JP2017039794A - Method for producing resin composition, method for producing resin particle, and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin particle containing a composite polymer formed by chemically bonding a crystalline polymer and a non-crystalline polymer and having a small degree of suppression of deformation upon heating, for example, into an aqueous medium such as suspension polymerization. Provided is a method for producing a polymer without impairing granulation properties by polymerization. A method for producing a resin composition, comprising: forming a resin composition by radical polymerization from a polymerizable composition containing a crystalline polymer, a radical polymerizable monomer, and a chain transfer agent, The crystalline polymer is a radical polymerizable polymer having a radical polymerizable functional group, wherein the radical polymerizable functional group is selected from an acryloyl group, a methacryloyl group, and a styryl group, and the chain transfer agent has a number average molecular weight of less than 1000. A method for producing a resin composition, characterized in that it is a low molecular chain transfer agent. [Selection diagram] None

Description

  The present invention relates to a resin composition and a method for producing resin particles.

  Resin particles are used in various industrial fields. When using resin particles as a resin binder for inkjet inks and electrophotographic toners, it is proposed to use resin particles consisting of a mixture of crystalline and non-crystalline polymers from the viewpoint of paralleling storage stability and low-temperature fixability. (Patent Document 1). However, when a combination of a crystalline polymer and an amorphous polymer is not appropriate, these polymers may macroseparate into two phases during heating, and the resin particles may not exhibit sufficient low-temperature fixability.

  For this problem, a method using resin particles containing a composite polymer formed by chemically bonding a crystalline polymer and an amorphous polymer is effective (Patent Document 2). However, since such a composite polymer has a large molecular weight, for example, if it is included in resin particles obtained by aqueous medium heterogeneous polymerization such as suspension polymerization, the viscosity of the polymerizable composition is increased, and the resin In some cases, the granulation properties of the particles are lowered.

  To solve the above-mentioned problem of decrease in granulation property, a method in which a crystalline polymer has a radical polymerizable polymer having a radical polymerizable functional group and a composite polymer is formed in resin particles in a suspension polymerization process. There is a possibility that it can be solved. However, since the resin particles obtained in this way have a three-dimensional network structure composed of a crystalline polymer and an amorphous polymer, deformation of the resin particles during heating is suppressed, and low-temperature fixability is impaired. There was a case.

JP 2010-145550 A JP 2010-139659 A

  Resin particles containing a composite polymer formed by chemically bonding a crystalline polymer and an amorphous polymer and having a low degree of suppression of deformation during heating are produced by, for example, aqueous medium heterogeneous polymerization such as suspension polymerization. Provided is a method for manufacturing without impairing grain properties.

The first invention is
A method for producing a resin composition comprising synthesizing a resin composition by radical polymerization using a polymerizable composition containing a crystalline polymer, a radical polymerizable monomer, and a chain transfer agent,
The crystalline polymer is a radical polymerizable polymer having a radical polymerizable functional group,
The radical polymerizable functional group is a functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group;
The chain transfer agent has a number average molecular weight of less than 1000;
The present invention relates to a method for producing a resin composition.

The second invention of the present invention is
A resin composition containing a composite polymer and an amorphous polymer,
The composite polymer is a branched polymer in which a crystalline polymer and an amorphous polymer are chemically bonded,
The resin composition has a vinylidene group.

  According to the present invention, a resin composition having excellent storage stability and low-temperature fixability can be obtained. In addition, resin particles having a sharp particle size distribution while having these excellent characteristics can be obtained.

It is a figure explaining the method to manufacture a resin particle using a radically polymerizable polymer. It is a figure explaining the method to manufacture a resin particle using a composite polymer. It is a figure explaining the method of forming a resin composition from polymeric composition containing a low molecular chain transfer agent. It is a figure explaining the method of forming a resin composition from polymeric composition which does not contain a low molecular chain transfer agent. It is a figure explaining the chemical reaction in which a chain transfer agent forms a vinylidene group by chain transfer reaction.

