JP2017039793A - Crystalline polyester, resin composition, method for producing resin composition, and method for producing resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide crystalline polyester and a resin composition which can obtain excellent low-temperature fixability when used for a toner and the like; a resin composition which can solve poor granulation that may be concerned when applied to resin particles obtained by water medium heterogeneous polymerization, and broadening of particle size distribution caused by the poor granulation, and a method for producing resin particles.SOLUTION: Crystalline polyester has (1) an endothermic peak measured by a differential scanning calorimetry, and has a half band width of the endothermic peak of 10°C or less; and has (2) a chain transfer group.SELECTED DRAWING: None

Description

  The present invention relates to a crystalline polyester, a resin composition, resin particles, and methods for producing them.

  Resin particles are used in various industrial fields. When resin particles are used as a resin binder for ink jet inks and electrophotographic toners, the property of abruptly changing the resin viscoelasticity with increasing temperature (hereinafter referred to as Sharp Melt) from the viewpoint of paralleling storage stability and low temperature fixability It is preferable to use resin particles having a characteristic). Examples of the resin particles having sharp melt characteristics include resin particles made of a crystalline polymer such as crystalline polyester. However, a crystalline polymer is remarkably brittle at room temperature, so it is difficult to use it alone. Thus, a method using resin particles made of a mixture of a crystalline polymer and an amorphous polymer has been proposed (Patent Document 1). When the crystalline polyester as the crystalline polymer and the styrene-acrylic resin as the non-crystalline polymer are mixed to form resin particles, when heated above the melting temperature of the crystalline polymer, the melted and liquefied crystallinity It is considered that the polyester melts the amorphous polymer and the resin particles are integrated and softened, so that the resin particles can be given sharp melt characteristics. However, when heated above the melting temperature of the crystalline polyester, the crystalline polyester and the styrene-acrylic resin are macro-separated into two phases, and the resin particles may not exhibit sufficient low-temperature fixability.

  As a method for solving this problem, there is a method using a composite polymer obtained by chemically bonding a crystalline polyester and an amorphous polymer (Patent Document 2). Since such a composite polymer has a higher affinity for the amorphous polymer than the crystalline polyester, the effect of suppressing the macro separation can be expected.

  However, since the composite polymer has a large molecular weight, for example, if it is contained in resin particles obtained by aqueous medium heterogeneous polymerization such as suspension polymerization, the viscosity of the polymerizable composition increases, and resin particles are produced. Graininess may be reduced.

JP 2010-145550 A JP 2010-139659 A

  The present invention provides a crystalline polyester and a resin composition capable of obtaining excellent low-temperature fixability when used in a toner or the like.

  Resin composition capable of solving poor granulation, which is a concern when applied to resin particles obtained by heterogeneous polymerization in aqueous medium, and broadening of particle size distribution due to poor granulation, and resin particles A manufacturing method is provided.

  The present invention has (1) an endothermic peak measured by differential scanning calorimetry, a half-value width of the endothermic peak is 10 ° C. or less, and (2) a chain transfer group. It relates to polyester.

  The present invention also provides a resin composition containing a composite polymer and an amorphous polymer, wherein the composite polymer is a block polymer in which a crystalline polyester and an amorphous polymer are chemically bonded, Relates to a resin composition having a vinylidene group.

  Furthermore, this invention relates to the manufacturing method of the resin composition characterized by synthesize | combining a resin composition by radical polymerization using the polymeric composition containing the said crystalline polyester and a radically polymerizable monomer.

  According to the present invention, it is possible to provide a crystalline polyester and a resin composition that can obtain excellent low-temperature fixability when used in toners and the like.

  Resin composition capable of solving poor granulation, which is a concern when applied to resin particles obtained by aqueous medium heterogeneous polymerization, and broadening of particle size distribution due to poor granulation, and resin A method for producing particles can be provided.

It is a figure which forms the resin particle which consists of a resin composition with the manufacturing method characterized by using crystalline polyester which has a chain transfer group. It is a figure formed by the manufacturing method characterized by using the composite polymer for the resin particle which consists of a resin composition. It is a figure explaining crystalline polyester which has a chain transfer group. It is a figure explaining the chemical reaction in which a chain transfer agent forms a vinylidene group by chain transfer reaction. It is a figure which shows the relationship between polymerization time and the peak molecular weight Mp of a composite polymer.

  Details of the present invention will be described below.

  One of the great features of the crystalline polyester of the present invention is that it has a chain transfer group. By producing resin particles made of a resin composition using this crystalline polyester, the viscosity of the polymerizable composition is lower than when the composite polymer is previously contained in the polymerizable composition. And the particle size distribution of the obtained resin particles can be narrowed. FIG. 1 shows a schematic diagram of the production method of the present invention characterized in that resin particles comprising a resin composition are obtained using a crystalline polyester having a chain transfer group. FIG. 2 also shows a conventional resin particle obtained by using a composite polymer (having no chain transfer group) separately prepared instead of a crystalline polymer having a chain transfer group. The schematic diagram of the manufacturing method of a well-known technique is shown. The production method of the present invention and the reason why the granulation property is improved by the present invention will be described below with reference to FIGS. However, the radical polymerization initiator is not shown in FIGS. 1 and 2 for the sake of simplicity.

  1 which is a manufacturing method of the present invention will be described. The polymerizable composition 1 contains a crystalline polyester 11 and a radical polymerizable monomer 12. In step 1 of FIG. 1, the polymerizable composition 1 is dispersed in an aqueous medium 13 to prepare a suspension 1 in which oil droplets A14 made of the polymerizable composition 1 are dispersed in the aqueous medium 13 (suspension process). ). In Step 2 of FIG. 1, the suspension 1 prepared in Step 1 is radically polymerized (polymerization step). Here, since the crystalline polyester 11 of the present invention has the chain transfer group 10, in step 2, the radically polymerizable monomers 12 are radically polymerized to form an amorphous polymer 15, and at the same time, the crystalline polymer 11 chain transfer groups 10 are also involved in radical polymerization based on the chain transfer reaction to form a composite polymer 18 composed of an amorphous polymer 16 chemically bonded to the crystalline polyester 11. As a result, resin particles 17 composed of a resin composition containing the composite polymer 18 and the amorphous polymer 15 are obtained.

  A conventionally known manufacturing method will be described with reference to FIG. The polymerizable composition 2 contains a composite polymer 18 formed by chemically bonding a crystalline polymer 11 and an amorphous polymer 16 chemically bonded to a crystalline polyester, a radical polymerizable monomer 12 and a radical polymerization initiator. . 2, the polymerizable composition 2 is dispersed in the aqueous medium 13, and the suspension 2 in which the oil droplets B19 made of the polymerizable composition 2 are dispersed in the aqueous medium 13 is prepared (suspension process). ). Then, in Step 4 of FIG. 2, the suspension 2 prepared in Step 3 is radically polymerized (polymerization step). In step 4, the radically polymerizable monomers 12 are radically polymerized to form an amorphous polymer 15. As a result, it is possible to form resin particles 17 made of a resin composition containing the composite polymer 18 in which the crystalline polyester 11 and the amorphous polymer 16 are chemically bonded, and the amorphous polymer 15.

  1 and 2, the resin particles 17 made of the resin composition containing the composite polymer 18 and the amorphous polymer 15 can be formed. However, the process 1 in FIG. 1 and the process 3 in FIG. Due to the difference, FIG. 1 is more advantageous than FIG. 2 in obtaining resin particles 17 made of a resin composition having a sharp particle size distribution. That is, the polymerizable composition 2 of FIG. 2 has a high viscosity because it contains the composite polymer 18 having a large molecular weight, and there is a risk of causing poor granulation when the suspension 2 is obtained by dispersing it in an aqueous medium. large. On the other hand, the polymerizable composition 1 in FIG. 1 has a low viscosity because it contains the crystalline polyester 11 having a molecular weight smaller than that of the composite polymer 18 in FIG. 2, and is dispersed in the aqueous medium 13 to obtain the suspension 1. At this time, the risk of causing poor granulation is extremely small.

