, claim 1-4 binder for toners according to any one resin. The binder resin for toner according to claim 1, wherein the crystalline polyester is dispersed in the amorphous polyester. The binder resin for toner according to any one of claims 1 to 6, obtained by melt-kneading crystalline polyester and amorphous polyester. Comprising the claims 1-7 for toner binder resin according to any one of a toner for electrophotography. The electrophotographic toner according to claim 8, which is obtained by a method comprising a step of melt-kneading a raw material containing at least a crystalline polyester and an amorphous polyester.