  Details of the present invention will be described below.

A first invention is a method for producing a resin composition in which a resin composition is synthesized by radical polymerization using a polymerizable composition containing a crystalline polymer, a radical polymerizable monomer, and a chain transfer agent,
The crystalline polymer is a radical polymerizable polymer having a radical polymerizable functional group,
The radical polymerizable functional group is a functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group;
The chain transfer agent has a number average molecular weight of less than 1000;
The present invention relates to a method for producing a resin composition.

  One of the great features in the first invention is that the polymerizable composition contains a radical polymerizable polymer. In FIG. 1, the schematic diagram in the case of manufacturing a resin particle using the radically polymerizable polymer of this invention is shown. FIG. 2 shows a schematic diagram when resin particles are produced using a non-reactive composite polymer having a crystalline unit and a polymer unit composed of a radical polymerizable monomer instead of the radical polymerizable polymer. However, the chain transfer agent is not shown in FIGS. 1 and 2 for the sake of simplicity.

  In step 11 of FIG. 1, a polymerizable composition 1 containing a radical polymerizable polymer 11, a radical polymerizable monomer 14 and a chain transfer agent is dispersed in an aqueous medium to prepare a suspension 1 of the polymerizable composition. It is a process. Step 12 in FIG. 1 is a radical polymerization of the suspension 1 of the polymerizable composition prepared in Step 11, and a composite polymer 15 (a polymer formed by a reaction between a radical polymerizable polymer and a radical polymerizable monomer) and This is a step of forming a dispersion 1 in which resin particles made of a resin composition 19 containing an amorphous polymer 18 (a polymer of a radical polymerizable monomer) having no unit derived from a composite polymer are dispersed.

  Step 21 in FIG. 2 is a step of preparing a suspension 2 of the polymerizable composition by dispersing the polymerizable composition 2 containing the non-reactive composite polymer 15 and the radical polymerizable monomer 14 in an aqueous dispersion. is there. Step 22 in FIG. 2 is a radical polymerization of the suspension 2 of the polymerizable composition prepared in Step 21, and a non-reactive composite polymer 15 and an amorphous polymer 18 (a polymer of a radical polymerizable monomer) not derived from the composite polymer. ) Containing the resin composition 19 is dispersed to form a dispersion 2 of the resin composition.

  Since the composite polymer 15 has a higher molecular weight than the radical polymerizable polymer 14, the polymerizable composition 2 has a higher viscosity than the polymerizable composition 1. When the polymerizable composition is dispersed in an aqueous medium, it is known that the larger the viscosity of the polymerizable composition, the broader the droplet size distribution of the suspension droplets of the polymerizable composition suspension. ing. From this, when the droplet size distribution of the suspension droplet is broad, the particle size distribution of the resin particles formed by radical polymerization is likely to be broad. Therefore, unlike FIG. 1, in FIG. 2, the risk of reducing the granulation property of the resin particles is great.

  Another major feature of the production method of the present invention is that the polymerizable composition contains a chain transfer agent. In FIG. 3, the schematic diagram in the case of forming a resin composition from the polymeric composition containing the chain transfer agent of this invention is shown. Moreover, the schematic diagram in the case of forming a resin composition from the resin composition which does not contain a chain transfer agent in FIG. 4 is shown. Unlike FIG. 3 in which the chain transfer agent 20 acts as a molecular weight regulator, FIG. 4 shows a composite polymer having a large molecular weight or a composite polymer having a very large molecular weight formed by chemically bonding a plurality of crystalline polymers with an amorphous polymer. Easy to form. Since these characteristic composite polymers function as a three-dimensional network structure in the resin composition, the resin composition 4 has a greater risk of suppressing deformation during heating than the resin composition 3.

  The radically polymerizable polymer of the present invention will be described. The radical polymerizable polymer of the present invention is a compound in which the crystalline polymer has a radical polymerizable functional group.