  The polymerizable composition of the present invention will be described. The polymerizable composition of the present invention is a composition containing a crystalline polyester having a chain transfer group and a radical polymerizable monomer.

  The half-width of the endothermic peak measured by differential scanning calorimetry is 10 ° C. or less in the crystalline polyester having a chain transfer group of the present invention.

  The crystalline polyester of the present invention is a polyester having a melting temperature. Specifically, the half-value width of the endothermic peak measured in the differential scanning calorimetry at a heating rate of 10 ° C./min is 10 ° C. or less. Since such polyester softens rapidly above the melting temperature, when used as a resin binder for inkjet inks or electrophotographic toners, there is an advantage that storage stability and low-temperature fixability can be easily combined.

  Furthermore, the crystalline polyester of the present invention preferably has a maximum endothermic peak in DSC measurement of 60 ° C. or higher and 110 ° C. or lower from the viewpoint of achieving both storage stability and low-temperature fixability. Moreover, it is preferable that the heat of crystal fusion ΔHm calculated from this maximum absorption peak is 50 J / g or more.

  The crystalline polyester of the present invention is preferably an aliphatic polyester having a unit represented by the following general formula (1) or general formula (2).

(R ₁ , R ₂ and R ₃ each independently represents a linear alkyl group having 2 to 22 carbon atoms or a branched alkyl group having 2 to 22 carbon atoms, and m and n are 5 Represents an integer of ~ 150)
When the crystalline polyester has a unit represented by at least one of the general formula (1) and the general formula (2), the main chain easily forms a folded structure, and the half-value width of the endothermic peak in DSC measurement is 10 ° C. It is preferable from the viewpoint that crystallinity is easily obtained. Further, other units may be used in combination as long as the object of the present invention can be achieved.

  Furthermore, in the crystalline polyester of the present invention, the alkyl group of the general formula (1) or the general formula (2) is preferably a linear alkyl group. This is because a linear alkyl group is easier to form a folded structure in the main chain than a branched alkyl group, and a large crystallinity is easily obtained. Such crystalline polyester is a method of polycondensing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms, or polycondensing an aliphatic monohydroxycarboxylic acid having 2 to 22 carbon atoms. Although it can synthesize | combine by the method, the method of ring-opening polymerization of C2-C22 lactone, etc., the crystalline polyester of this invention is not limited to these, It can synthesize | combine by a conventionally well-known method.

  The aliphatic diol having 2 to 22 carbon atoms is not particularly limited, but a linear aliphatic diol is preferable. Examples of such aliphatic diols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1,20-icosanediol, 1,21-henicosanediol, 1, 22-docosanediol and the like can be mentioned. As long as the object of the present invention can be achieved, a plurality of polyhydric alcohols may be used in combination when the crystalline polyester is synthesized. When a plurality of polyhydric alcohols are used in combination, it is preferable that 50 mol% or more, more preferably 70 mol% or more, is an aliphatic diol having 2 to 22 carbon atoms.

  The aliphatic dicarboxylic acid having 2 to 22 carbon atoms is not particularly limited, but a linear aliphatic dicarboxylic acid is preferable. Examples of such aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10- Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,16-hexadecane Dicarboxylic acid, 1,17-heptadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, 1,19-nonadecanedicarboxylic acid, 1,20-icosanedicarboxylic acid, 1,21-henicosanedicarboxylic acid, 1, 22-docosanedicarboxylic acid and the like, and these acid anhydrides or lower alkyls. Ester can be a used as well, such as hydrolysates. In addition, a plurality of polyvalent carboxylic acids may be used when synthesizing the crystalline polyester as long as the object of the present invention can be achieved. When a plurality of polyvalent carboxylic acids are used in combination, preferably 50 mol% or more, more preferably 70 mol% or more is an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.

  The aliphatic monohydroxycarboxylic acid having 2 to 22 carbon atoms is not particularly limited, but a linear aliphatic monohydroxycarboxylic acid is preferable. Examples of such aliphatic monohydroxycarboxylic acids include hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutanoic acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, and 8-hydroxyoctane. Acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 13-hydroxytridecanoic acid, 14-hydroxytetradecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid , 17-hydroxyheptadecanoic acid, 18-hydroxyoctadecanoic acid, 19-hydroxynonadecanoic acid, 20-hydroxyicosanoic acid, 21-hydroxyhenicosanoic acid, 22-hydroxydocosanoic acid and the like. Examples of the lactone having 2 to 22 carbon atoms include γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octanolide, 9-nonanolide, 10-decanolide, 11-undecanolide, 12-dodecanolide, 13 -Tridecanolide, 14-tetradecanolide, 15-pentadecanolide, 16-hexadecanolide, 17-heptadecanolide, 18-octadecanolide, 19-nonadecanolide and the like. As long as the object of the present invention can be achieved, a plurality of aliphatic monohydroxycarboxylic acids or lactones may be used in combination. When a plurality of aliphatic monohydroxycarboxylic acids or lactones are used in combination, preferably 50% or more, more preferably 70% or more is an aliphatic monohydroxycarboxylic acid having 2 to 22 carbon atoms or 2 to 2 carbon atoms. It is preferred to use 22 lactones.

  The molecular weight of the crystalline polyester of the present invention is such that the main peak (peak molecular weight (Mp)) in the molecular weight distribution evaluated as polystyrene conversion is 3000 using gel permeation chromatography (hereinafter referred to as GPC) and chloroform as a developing solvent. It is preferably ˜50000. If it is in the said range, a principal chain will be easy to form a folding structure, and it can suppress that the viscosity of the polymeric composition 1 rises too much.

  The crystalline polyester having a chain transfer group in the present invention is a crystalline polyester in which chain transfer groups are chemically bonded.

  The chain transfer group of the present invention is a functional group involved in the chain transfer reaction of radical polymerization. In general, a compound having such a functional group is called a chain transfer agent. The chain transfer reaction is a reaction in which radicals of a growing polymer move to another compound in radical polymerization, and whether or not the radical that has moved to another compound attacks the monomer again to restart radical polymerization. , Determined by a chain transfer constant described later.

  Here, the chain transfer constant is a value determined by a growth reaction rate constant, which is one of elementary reactions of radical polymerization, and a chain transfer reaction rate constant. Specifically, it is a value obtained by dividing the rate constant of the chain transfer reaction by the rate constant of the growth reaction, and it is known that the restart ability is high when the chain transfer constant is 0.01 or more and 60 or less. Therefore, the chain transfer constant of the chain transfer group of the present invention is preferably from 0.01 to 60 with respect to the radical polymerizable monomer of the present invention.

  Moreover, it is preferable that the chain transfer group used for this invention contains a sulfur element.

  As a result of investigation by the inventors using a chain transfer group containing sulfur element, the reason is not clear, but in any case, the object of the present invention was achieved. Although it does not specifically limit as a chain transfer group containing a sulfur element, For example, a thiol group etc. are mentioned.

  Whether or not the chain transfer group contains sulfur element can be confirmed by a conventionally known method, and can be confirmed by a method such as elemental analysis such as combustion ion chromatography.

  The position where the chain transfer group of the present invention is chemically bonded to the crystalline polyester will be described with reference to FIG. The chain transfer group 10 is present at both ends of the main chain of the crystalline polyester 11 (FIG. 3A), at the end of one main chain (FIG. 3B), or from the crystalline polyester. Any of them may be present in the main chain or in the side chain (FIG. 3 (c)). Moreover, in this invention, as crystalline polyester which has a chain transfer group, you may use 1 type in FIG.3 (a), FIG.3 (b), FIG.3 (c), or these mixtures are used. May be. Among these, FIG. 3A or FIG. 3B is particularly preferable. This is because the main chain is more likely to form a folded structure in FIG. 3 (a) and FIG. 3 (b) than in FIG. 3 (c).