  The crystalline polymer of the present invention is a polymer compound having a melting temperature. Specifically, it is a polymer compound having a half-value width of an endothermic peak measured by differential scanning calorimetry at a temperature rising rate of 10 ° C./min of 10 ° C. or less. Since such a polymer compound 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.

  The crystalline polymer 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 related to this maximum absorption peak is 50 J / g or more.

  In the present invention, a conventionally known crystalline polymer such as an acrylic (including methacrylic) polymer having a long-chain alkyl group having 15 or more carbon atoms in the side chain, a crystalline polyester, or the like is used as the crystalline polymer. be able to.

  In the present invention, from the viewpoint of toughness and spreadability, it is preferable to use a crystalline polyester as the crystalline polymer. The crystalline polyester is a polycondensate of polyvalent carboxylic acids such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester, polyhydric alcohol, and polyester such as polycaprolactone, It is a polymer compound having the above melting temperature. When used as a resin binder for inkjet inks or electrophotographic toners, it is preferable to apply a crystalline polyester having a melting temperature of 60 ° C. or higher and 110 ° C. or lower to the present invention.

  The crystalline polyester of the present invention is preferably an aliphatic polyester having a unit represented by at least one of the following general formula (1) and general formula (2). This is because such a polyester easily forms a fold structure in the main chain and easily obtains crystallinity.

(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.)
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. The crystalline polyester of the present invention is not limited to these, and can be synthesized by a conventionally 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 hydrolysates such as ¥ may also be used. 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 mol% or more, more preferably 70% or more is an aliphatic monohydroxycarboxylic acid having 2 to 22 carbon atoms or 2 carbon atoms. It is preferred to use -22 lactones.

  As for the molecular weight of the crystalline polymer of the present invention, the main peak (peak molecular weight: Mp) in the molecular weight distribution evaluated as styrene conversion by gel permeation chromatography (hereinafter referred to as GPC) is preferably 3000 to 50000. Within the above range, the main chain can easily form a folded structure, and the viscosity of the polymerizable composition can be suppressed from becoming excessively high.

  The radical polymerizable functional group of the radical polymerizable polymer of the present invention is selected from an acryloyl group, a methacryloyl group, and a styryl group. These functional groups have an advantage that they have good copolymerizability with a radical polymerizable monomer described later and can efficiently form a composite polymer by radical polymerization.

  The crystalline polymer preferably has a radical polymerizable functional group at the main chain terminal. When the crystalline polymer has a radical polymerizable functional group in the main chain, formation of a folded structure of the main chain may be inhibited, and the crystallinity of the radical polymerizable polymer may be impaired. The number of functional groups of the radical polymerizable polymer of the present invention is preferably 0.3 or more and 2.0 or less per one radical polymerizable polymer. By being within the above range, the ratio of the crystalline polymer present as a composite polymer in the resin composition becomes appropriate, and the generation of a special composite polymer as shown in FIG. 4 can be satisfactorily suppressed by radical polymerization. In addition, the radically polymerizable polymer of the present invention can be synthesized by a conventionally known method.

  Whether or not the radically polymerizable polymer of the present invention has a radically polymerizable functional group can be confirmed by identifying peaks derived from these functional groups from the 1H-NMR spectrum. For example, the presence or absence of an acryloyl group can be confirmed by a peak of 5.7 to 6.2 ppm. The presence or absence of a methacryloyl group can be confirmed by a peak at 5.1 to 5.6 ppm. The presence or absence of a styryl group can be confirmed by a peak at 6.5 to 7.0 ppm.

  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. As shown in FIG. 3 and FIG. 4, in the present invention, a chain transfer agent is used for the purpose of suppressing the formation of a special complex polymer such as a complex polymer having a large molecular weight or a complex polymer having a very large molecular weight in the resin composition. Use. According to the study by the inventors, it has been found that such a special composite polymer is remarkably formed in the late stage of radical polymerization, and in the case of a chain transfer agent having a poor number of diffusibility and a number average molecular weight of more than 1000, the inventors Does not produce the expected effect. 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 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. The chain transfer constant is a value determined by the rate constant of the growth reaction, which is one of the elementary reactions of radical polymerization, and the rate constant of the chain transfer reaction. 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 the 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. This is consistent with the object of the present invention. A more preferable range of the chain transfer constant of the chain transfer agent of the present invention is 0.1 or more and 10 or less, and a more preferable range is 0.1 or more and 1 or less. Most of the chain transfer agents having a chain transfer constant larger than 10 are consumed in the first stage of radical polymerization, and therefore, specially formed in the latter stage of radical polymerization as compared with a low molecular chain transfer agent having a chain transfer constant of 10 or less. The ability to suppress complex polymers is small. A chain transfer agent having a chain transfer constant of 1 or less has a high ability to suppress a special composite polymer that is remarkably formed in the late stage of radical polymerization because the unconsumed rate in the late stage of radical polymerization is large.

  As the chain transfer agent of 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. 5 shows a chemical reaction in which a chain transfer agent undergoes β-cleavage by a chain transfer reaction to form a vinylidene group, taking methyl methacrylate dimer as an example. The radical 22 of the growth polymer 21 moves to the methyl methacrylate dimer 23 which is a chain transfer agent, and the methyl methacrylate dimer 23 is added to the end of the main chain of the growth polymer 21. Next, cleavage of the carbon-carbon bond at the α-position and β-position occurs, and the tertiary carbo radical 25 is eliminated, whereby a vinylidene group 24 is formed at the terminal of the growth polymer 21.

  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. When the amount is more than 50 mol%, the polymerization conversion rate of radical polymerization may decrease. If it is less than 1 mol%, the molecular weight adjusting action by the chain transfer agent does not function sufficiently, and by radical polymerization, a special composite polymer such as a composite polymer having a large molecular weight or a composite polymer having a very large molecular weight as shown in FIG. There may be significant formation in the composition.

  As the radical polymerizable monomer of the present invention, a conventionally known radical polymerizable monomer can be used as long as the object of the present invention can be achieved. Among these, it is preferable to use styrene, a styrene derivative, an acrylic ester, or a methacrylic ester as a main component. Examples of other monomers include acrylonitrile, methacrylonitrile, acrylamide, and the like.

  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 to the radical polymerizable monomer having one radical polymerizable functional group in the compound as described above, in the present invention, divinylbenzene, 1,6-hexanediacrylate, 1,6-hexanedimethacrylate, etc. As described above, a radical polymerizable monomer having a plurality of radical polymerizable functional groups in the compound can also be used. In the present invention, a plurality of radical polymerizable monomers may be used in combination.

  The amount of the radically polymerizable monomer and the radically polymerizable polymer of the present invention is not limited within a range in which the object of the present invention can be achieved, but 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the radically polymerizable monomer. It is preferable to use the radically polymerizable polymer. If it is said ratio, the raise of the viscosity of polymeric composition can be suppressed, the fall of the granulation property of a resin particle can be suppressed, and low temperature fixability can be achieved.

  The polymerizable composition of the present invention can contain a compound other than the radically polymerizable polymer, the radically polymerizable monomer, and the chain transfer agent as long as the object of the present invention can be achieved. Specific examples include radical polymerization initiators, organic solvents, and dispersion aids, but are not limited thereto.