  The chain transfer group can be chemically bonded to the crystalline polyester by a conventionally known method. General crystalline polyester has either a hydroxyl group, a carboxyl group, or both at the end of the main chain. For example, in the case of a crystalline polyester having a hydroxyl group at the end of the main chain, a chain transfer agent having a carboxyl group in the molecular structure is used, and the hydroxyl group and the carboxyl group are esterified to convert the chain transfer group into a crystalline polyester. Can be chemically bonded. Examples of the method for esterifying a hydroxyl group and a carboxyl group include a method of heating using an acid catalyst, a method of using a dehydration condensing agent containing carbodiimide, and the present invention is not limited thereto. Instead of the chain transfer agent having a carboxyl group, an acid halide, an acid anhydride, or a chain transfer agent having a lower carboxylic acid ester can also be used. For example, in the case of a polyester having a carboxyl group at the end of the main chain, a chain transfer agent having a hydroxyl group in the molecular structure is used, and the carboxyl group and the hydroxyl group are esterified to chemically bond the chain transfer group to the crystalline polyester. Can be made.

  The crystalline polyester having a chain transfer group of the present invention is 3 to 40 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer from the viewpoint of suppressing an increase in viscosity of the polymerizable composition and obtaining good fixability. It is preferably used in the proportion of parts.

  The radical polymerizable monomer of the present invention preferably contains styrene, a styrene derivative, acrylic acid ester, or methacrylic acid ester as a main component. As long as the object of the present invention can be achieved, other monomers may be used as the radical polymerizable monomer of the present invention as long as it is less than 50% by mass, such as acrylonitrile, methacrylonitrile, acrylamide and the like. It is done.

  Although it does not specifically limit as styrene or a styrene derivative, Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene etc. are mentioned. Moreover, as long as the object of the present invention can be achieved, both styrene and a styrene derivative or a plurality of styrene derivatives may be used as the radical polymerizable monomer of the present invention.

  The acrylic ester or methacrylic ester is not particularly limited, but methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate , 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate , Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like. In addition, a plurality of acrylic acid esters or methacrylic acid esters may be used as the radical polymerizable monomer of the present invention as long as the object of the present invention can be achieved. The above exemplifies a radical polymerizable monomer having one radical polymerizable vinyl group in the compound, but in the present invention, such as divinylbenzene, 1,6 hexane diacrylate, and 1,6 hexane dimethacrylate, etc. In addition, a radical polymerizable monomer having a plurality of radical polymerizable vinyl groups in the compound may be used. In the present invention, a plurality of radical polymerizable monomers may be used in combination.

  The polymerizable composition used in the present invention is characterized in that it contains a crystalline polyester having a chain transfer group and a radical polymerizable monomer. For example, chain transfer can be performed as long as the object of the present invention can be achieved. An agent, a radical polymerization initiator, an organic solvent, a dispersion aid, a wax, a colorant and the like can be contained. For example, when resin particles are produced by adding a wax and a colorant to the polymerizable composition, the resin particles can be used as a toner.

  A chain transfer agent is a compound involved in a chain transfer reaction, which is one of elementary reactions of radical polymerization. The chain transfer reaction is a reaction in which radicals of a growing polymer move to another compound in radical polymerization, and whether or not the radical that has moved to another compound attacks the monomer again to restart radical polymerization. , Determined by a chain transfer constant described later. Generally, it is used for the purpose of adjusting the molecular weight of the polymer or introducing a chain transfer agent residue at the end of the main chain of the polymer.

  The chain transfer agent of the present invention is a low molecular chain transfer agent having a number average molecular weight of 1000 or less. According to the study by the inventors, when such a low molecular chain transfer agent is used, the low molecular chain transfer agent has a molecular weight adjusting action of the amorphous polymer chemically bonded to the crystalline polyester in the composite polymer. It has been found that the molecular weight tends to increase, that is, the formation efficiency of the composite polymer increases. The reason why the formation efficiency of the composite polymer is increased is not clear, but the inventors have found that the chain transfer group of the crystalline polyester and the low molecular chain transfer agent are competitively reacted in radical polymerization. I think that this phenomenon will occur.

  According to the study by the inventors, it has been found that a chain transfer agent having a poor number of diffusibility and a number average molecular weight of more than 1000 does not exhibit the effect expected by the inventors. From the viewpoint of diffusibility, it is more preferable to use a low-molecular chain transfer agent having a number average molecular weight of 500 or less.

  The low molecular chain transfer agent of the present invention preferably has a chain transfer constant of 0.01 to 60 with respect to the radical polymerizable monomer of the present invention. A low-molecular chain transfer agent having a chain transfer constant of 0.01 or more and 60 or less is excellent in the ability to restart radical polymerization, and is consistent with the object of the present invention.

  As the chain transfer agent in the present invention, a conventionally known chain transfer agent can be applied as long as the object of the present invention can be achieved. Although the specific example of the chain transfer agent applicable to this invention is given to the following, this invention is not limited to these. Specific examples of chain transfer agents having a chain transfer constant greater than 10 and less than or equal to 60 include n-butyl mercaptan, t-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, 2-methylbutyl mercaptan, n-hexyl mercaptan, n- Heptyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t-nonyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, n-pentadecyl mercaptan, n-hexadecyl Examples thereof include alkyl mercaptans such as mercaptan, t-hexadecyl mercaptan and stearyl mercaptan. Specific examples of the chain transfer agent having a chain transfer constant greater than 0.1 and 10 or less include methyl methacrylate dimer, α-methylstyrene dimer, methyl 2-bromomethyl acrylate, and diphenyl disulfide. Specific examples of the chain transfer agent having a chain transfer constant of 0.01 or more and 0.1 or less include bromoacetic acid, 4- (benzyloxy) phenol, and 4-methoxyphenol.

  Furthermore, the chain transfer agent of the present invention is preferably a chain transfer agent that undergoes β-cleavage by a chain transfer reaction to form a vinylidene group. When these chain transfer agents are used, a vinylidene group can be introduced into the end of the main chain of the non-crystalline polymer or the composite polymer or both of the resin composition, and the resin composition is polymerizable or reactive. This is because there is an advantage that can be provided. Examples of the chain transfer agent that causes β-cleavage by a chain transfer reaction and forms a vinylidene group include methyl 2-bromomethyl acrylate and methyl methacrylate dimer, but the present invention is not limited thereto. FIG. 4 shows a chemical reaction in which a chain transfer agent causes β-cleavage by a chain transfer reaction to form a vinylidene group, taking methyl methacrylate dimer as an example. The radical 21 of the growing polymer 20 moves to the methyl methacrylate dimer 22 that is a chain transfer agent, and the methyl methacrylate dimer 22 is added to the terminal of the growing polymer 20. Next, cleavage of the carbon-carbon bond at the α-position and β-position occurs, and the tertiary carbo radical 24 is eliminated, whereby a vinylidene group 23 is formed at the terminal of the growing polymer 20.

  Although the usage-amount of the chain transfer agent in this invention is not limited in the range which can achieve the objective of this invention, It is preferable that they are 1 mol% or more and 50 mol% or less with respect to a radical polymerization initiator.

  As the radical polymerization initiator contained in the polymerizable composition of the present invention, various substances such as a peroxide polymerization initiator and an azo polymerization initiator can be used. Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other examples include t-butyl peroxyallyl monocarbonate and the like. It is. Examples of the azo polymerization initiator that can be used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), etc. Illustrated. However, the radical polymerization initiator is not limited to these as long as the object of the present invention can be achieved. Further, one kind of radical polymerization initiator may be used, or a plurality of radical polymerization initiators may be appropriately mixed and used.

  Moreover, it is preferable that the said radical polymerization initiator is contained in the ratio of 0.5 to 20 mass parts with respect to 100 mass parts of radically polymerizable monomers.

  The radical polymerization initiator may be contained in the polymerizable composition before the suspending step or within the suspending step or after the suspending step as long as the object of the present invention can be achieved. .

  The organic solvent contained in the polymerizable composition of the present invention preferably has low solubility in water and high solubility in radically polymerizable monomers. Thus, in the suspension 1 of FIG. 1, the organic solvent can remain in the oil droplets without being dissolved from the oil droplets made of the polymerizable composition into the aqueous medium. For example, toluene, xylene, hexane, etc. are mentioned. These can be used alone or in admixture of two or more.

  The dispersion aid contained in the polymerizable composition of the present invention is soluble in the polymerizable composition of the present invention and is typified by a carboxyl group, a phosphoric acid group, a sulfonic acid group, and metal salts thereof. Examples include polymers containing charged groups. As shown in FIG. 1, such a polymer is obtained by dispersing the polymerizable composition 1 in an aqueous medium to obtain a suspension 1 of the polymerizable composition 1. It can be said that the compound is useful in achieving the object of the present invention because it can be expected to have a function of improving the dispersion stability of the suspension 1 by being unevenly distributed at the interface between the aqueous medium and the aqueous medium. It has been found by experiments of the inventors that the dispersion aid of the present invention is preferably insoluble or insoluble in water in order to improve the dispersion stability of the suspension.

  In the present invention, the following solubility test is applied as a method for judging the solubility, insolubility, and poor solubility of the dispersion aid. The radical polymerizable monomer of the present invention or ion-exchanged water having a pH of 5 to 9 is mixed with a dispersion aid so as to be 3% by mass to obtain a mixed solution, which is shaken at 80 ° C. for 24 hours and then up to 60 ° C. The temperature is lowered and left for 24 hours. At this time, it is judged that the case where it exists as a homogeneous solution is soluble, the incompletely dissolved state showing a gel or granular appearance is hardly soluble, and the state where there is no gel or swelling is insoluble.

  The peak molecular weight of the polymer used for the dispersion aid is preferably 1,000 to 50,000 in terms of molecular weight distribution evaluated using GPC, chloroform as a developing solvent, and styrene conversion. When the peak molecular weight is smaller than 1000, when the polymerizable composition 1 is dispersed in the aqueous medium 13 to obtain the suspension 1 of the polymerizable composition 1 as shown in FIG. In some cases, it is difficult to improve the dispersion stability of the suspension 1 because the ability to be unevenly distributed at the interface between the aqueous medium 13 and the aqueous medium 13 is small. Moreover, when the peak molecular weight is larger than 50000, the viscosity of the polymerizable composition 1 may increase, and the granulation property of the resin particles may decrease.

  As the wax to be included in the polymerizable composition, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic Block copolymer of hydrocarbon wax; wax mainly composed of fatty acid ester such as carnauba wax, sazol wax, and montanic acid ester wax; and partially or fully deoxidized fatty acid ester such as deoxidized carnauba wax And a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The molecular weight distribution of the wax is preferably GPC, chloroform as a developing solvent, and the main peak evaluated as styrene conversion is in the region of molecular weight 400 to 2400, more preferably in the region of 430 to 2000. preferable. Thereby, preferable thermal characteristics can be imparted to the toner. The amount of the wax added is preferably 2.50 parts by mass or more and 40.0 parts by mass or less, and 3.00 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the radical polymerizable monomer. It is more preferable.

  As the colorant to be contained in the polymerizable composition of the present invention, a known colorant such as various conventionally known dyes and pigments can be used.

  Examples of the color pigment for yellow include C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, 185. Examples of the color pigment for magenta include C.I. I. Pigment red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 178, 179, 190, 202, C.I. I. Pigment Violet 19, 23. Such a pigment may be used alone, or a dye and a pigment may be used in combination. Examples of the color pigment for cyan include C.I. I. Pigment Blue 15, 15: 1, 15: 3, or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton. As the black colorant, carbon black, aniline black, acetylene black, titanium black, and those which are toned in black using the yellow / magenta / cyan colorant shown above can be used.

  The aqueous medium in the present invention is a liquid containing water as a main component. Specific examples include water itself, water added with a pH adjusting agent, water added with a dispersant, and the like. As long as the dispersion stability of the suspension 1 in FIG. 1 is not impaired, a mixed liquid of water and a water-soluble organic solvent such as alcohol may be used.

  The pH adjuster that can be used in the aqueous medium of the present invention is not limited within a range in which the object of the present invention can be achieved. For example, a compound that exhibits acidity when dissolved in water, such as hydrochloric acid, sodium hydroxide, etc. Examples of compounds that exhibit alkalinity when dissolved in water are as follows.

  In the present invention, a dispersant may be contained in the aqueous medium for the purpose of improving the dispersion stability of the suspension. As long as the object of the present invention can be achieved, the dispersing agent may be contained at any timing before, during or after the suspension step, but preferably before or during the suspension step. In process. In the present invention, conventionally known dispersants can be used. For example, anionic low molecular surfactant, cationic low molecular surfactant, nonionic low molecular surfactant, anionic polymer dispersant, cationic polymer dispersant, nonionic polymer dispersant, inorganic dispersant Among these, inorganic dispersants are preferable because they have a large dispersion stabilizing effect and exhibit excellent stability against temperature changes. The use of an inorganic dispersant is also preferable from the viewpoint that separation and purification of the target resin particles can be facilitated. Examples of such inorganic dispersants include calcium phosphate, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate and other phosphate polyvalent metal salts, calcium carbonate, magnesium carbonate and other carbonates, calcium metasilicate, sulfuric acid Examples thereof include inorganic salts such as calcium and barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina. However, the inorganic dispersant is not limited to these as long as the object of the present invention can be achieved. A dispersing agent can be used alone or in combination of two or more.

  In the suspension step of the present invention, a conventionally known stirring / shearing device can be used. For example, a suspension can be obtained based on mechanical energy application, such as a high shear type homomixer, an ultrasonic homogenizer, a high pressure homogenizer, and a thin film swirl type high speed mixer. These methods can be used alone or in combination.

  In the production method of the present invention, as a method for inducing radical polymerization, a general method for inducing radical polymerization such as heating or ultraviolet irradiation can be applied. Among these, heating is preferable from the viewpoint of workability and controllability of chemical reaction, and is preferable.

  In the method for producing resin particles of the present invention, if necessary, if a radical polymerizable monomer remains in the resin particles after obtaining the resin particles, it can be removed by a purification operation such as distillation.

  The resin composition of the present invention will be described.

  The resin composition of the present invention contains a composite polymer and an amorphous polymer, and the composite polymer is a block polymer formed by chemically bonding a crystalline polymer and an amorphous polymer.

  The crystalline polymer of the present invention is as described above.

  The amorphous polymer of the present invention is a polymer obtained by radical polymerization of the radical polymerizable polymer of the present invention, or a copolymer thereof.

  The amorphous polymer of the present invention is not particularly limited as long as the object of the present invention can be achieved. When using the resin composition of the present invention as a resin binder for, for example, an inkjet ink or an electrophotographic toner, when the storage stability and the low-temperature fixability are aligned, the following ranges of non-crystallized peak molecular weight and glass transition temperature: It is preferable to use a conductive polymer. The peak molecular weight is 2000 or more and 50000 or less, and more preferably 2000 or more and 30000 or less. Further, the glass transition temperature is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 55 ° C. or higher and 75 ° C. or lower.

  In the present invention, when obtaining the peak molecular weight and glass transition temperature of an amorphous polymer, an amorphous polymer not derived from a composite polymer extracted from a resin composition by the following method is used. A resin composition and acetone are mixed and stirred at 40 ° C. for 30 minutes to form a mixed solution. The mixed solution is cooled to room temperature and then centrifuged to obtain a non-crystal derived from a composite polymer that is an acetone-soluble component. The supernatant liquid containing the functional polymer is recovered. Acetone is removed from the supernatant by drying under reduced pressure to obtain an amorphous polymer for obtaining the peak molecular weight and the glass transition temperature.

  The molecular weight of the composite polymer of the present invention is not limited as long as the object of the present invention can be achieved, but the peak molecular weight is preferably 5000 or more and 200,000 or less, and more preferably 5000 or more and 100,000 or less. The composite polymer is a block polymer formed by chemically bonding a crystalline polymer and an amorphous polymer. When the peak molecular weight is less than 5000, the main chain of the crystalline polymer is difficult to form a folded structure, and the crystallinity is reduced. May decrease. On the other hand, when the peak molecular weight is greater than 100,000, the entanglement between the composite polymers becomes remarkable, and a pseudo three-dimensional network structure is formed in the resin composition, so that the degree of inhibition of deformation of the resin composition upon heating is large. There is a case.