  In the present invention, a conventionally known radical polymerization initiator can be used as long as the object of the present invention can be achieved. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2-methylpropanenitrile), 2,2′-azobis- (2,4-dimethylpentanenitrile), 2 , 2′-azobis- (2-methylbutanenitrile), 1,1′-azobis- (cyclohexanecarbonitrile), 2,2′-azobis- (2,4-dimethyl-4-methoxyvaleronitrile), 2, Azo polymerization initiators such as 2′-azobis- (2,4-dimethylvaleronitrile), dibenzoyl peroxide, cumene hydroperoxide, di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxy Dicarbonate, acetyl peroxide, peracid esters (eg t-butyl peroctate, α-cumyl peroxypivalate and t-butyl) It can be exemplified an organic peroxide-based polymerization initiators such as Peruokuteto). Moreover, photo radical polymerization initiators such as acetophenone and ketal are also applicable. 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.

  Although the usage-amount of the radical polymerization initiator of this invention and a radically polymerizable monomer is not limited in the range which can achieve the objective of this invention, 0.5 mass part or more and 20 masses with respect to 100 mass parts of radically polymerizable monomers. It is preferable to use a radical polymerization initiator of less than or equal to part. When the amount is less than 0.5 parts by mass, the polymerization conversion rate of radical polymerization may decrease. On the other hand, when the amount is more than 20 parts by mass, the polymerization heat derived from radical polymerization is excessively generated, and the safety management in the experiment may be difficult.

  There is no particular limitation on the timing of adding the radical polymerization initiator to the polymerizable composition of the present invention as long as the object of the present invention can be achieved.

  In the present invention, the organic solvent that can be contained in the polymerizable composition is not limited as long as the object of the present invention can be achieved. However, for example, the solubility in water such as toluene, xylene, hexane, etc. is low. An organic solvent having high solubility in the radical polymerizable monomer can be used. An organic solvent may be used independently and may be used in mixture of 2 or more types.

  There is no particular limitation on the timing of adding the organic solvent to the polymerizable composition of the present invention as long as the object of the present invention can be achieved.

  In the present invention, as a dispersion aid that can be contained in the polymerizable composition, it is soluble in the polymerization composition of the present invention, and is also used for carboxyl groups, phosphoric acid groups, sulfonic acid groups, and metal salts thereof. Examples thereof include a polymer containing a charged group. Such a polymer is unevenly distributed at the interface between the polymerizable composition of the dispersion and the aqueous medium when the polymerizable composition is dispersed in the aqueous medium to obtain a dispersion of the polymerizable composition as shown in FIG. Thus, the compound has a function of improving the dispersion stability of the dispersion, and thus can be said to be a useful compound for achieving the object of the present invention. It has been found through experiments by 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 dispersion.

  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 1000 or more and 50000 or less in the molecular weight distribution evaluated by GPC as styrene conversion. When the peak molecular weight is less than 1000, when the polymerizable composition is dispersed in an aqueous medium as shown in FIG. 1 to obtain a dispersion of the polymerizable composition, the dispersion is unevenly distributed at the interface between the polymerizable composition and the aqueous medium. In some cases, it is difficult to improve the dispersion stability of the dispersion. Moreover, when a peak molecular weight is larger than 50000, the viscosity of a polymeric composition may rise and the granulation property of a resin particle may fall.

  There is no particular limitation on the timing of adding the dispersion aid to the polymerizable composition as long as the object of the present invention can be achieved.

  The aqueous medium of the present invention is a liquid mainly composed of water. 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 dispersion 1 of the polymerizable composition in FIG. 1 is not impaired, a mixed liquid of water and a water-soluble organic solvent such as alcohol may be used. However, the aqueous medium of the present invention is not limited to these as long as the object of the present invention can be achieved.

  The pH adjuster that can be used in the aqueous medium of the present invention is not particularly limited as long as 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 Examples thereof include compounds that exhibit alkalinity when dissolved in water.

  The dispersant that can be used in the aqueous medium is not particularly limited as long as the object of the present invention can be achieved, and examples thereof include an anionic low molecular surfactant, a cationic low molecular surfactant, and a nonionic low molecular surfactant. Agents, anionic polymer dispersants, cationic polymer dispersants, nonionic polymer dispersants, inorganic dispersants, and the like. 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.

  In the method for producing resin particles of the present invention, a conventionally known stirring / shearing method can be used as a method for forming a dispersion in which the polymerizable composition is dispersed in an aqueous medium. For example, a method of forming a dispersion liquid based on mechanical energy application such as a high shear type homomixer, an ultrasonic homogenizer, a high pressure homogenizer, a thin film swirl type high speed mixer, etc. may be mentioned, but the present invention is not limited thereto. These methods can be used alone or in combination.

  In the present invention, the method for inducing radical polymerization is the same as the method for inducing general radical polymerization. Specifically, conventionally known methods such as heating, light irradiation, and addition of a reducing agent can be applied. . Among these, heating is preferable from the viewpoint of workability and controllability of chemical reaction, and is preferable. When the growth period is induced by heating, it is preferable to heat at least one kind of radical polymerization initiator in the range of not less than 10 hours half temperature and not more than 30 ° C. higher than 10 hours half temperature. More preferably, the heating is performed in a range of 10 hours half-temperature or higher and 20 hours or less higher than the 10-hour half-temperature. When heating at a temperature higher by 30 ° C. than the half-temperature for 10 hours, the controllability of the polymerization reaction may be significantly impaired. Further, when heating at a temperature lower than the 10-hour half-temperature, the working time for the polymerization process becomes extremely long, which is not preferable from the viewpoint of controllability of the polymerization reaction and work efficiency. In the polymerization step of the present invention, the heating temperature may be raised or lowered. Further, a radical polymerization initiator may be additionally added during radical polymerization.

A second invention is a resin composition containing a composite polymer and an amorphous polymer,
The composite polymer is a branched polymer in which a crystalline polymer and an amorphous polymer are chemically bonded,
The said resin composition is related with the resin composition characterized by having a vinylidene group.

  In the first invention, when a compound that undergoes β-cleavage by radical polymerization to form a vinylidene group is used as the chain transfer agent, the resin composition obtained is the resin composition of the second invention.

  The amorphous polymer of the present invention is a polymer formed by reaction of a radical polymerizable monomer in the first invention. There is no particular limitation 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 that it is 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. The glass transition temperature is 50 ° C. or higher and 110 ° C. or lower, 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 having no unit 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 branched polymer of the present invention is a graft polymer having a branched structure in which different types of branched polymers are chemically bonded to a main polymer, and includes multi-branched polymers having a large number of branches such as dendrimers and hyperbranched polymers. . In the branched polymer of the present invention, either a crystalline polymer or an amorphous polymer may constitute a trunk or a branch.

  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 branched 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 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 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 that does not have a unit derived from the composite 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 having no unit 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.

  It is preferable that the resin composition of this invention contains the vinylidene group which shows a peak in 5.1-5.4 ppm and 5.6-5.9 ppm in 1H-NMR spectrum. This vinylidene group is a non-crystalline polymer in the case of using a chain transfer agent that forms a vinylidene group by generating a β-cleavage by a chain transfer reaction when radically polymerizing the polymerizable composition of the present invention to obtain a resin composition. Derived from vinylidene groups introduced into the 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 and amorphous polymer of the present invention as long as the object of the present invention can be achieved.

  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 ink or electrophotographic toner, the number average particle size of the resin particles of the present invention is 0.05 μm or more and 8 μm or less, and the value obtained by dividing the volume average particle size by the number average particle size. The particle size distribution index defined as is preferably 1.0 or more and 1.4 or less.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

(Measurement method of molecular weight)
This molecular weight is obtained by gel permeation chromatography (equipment: HLC-8120GPC manufactured by Tosoh Corporation, column: TSKgel G2000HXL / G3000HXL / G4000HXL manufactured by Tosoh Corporation), and a polystyrene-equivalent number average molecular weight (Mn) using chloroform as a developing solvent, or The peak molecular weight (Mp) was measured.