  The molecular weight of the amorphous polymer and the composite polymer of the present invention is a main peak in GPC measurement when chloroform is used as a developing solvent, and is a value calculated in terms of polystyrene.

  The composite polymer contained in the resin composition of the present invention is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the amorphous polymer. When the amount is less than 5 parts by mass, the resin composition of the present invention may not exhibit sufficient low-temperature fixability when used as a resin binder for inkjet inks or electrophotographic toners. On the other hand, when the amount is more than 60 parts by mass, the entanglement between the composite polymers becomes remarkable, and a pseudo three-dimensional network structure is formed in the resin composition, so that the degree of suppression of deformation during heating of the resin composition increases. There is a case. However, the proportion of the amorphous polymer not derived from the composite polymer and the composite polymer contained in the resin composition is not limited to the above as long as the object of the present invention can be achieved.

  The ratio of the composite polymer contained in the resin composition and the amorphous polymer not derived from the composite polymer can be evaluated by the following method. A resin composition and acetone are mixed and stirred at 40 ° C. for 30 minutes to form a mixed solution. The mixed solution is cooled to room temperature and then centrifuged to obtain a non-crystal derived from a composite polymer that is an acetone-soluble component. The supernatant liquid containing the functional polymer and the precipitate derived from the composite polymer are recovered. Acetone is removed from the supernatant and the precipitate by drying under reduced pressure to obtain an amorphous polymer not derived from the composite polymer and the composite polymer, and then the respective masses are measured.

  The resin composition of the present invention is characterized by containing a vinylidene group. The presence or absence of a vinylidene group in the resin composition can be confirmed by analyzing a 1H-NMR spectrum. Specifically, the 1H-NMR spectrum obtained by dissolving the resin composition of the present invention in deuterated chloroform and measuring 1H-NMR is 5.6 to 5.9 ppm, and 5.1 to 5 When there is a peak of 4 ppm, vinylidene groups are present in the resin composition. This vinylidene group is derived from a composite polymer when a chain transfer agent that forms a vinylidene group is generated by β-cleavage by a chain transfer reaction when radically polymerizing the polymerizable composition of the present invention to obtain a resin composition. Derived from the vinylidene group introduced into the non-crystalline polymer or non-crystalline polymer derived from the composite polymer, or both. Various functions can be imparted to such a resin composition having a vinylidene group by utilizing its polymerizability and reactivity. For example, when such a resin composition is used as a resin binder for an inkjet ink or an electrophotographic toner, an advantage that a polymerization reaction derived from a vinylidene group is induced at the time of heat-fixing and can provide fastness to an image to be formed. Can be expected.

  The resin composition of the present invention may contain a compound other than the composite polymer or amorphous polymer of the present invention such as a wax or a colorant, as long as the object of the present invention can be achieved. Resin particles comprising a resin composition containing a wax and a colorant can be used as a toner. In this case, it can be used as it is as a one-component developer or as a two-component developer by mixing with a magnetic carrier. When used as a two-component developer, the average particle size of the carrier to be mixed is preferably 10 to 100 μm, and the toner concentration in the developer is preferably 2 to 15% by mass.

  The resin particles of the present invention are resin particles comprising the resin composition of the present invention. When the resin particles are used as a resin binder for inkjet inks or electrophotographic toners, the number average particle size of the resin particles of the present invention is 0.05 to 8 μm, and the volume average particle size is divided by the number average particle size. The defined particle size distribution index (Dv / Dn) is preferably 1.0 to 1.4.

  Examples of the resin particles in the present invention will be described below, but the present invention is not limited to these examples.

(Granulation property)
The value of the ratio (D4 / D1) of the weight average particle size (D4) and the number average particle size (D1) of “Coulter Counter Multisizer 3” was evaluated as an index of granulation properties. In the present invention, “good” and “fair” were judged to have good granulation properties, and “bad” was judged to have poor granulation properties.
Evaluation criteria good: D4 / D1 is less than 1.20 fair: D4 / D1 is 1.20 or more and less than 1.40 bad: D4 / D1 is 1.40 or more

(Evaluation of half width of endothermic peak of crystalline polyester and heat of crystal melting ΔHm)
Using a differential scanning calorimeter (DSC, DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd.), 0.01 to 0.02 g of the sample was measured on an aluminum pan, and the temperature rising rate from −20 ° C. to 150 ° C. was 10 ° C./min. (2ndRUN) and kept in that state for 5 minutes, then rapidly cooled to −20 ° C. at a temperature drop rate of 1 ° C./min, and again heated from −20 ° C. to 150 ° C. at a temperature rise rate of 10 ° C./min (2ndRUN). ). Then, the half-value width of the endothermic peak was calculated from the peak of heat of crystal fusion in the differential scanning calorimetry chart obtained at 2ndRUN, and the heat of crystal fusion ΔHm was calculated from the peak area.

(Method of measuring molecular weight of composite polymer and radical polymerizable monomer polymer)
After mixing resin particles and acetone and stirring at 40 ° C. for 30 minutes to obtain a mixed solution, the mixed solution is cooled to room temperature and then centrifuged to contain a radical polymerizable monomer polymer which is an acetone-soluble component. Collect the supernatant. Acetone is removed from the supernatant by drying under reduced pressure to obtain a radical polymerizable monomer polymer for obtaining the molecular weight.

  Further, the composite polymer is recovered from the acetone insoluble component.

  The molecular weight was measured by gel permeation chromatography (apparatus: HLC-8120GPC manufactured by Tosoh Corporation, column: TSKgel G2000HXL / G3000HXL / G4000HXL manufactured by Tosoh Corporation) using the peak molecular weight (Mp). After dissolving the sample in chloroform using chloroform as a solution, GPC measurement was performed and the molecular weight was evaluated in terms of styrene.

(Synthesis of crystalline polyester 1)
Ω-pentadecalactone: 100 parts by mass ε-caprolactone: 23.7 parts by mass benzyl alcohol: 0.45 parts by mass 1,5,7-triazabicyclo [4.4.0] dec-5- En: 0.58 parts by mass The above raw materials were charged into a pressure-resistant reaction vessel. The inside of the system was replaced with nitrogen and the pressure-resistant reaction vessel was sealed, then immersed in an oil bath at 180 ° C. and stirred for 6 hours with a magnetic stirrer. Next, a solution prepared by dissolving 17 parts by mass of 11-mercaptoundecanoic acid (manufactured by Aldrich) in 17 parts by mass of toluene was added with nitrogen pressurization, followed by stirring for 3 hours. Thereafter, the product was taken out from the oil bath and cooled to room temperature, and chloroform was added to the system to dissolve the product, which was poured into a large amount of methanol. Crystalline polyester 1 (peak molecular weight (Mp): 29,000) was synthesized by filtering the precipitate and performing vacuum drying.

  When the half width of the endothermic peak and the crystal melting heat ΔHm of the obtained crystalline polyester 1 were measured by DSC, the half width was 6 ° C. and ΔHm was 140.

  Moreover, when it analyzed by the combustion ion chromatography of the crystalline polyester 1, it was confirmed that the sulfur element contains. Crystalline polyester 1 was analyzed by NMR. The reaction was stopped immediately before 11-mercaptoundecanoic acid was added, and the recovered crystalline polyester was subjected to 1H-NMR measurement. As a result, the peak intensity ratio derived from methylene contacting the hydroxyl group at the polymer terminal and the peak intensity derived from the methylene group of the main chain From this, it was confirmed that one end of the polymer was a hydroxyl group. Furthermore, when 1H-NMR of crystalline polyester 1 recovered after the reaction by adding 11-mercaptoundecanoic acid was measured, the methylene-derived peak in contact with the hydroxyl group at the end of the polymer disappeared, but adjacent to the thiol group. A peak derived from methylene was measured. Therefore, it was confirmed that the crystalline polyester 1 has a thiol group on one end of the polymer.

(Synthesis of crystalline polyester 2)
-1,12-dodecanediol 100 mass parts-Sebacic acid 90.9 mass parts The said raw material was prepared to the three necked flask. The inside of the system was purged with nitrogen by depressurization, and then immersed in an oil bath at 160 ° C. with nitrogen flowing. After the raw material was melted, 0.17 part by mass of tetrabutyl orthotitanate was added to the system, and the mixture was stirred for 3 hours with a mechanical stirrer. Thereafter, the temperature was gradually raised to 180 ° C. under reduced pressure while continuing the stirring, and was further maintained for 3 hours. Next, a solution in which 17 parts by mass of 11-mercaptoundecanoic acid was dissolved in 17 parts by mass of toluene was added with nitrogen pressurization, followed by stirring for 3 hours. Thereafter, nitrogen was introduced into the system and cooled to stop the reaction. Chloroform was added to the system to dissolve the product, which was poured into a large amount of methanol. Crystalline polyester 2 (peak molecular weight (Mp): 24,800) was synthesized by filtering the precipitate and performing vacuum drying.

  When the half width of the endothermic peak and the crystal melting heat ΔHm of the obtained crystalline polyester 2 were measured by DSC, the half width was 6 ° C. and ΔHm was 135 J / g.

  Moreover, when the crystalline polyester 2 was analyzed by combustion ion chromatography, it was confirmed that sulfur element was contained. Crystalline polyester 2 was analyzed by NMR. The reaction was stopped immediately before 11-mercaptoundecanoic acid was added, and 1H-NMR of the recovered crystalline polyester was measured. As a result, the peak intensity derived from methylene contacting the hydroxyl group of the polymer terminal and the peak intensity derived from the methylene group of the main chain were measured. From the ratio, it was confirmed that both ends of the polymer were hydroxyl groups. Furthermore, when 1H-NMR of crystalline polyester 2 recovered after the reaction by adding 11-mercaptoundecanoic acid was measured, the methylene-derived peak in contact with the hydroxyl group at the end of the polymer disappeared, but adjacent to the thiol group. A peak derived from methylene was measured. Therefore, it was confirmed that the crystalline polyester 2 has thiol groups at both ends of the polymer.

(Synthesis of crystalline polyester 3)
45 g of crystalline polyester 2 is placed in a 1000 ml three-necked glass flask, and a septum, a thermometer, and a nitrogen inlet tube are attached, and nitrogen flow is performed for 2 hours. Thereafter, 140 g of dehydrated chloroform (manufactured by Kanto Chemical Co., Inc.) is added using a syringe and stirred to dissolve completely. Then, while cooling the flask in an ice bath, 2.3 g of triethylamine (manufactured by Kanto Chemical Co.), which has been dehydrated in advance, is added and stirred well. Next, 7 g of 2-bromoisobutyryl bromide (manufactured by Aldrich) was gradually added dropwise while cooling the flask with an ice bath so that the temperature of the solution was 10 ° C. or less. Continue stirring at room temperature for 24 hours. After 24 hours, when the reaction was completed, the contents in the glass container were put into a large amount of ethanol, and the precipitate was collected. This precipitate was dried under reduced pressure to obtain powdery crystalline polyester 3.

(Synthesis of composite polymer 1)
-Crystalline polyester 3: 100 parts by mass-Styrene: 2000 parts by mass-Dimethylformamide: 400 parts by mass-N, N, N ', N ", N" -pentamethyldiethylenetriamine: 4.1 parts by mass Of raw materials. After stirring and dissolving all, vacuum freeze degassing was repeated three times using liquid nitrogen, and after stirring again to dissolve everything, nitrogen bubbling was performed for 1 hour. Thereafter, 3.40 parts by mass of copper (I) bromide was added under a nitrogen flow and stirred for 1 minute, and then the polymerization reaction was started in an oil bath at 100 ° C. One hour after starting the reaction, the reaction solution was cooled and poured into a large amount of ethanol. The precipitate was filtered and vacuum dried to obtain a composite polymer (peak molecular weight (Mp): 53,000). From the 1H-NMR measurement using deuterated chloroform as a solvent, the weight fraction of the crystalline polyester and polystyrene in the composite polymer 1 was estimated to be 30% and 70%, respectively.

(Synthesis of chain transfer agent 1)
In a sealed container, methyl methacrylate is dissolved in toluene and heated at 60 ° C. for 30 hours in the presence of a cobalt (III) complex (etc.) as a catalyst. Thereafter, the reaction solution was purified with a silica gel column and fractionated by distillation to obtain a chain transfer agent 1 having a molecular weight of 200. The compound was identified using NMR. (Reference: Journal of Polymer Science Part A: Polymer Chemistry, Vol 32, 2745-2754 (1994))

(Synthesis of polystyrene 1, 2, 3)
-Styrene: 204 parts by mass-VA057 (Wako Pure Chemical Industries): 20 parts by mass-Ethanol / toluene mixed solvent: 300 parts by mass The following raw materials were charged into a three-necked flask. The system was purged with nitrogen by nitrogen bubbling, and then stirred at 70 ° C. for 3 hours in a nitrogen flow state. Thereafter, the reaction solution was poured into a large amount of methanol / toluene mixed solvent. The precipitate was collected and vacuum dried to obtain polystyrene. Here, polystyrene 1 having different number average molecular weights (number average molecular weight (Mn): 2000) is obtained by performing an experimental operation of arbitrarily changing the ratio of methanol and toluene in the methanol / toluene mixed solvent to collect precipitates. Polystyrene 2 (number average molecular weight (Mn): 1100) and polystyrene 3 (number average molecular weight (Mn): 600) were obtained.

(Synthesis of chain transfer agent 2)
Polystyrene 1: 100 parts by mass 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride: 47.9 parts by mass The following raw materials were charged in a two-necked flask. After substituting the inside of the system with nitrogen by a depressurization operation, 100 parts by mass of dehydrated chloroform was added in a nitrogen flow state. The flask was immersed in an ice bath, 23.0 parts by mass of 3-mercapto-1-propanol and 3.1 parts by mass of N, N-dimethylaminopyridine were added, followed by stirring at room temperature for 6 hours. Thereafter, the reaction solution was poured into a large amount of methanol. The precipitate was filtered and vacuum dried to synthesize chain transfer agent 2 (peak molecular weight (Mp): 2200).

(Synthesis of chain transfer agent 3)
Instead of polystyrene 1, polystyrene 2 was replaced with 76.7 parts by mass of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 36.9 parts by mass of 3-mercapto-1-propanol, N, N-dimethyl. A chain transfer agent 3 (peak molecular weight (Mp): 1200) was synthesized in the same manner as the chain transfer agent 2 except that the aminopyridine was changed to 4.9 parts by mass.

(Synthesis of chain transfer agent 4)
Instead of polystyrene 1, polystyrene 3 was replaced with 124.6 parts by mass of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 60.0 parts by mass of 3-mercapto-1-propanol, N, N- Chain transfer agent 4 (peak molecular weight (Mp): 800) was synthesized in the same manner as chain transfer agent 2 except that dimethylaminopyridine was changed to 7.9 parts by mass.

(Synthesis of dispersion aid)
A 500 ml flask equipped with a stirrer, a condenser tube, a thermometer, and a nitrogen inlet tube was charged with 100 g of toluene, 100 g of styrene, 4.0 g of methacrylic acid, and 0.5 g of azobisisobutyronitrile (AIBN). Under stirring and introduction of nitrogen, solution polymerization was performed at 60 ° C. for 10 hours, the contents were taken out from the flask, and the precipitate was collected by filtration. Subsequently, the dispersion aid 2 (peak molecular weight: 12,000) having styrene as a hydrophobic unit and methacrylic acid as a hydrophilic unit was obtained by drying at 40 ° C. under reduced pressure.