(Measurement method of half width by DSC)
Melting | fusing point of this crystalline polyester, block polymer, and wax was measured on condition of the following using DSC 7020 (made by Seiko Instruments Inc.).
・ Raising rate: 10 ° C / min
-Measurement start temperature: 20 ° C
-Measurement end temperature: 200 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 3 mg of a sample is precisely weighed, placed in a silver pan, and measured using an empty silver pan as a reference. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 20 ° C., and then heated again. In the first temperature raising process, the peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 20 ° C. to 200 ° C. is defined as the melting point. The maximum endothermic peak means a peak having the largest endothermic amount when there are a plurality of peaks. Furthermore, the temperature width at half maximum of the peak height of the maximum endothermic peak is defined as half width (° C.).

(Synthesis of crystalline polyester A)
-1,12-dodecanediol: 100 mass parts-Sebacic acid: 90.9 mass parts Said raw material was prepared to the three necked flask. After substituting the inside of the system with nitrogen by this depressurization operation, the system was 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 4 hours. When it became a viscous state, the heating was stopped, nitrogen was introduced into the system and the system was 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 A (peak molecular weight (M _p ): 30800) was synthesized by filtering the precipitate and performing vacuum drying.

(Synthesis of radical polymerizable polymer 1)
Crystalline polyester A: 100 parts by mass 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride: 15.3 parts by mass The above raw materials were charged into 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, and 5.8 parts by mass of acrylic acid and 0.98 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 a radical polymerizable polymer 1 having an acryloyl group as a radical polymerizable functional group (peak molecular weight (M _p ): 31500). From a peak integrated value derived from an acryloyl group evaluated using a 1-NMR spectrum acquired using deuterated chloroform and a number average molecular weight evaluated using GPC, 1.2 of one radical polymerizable polymer were obtained. It was calculated to have an acryloyl group.

(Synthesis of radical polymerizable polymer 2)
Crystalline polyester A: 100 parts by mass 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride: 15.3 parts by mass The above raw materials were charged into 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, 6.9 parts by mass of methacrylic acid and 0.98 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 a radical polymerizable polymer 2 having a methacryloyl group as a radical polymerizable functional group (peak molecular weight (M _p ): 32000). 1.1 for one radical polymerizable polymer 2 from the peak integrated value derived from methacryloyl group evaluated using 1-NMR spectrum obtained using deuterated chloroform and the number average molecular weight evaluated using GPC. It was calculated to have a methacryloyl group.

(Synthesis of radical polymerizable polymer 3)
Crystalline polyester 1: 100 parts by mass N, N-dimethylformamide: 100 parts by mass The above raw materials were charged into a two-necked flask. After substituting the system with nitrogen by depressurization, the flask was immersed in an ice bath in a nitrogen flow state, and 3.2 parts by mass of sodium hydride (60%) and 12.2 parts by mass of 4-vinylbenzyl chloride were added. Stirring was performed 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 a radical polymerizable polymer 3 having a styryl group as a radical polymerizable functional group (peak molecular weight (M _p ): 31200). From the peak integrated value derived from a styryl group evaluated using a 1-NMR spectrum obtained using deuterated chloroform and the number average molecular weight evaluated using GPC, 0.9 for one radical polymerizable polymer 3 It was calculated to have a styryl group.

(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 number average 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. Next, 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 above raw materials were charged into 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 (M _p ): 2200).

(Synthesis of chain transfer agent 3)
Instead of polystyrene 1, polystyrene 2 was replaced with 76.7 parts by weight of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 36.9 parts by weight of 3-mercapto-1-propanol, and N, N-dimethyl. A chain transfer agent 3 (peak molecular weight (M _p ): 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)
Polystyrene 3 instead of polystyrene 1, 14.6 parts by mass of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 60.0 parts by mass of 3-mercapto-1-propanol, N, N- A chain transfer agent 4 (peak molecular weight (M _p ): 800) was synthesized in the same manner as the 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 (peak molecular weight: 12000) was obtained by drying under reduced pressure at 40 ° C.