Example 1
<Preparation of resin particle 1>
130 g of ion-exchanged water was placed in a 200 ml three-necked flask, 2.53 g of calcium phosphate was added thereto, and the mixture was stirred at 15,000 rpm using a homomixer to prepare an aqueous medium.
・ Styrene 15.4g
・ N-butyl acrylate 3.8 g
-Crystalline polyester 1 3.9 g
・ Radical polymerization initiator (trade name “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.); 10 hour half-life temperature 51 ° C.) 0.35 g
・ Dispersing aid 1.3g
The above materials are mixed to obtain a polymerizable composition, which is added to the aqueous medium stirred (10,000 rpm) at a suspension temperature of 60 ° C. and stirred for 15 minutes (15,000 rpm) with a homomixer. As a result, a suspension was prepared by forming oil droplets of the polymerizable composition in water. Next, nitrogen suspension was performed for 30 minutes while stirring the suspension (200 rpm), and then the polymerization temperature was set to 60 ° C. and maintained for 6 hours while stirring (200 rpm) to obtain an aqueous dispersion of resin particles. Prepared. Finally, concentrated hydrochloric acid was added to the aqueous dispersion, followed by filtration washing and drying under reduced pressure, and the powdered resin particles 1 were recovered.

  The resin particles 1 and acetone are mixed and stirred at 40 ° C. for 30 minutes to obtain a mixed solution, and then the mixed solution is cooled to room temperature and then centrifuged to contain an amorphous polymer that is an acetone-soluble component. Collect the supernatant. Acetone was removed from the supernatant by drying under reduced pressure to obtain an amorphous polymer. When the molecular weight was measured, the peak molecular weight Mp was 15,000.

  Further, a composite polymer in which a polymer of a radical polymerizable monomer was added to the chain transfer group of the crystalline polyester was recovered from the acetone insoluble component. When the molecular weight of this insoluble component was measured, the peak molecular weight Mp was 53,500.

  Regarding the granulation property, it was good when evaluated as described above.

  Table 1 summarizes the characterization of the resin particles 1 obtained.

  In addition, from the time when the suspension temperature was heated to 60 ° C., 2 ml of the suspension was sampled after 15, 30, 60, 120, 240, and 360 minutes, respectively, and the composite polymer was recovered from the acetone-insoluble component of each sample, The molecular weight was measured by GPC to obtain the relationship between the polymerization time and the peak molecular weight Mp of the composite polymer (FIG. 5).

(Example 2)
<Preparation of resin particle 2>
Resin particles 2 were obtained in the same manner except that the crystalline polyester 2 was used instead of the crystalline polyester 1 in the operation of Example 1.

  The molecular weights of the acetone-soluble component and the insoluble component of the resin particle 2 were measured in the same manner as in Example 1. As a result, the acetone-soluble component had a peak molecular weight Mp16,000, and the acetone-insoluble component had a peak molecular weight Mp52,000. .

  Regarding the granulation property, it was good when evaluated as described above.

  Table 1 summarizes the characterization of the resin particles 2 obtained.

(Example 3)
<Preparation of resin particle 3>
To the polymerizable composition in Example 1, 0.08 g of chain transfer agent 2 was further added to prepare a polymerization composition. Otherwise in the same manner as in Example 1, resin particles 3 were obtained.

  The molecular weights of the acetone-soluble component and the insoluble component of the resin particle 3 were measured in the same manner as in Example 1. As a result, the acetone-soluble component had a peak molecular weight Mp17,000, and the acetone-insoluble component had a peak molecular weight Mp55,000. .

  Regarding the granulation property, it was good when evaluated as described above.

  Table 1 summarizes the characterization of the resin particles 3 obtained.

  In addition, from the time when the suspension temperature was heated to 60 ° C., 2 ml of the suspension was sampled after 15, 30, 60, 120, 240, and 360 minutes, respectively, and the composite polymer was recovered from the acetone-insoluble component of each sample, The molecular weight was measured by GPC to obtain the relationship between the polymerization time and the peak molecular weight Mp of the composite polymer (FIG. 5).

Example 4
<Preparation of Resin Particle 4>
Resin particles 4 were obtained in the same manner as in Example 3 except that 0.08 g of chain transfer agent 3 was used instead of 0.08 g of chain transfer agent 2 in the operation of Example 3.

  When the molecular weights of the acetone-soluble component and the insoluble component of the resin particle 4 were measured by the same method as in Example 1, the acetone-soluble component had a peak molecular weight Mp17,000 and the acetone-insoluble component had a peak molecular weight Mp55,000. .

  Regarding the granulation property, it was good when evaluated as described above.

  Table 1 summarizes the characterization of the resin particles 4 obtained.

  In addition, from the time when the suspension temperature was heated to 60 ° C., 2 ml of the suspension was sampled after 15, 30, 60, 120, 240, and 360 minutes, respectively, and the composite polymer was recovered from the acetone-insoluble component of each sample, The molecular weight was measured by GPC to obtain the relationship between the polymerization time and the peak molecular weight Mp of the composite polymer (FIG. 5).

(Example 5)
<Preparation of resin particle 5>
Resin particles 5 were obtained in the same manner as in Example 3 except that 0.08 g of chain transfer agent 4 was used instead of 0.08 g of chain transfer agent 2 in the operation of Example 3.

  When the molecular weights of the acetone soluble component and the insoluble component of the resin particle 5 were measured in the same manner as in Example 1, the acetone soluble component had a peak molecular weight Mp18,000 and the acetone insoluble component had a peak molecular weight Mp54,500. .

  Regarding the granulation property, it was good when evaluated as described above.

  Table 1 summarizes the characterization of the resin particles 5 obtained.

  In addition, from the time when the suspension temperature was heated to 60 ° C., 2 ml of the suspension was sampled after 15, 30, 60, 120, 240, and 360 minutes, respectively, and the composite polymer was recovered from the acetone-insoluble component of each sample, The molecular weight was measured by GPC to obtain the relationship between the polymerization time and the peak molecular weight Mp of the composite polymer (FIG. 5).

(Example 6)
<Preparation of resin particle 6>
Resin particles 6 were obtained in the same manner as in Example 3 except that 0.08 g of chain transfer agent 1 was used instead of 0.08 g of chain transfer agent 2 in the operation of Example 3.

  When the molecular weights of the acetone soluble component and the insoluble component of the resin particle 6 were measured in the same manner as in Example 1, the acetone soluble component had a peak molecular weight Mp17,500, and the acetone insoluble component had a peak molecular weight Mp55,000. .

  Regarding the granulation property, it was good when evaluated as described above. Table 1 summarizes the characterization of the resin particles 6 obtained.

  In addition, from the time when the suspension temperature was heated to 60 ° C., 2 ml of the suspension was sampled after 15, 30, 60, 120, 240, and 360 minutes, respectively, and the composite polymer was recovered from the acetone-insoluble component of each sample, The molecular weight was measured by GPC to obtain the relationship between the polymerization time and the peak molecular weight Mp of the composite polymer (FIG. 5).

  Moreover, when the resin particle 6 was melt | dissolved in deuterated chloroform and 1H-NMR was measured, the peaks of 5.7 ppm and 5.2 ppm derived from the vinylidene group structure were observed.

(Example 7)
<Preparation of resin particle 7>
Resin particles 7 were obtained in the same manner as in Example 3 except that 0.08 g of methyl 2-bromomethylacrylate was used in place of 0.08 g of chain transfer agent 2 in the operation of Example 3.

  When the molecular weights of the acetone soluble component and the insoluble component of the resin particle 7 were measured by the same method as in Example 1, the acetone soluble component had a peak molecular weight Mp18,000 and the acetone insoluble component had a peak molecular weight Mp54,500. .

  Regarding the granulation property, it was good when evaluated as described above.

  Table 1 summarizes the characterization of the resin particles 6 obtained.

  In addition, from the time when the suspension temperature was heated to 60 ° C., 2 ml of the suspension was sampled after 15, 30, 60, 120, 240, and 360 minutes, respectively, and the composite polymer was recovered from the acetone-insoluble component of each sample, The molecular weight was measured by GPC to obtain the relationship between the polymerization time and the peak molecular weight Mp of the composite polymer (FIG. 5).

  Moreover, when the resin particle 7 was melt | dissolved in deuterated chloroform and 1H-NMR was measured, the peaks of 5.7 ppm and 5.2 ppm derived from the vinylidene group structure were observed.

(Comparative Example 1)
Instead of the crystalline polyester 1 in the operation of Example 1, the composite polymer 1 was used. The amount of the mixed resin added was 8.2 g so that the mass part of the crystalline polyester component was 20.5 parts by mass as in Example 1. Otherwise, the same conditions were used to obtain resin particles 8 containing composite polymer 1.

  When the molecular weights of the acetone soluble component and the insoluble component of the resin particle 8 were measured in the same manner as in Example 1, the acetone soluble component had a peak molecular weight Mp16,000, and the acetone insoluble component had a peak molecular weight Mp57,000. .

  Regarding the granulation property, it was bad when evaluated as described above.

(Example 8)
<Preparation of Toner 1>
To 1300.0 parts by mass of ion-exchanged water heated to 60 ° C., 9.0 parts by mass of tricalcium phosphate was added, and the stirring speed was adjusted to 15,000 rpm using a TK homogenizer (manufactured by Tokushu Kika Kogyo). And stirred to prepare an aqueous medium.

Moreover, the liquid mixture was prepared, stirring the following resin material with the stirring speed of 100 rpm with the propeller-type stirring apparatus.
-Styrene: 61.0 parts by mass-n-Butyl acrylate: 18.5 parts by mass-Crystalline polyester 1: 20.5 parts by mass Next,
Cyan colorant (CI Pigment Blue 15: 3): 6.5 parts by mass Negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co.): 0.5 parts by mass Hydrocarbon wax (Tm = (78 ° C.): 9.0 parts by mass, negative charge control resin 1: 0.7 parts by mass, polar resin: 5.0 parts by mass (styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, acid 10 mg KOH / g, Tg = 80 ° C., Mw = 15,000)
After that, the mixture was heated to a temperature of 65 ° C. and then stirred with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a stirring speed of 10,000 rpm to dissolve and disperse the polymerizable monomer composition. Was prepared.

  Subsequently, the polymerizable monomer composition is charged into the aqueous medium, and 6.0 parts by mass of perbutyl PV (10-hour half-life temperature 54.6 ° C. (Nippon Oily)) is added as a polymerization initiator. Using a TK homomixer at 70 ° C., the mixture was stirred for 20 minutes at a stirring speed of 15,000 rpm and granulated.

  It is transferred to a propeller type stirring device and stirred at a stirring speed of 200 rpm, and the styrene and n-butyl acrylate, which are polymerizable monomers in the polymerizable monomer composition, are subjected to a polymerization reaction at a temperature of 85 ° C. for 5 hours to contain toner particles. A slurry was produced. After completion of the polymerization reaction, the slurry was cooled. Hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Then, it wash | cleaned with the amount of water 10 times the slurry, and after filtering and drying, the particle diameter was adjusted by classification and the particle | grain 1 was obtained.

Hydrophobic silica fine particles (primary particle diameter: 7 nm, BET specific surface area) treated with 20% by mass of dimethyl silicone oil as an external additive with respect to 100.0 parts by mass of the particles 1 as an external additive. The toner 1 was obtained by mixing 1.5 parts by mass of 130 m ^{2 /} g) with a Henschel mixer (manufactured by Mitsui Miike) at a stirring speed of 3000 rpm for 15 minutes.
Regarding the granulation property, it was good when evaluated as described above.
Table 2 summarizes the characterization of toner 1 obtained.

Example 9
<Preparation of Toner 2>
Toner 2 was obtained in the same manner as in Example 8, except that crystalline polyester 2 was used instead of crystalline polyester 1.
Regarding the granulation property, it was good when evaluated as described above.
Table 2 summarizes the characterization of toner 2 obtained.

(Example 10)
<Preparation of Toner 3>
To the polymerizable composition in Example 8, 0.9 part by mass of chain transfer agent 1 was further added to prepare a polymerizable composition. Other than that, Toner 3 was obtained in the same manner as in Example 8.

Regarding the granulation property, it was good when evaluated as described above.
Table 2 summarizes the characterization of toner 3 obtained.
Further, when the toner 3 was dissolved in deuterated chloroform and 1H-NMR was measured, peaks of 5.7 ppm and 5.2 ppm derived from the vinylidene group structure were observed.

(Comparative Example 2)
Instead of the crystalline polyester 1 in the operation of Example 8, the composite resin 1 was used. The addition amount was adjusted so that the mass part of the crystalline polyester component was the same as in Example 8. Otherwise, the same conditions were used, and toner 4 containing composite resin 1 was obtained.

  Regarding the granulation property, it was bad when evaluated as described above.

DESCRIPTION OF SYMBOLS 10 Chain transfer group 11 Crystalline polyester 12 Radical polymerizable monomer 13 Aqueous medium 14 Oil droplet A
DESCRIPTION OF SYMBOLS 15 Amorphous polymer 16 Amorphous polymer chemically bonded to crystalline polyester 17 Resin particle comprising resin composition 18 Composite polymer 19 Oil droplet B
20 Growing polymer 21 Radical 22 Methyl methacrylate dimer 23 Vinylidene group 24 Tertiary carboradical 30 Relationship between polymerization time for resin particle 1 and peak molecular weight Mp of composite polymer 31 Polymerization time for resin particle 3 and peak molecular weight Mp of composite polymer 32 Relationship between polymerization time for resin particle 4 and peak molecular weight Mp of composite polymer 33 Relationship between polymerization time for resin particle 5 and peak molecular weight Mp of composite polymer 34 Relationship between polymerization time for resin particle 6 and peak molecular weight Mp of composite polymer 35 Relationship between polymerization time for resin particle 7 and peak molecular weight Mp of composite polymer

Claims (11)

(1) having an endothermic peak measured by differential scanning calorimetry, the half-value width of the endothermic peak being 10 ° C. or less,
(2) having a chain transfer group,
A crystalline polyester characterized by that. The crystalline polyester according to claim 1, wherein the crystalline polyester has a unit represented by the following general formula (1) or general formula (2).

(R ₁ , R ₂ and R ₃ each independently represents a linear alkyl group having 2 to 22 carbon atoms or a branched alkyl group having 2 to 22 carbon atoms, Represents an integer of 5 to 150.)   The crystalline polyester according to claim 1 or 2, wherein the chain transfer group contains a sulfur element.   The crystalline polyester according to claim 2, wherein the chain transfer group is a thiol group.   The crystalline polyester according to any one of claims 1 to 4, wherein the chain transfer group has the chain transfer group at the end of the crystalline polyester. A resin composition containing a composite polymer and an amorphous polymer,
The composite polymer is a block polymer in which a crystalline polyester and an amorphous polymer are chemically bonded,
The resin composition having a vinylidene group. The resin composition according to claim 6, wherein the crystalline polyester has a unit represented by the following general formula (1) or general formula (2).

(R ₁ , R ₂ and R ₃ each independently represents a linear alkyl group having 2 to 22 carbon atoms or a branched alkyl group having 2 to 22 carbon atoms, and m and n are each 5 Represents an integer of ~ 150.)   A resin composition comprising a resin composition synthesized by radical polymerization using the polymerizable composition containing the crystalline polyester according to any one of claims 1 to 5 and a radical polymerizable monomer. Manufacturing method. The polymerizable composition further contains a chain transfer agent,
The method for producing a resin composition according to claim 8, wherein the chain transfer agent has a number average molecular weight of 1000 or less.   The method for producing a resin composition according to claim 8 or 9, wherein the chain transfer agent is a compound that undergoes β-cleavage by radical polymerization to form a vinylidene group.   A suspension comprising particles of the polymerizable composition, wherein the polymerizable composition containing the crystalline polyester according to any one of claims 1 to 5 and a radical polymerizable monomer is dispersed in an aqueous medium. And a resin composition particle is formed by radical polymerization to form a resin composition particle.

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