(Characteristics of resin particles)
<Evaluation of granulation>
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.
Good: less than 1.20 Fair: 1.20 or more and less than 1.40 Bad: 1.40 or more

<Evaluation of deformability during heating>
Deformability during heating is based on resin particles molded into pellets at 4 MPa, using a rheometer AR2000ex (manufactured by TA Instruments), loss elastic modulus G ″ with respect to temperature, and storage elastic modulus G ′. Evaluation was made using the value at 100 ° C. of the loss tangent tan δ (= G ″ / G ′) calculated from the change in. In the present invention, it was determined that A to C were easy to deform during heating, and D was determined to be defective.
A: 1.9 or more B: 1.6 or more and less than 1.9 C: 1.3 or more and less than 1.6 D: Less than 1.3

[Example 1]
To 130 g of ion-exchanged water, 2.53 g of calcium phosphate was added, and stirred at 10,000 rpm using a homomixer to prepare an aqueous medium.

next,
・ Styrene 15.4g
・ N-butyl acrylate 3.8 g
・ Divinylbenzene 0.3g
・ Radically polymerizable polymer 1 3.9 g
Polymerization initiator V-65 (2,2′-azobis- (2,4-dimethylvaleronitrile))
0.7g
・ Dispersing aid 1.3g
・ Chain transfer agent 1 0.08g
Were mixed to prepare a polymerizable composition. The polymerizable composition was mixed with the previously prepared aqueous medium and stirred at 10,000 rpm at room temperature to prepare a suspension of the polymerizable composition. This suspension was put into a 300 ml three-necked flask, nitrogen bubbled for 30 minutes while stirring at 200 rpm, and then kept at 70 ° C. for 8 hours to prepare a dispersion of a resin composition. Finally, after adding concentrated hydrochloric acid to the dispersion of the resin composition, filtration washing and drying under reduced pressure were performed, and the powdered resin particles 1 were recovered. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 1. When the resin particle 1 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.

[Example 2]
Resin particles 2 were obtained in the same manner except that 0.07 g of methyl α-bromomethylacrylate (manufactured by Sigma Aldrich) was used in place of the chain transfer agent 1 in Example 1. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 2. When the resin particle 2 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.

[Example 3]
Resin particles 3 were obtained in the same manner except that n-dodecyl mercaptan (manufactured by Sigma Aldrich) was used in place of the chain transfer agent 1 in Example 1. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 3.

[Example 4]
Resin particles 4 were obtained in the same manner except that the radical polymerizable polymer 2 was used instead of the radical polymerizable polymer 1 in Example 3. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 4.

[Example 5]
Resin particles 5 were obtained in the same manner except that the radical polymerizable polymer 3 was used instead of the radical polymerizable polymer 1 in Example 3. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 5.

[Example 6]
Resin particles 6 were obtained in the same manner except that 0.32 g of the chain transfer agent 4 was used instead of the chain transfer agent 1 in Example 1. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 6.

[Comparative Example 1]
・ Radiopolymerizable polymer 1 10g
・ Styrene 5.1g
・ Normal butyl acrylate 1.2g
・ Lupelox 11 0.53g
Was dissolved in 100 g of toluene to obtain a solution. Next, this solution was subjected to nitrogen bubbling for 30 minutes while stirring at 200 rpm, and then kept at 75 ° C. for 8 hours. Thereafter, the precipitate obtained by pouring the solution into a large amount of methanol was recovered, and the precipitate was dried under reduced pressure. Further, the precipitate was mixed with acetone to form a mixture, and the mixture was stirred at 40 ° C. for 30 minutes and then centrifuged to collect the precipitate. This precipitate was dried under reduced pressure to obtain a composite polymer 1 having a peak molecular weight of 63,000.

  Next, 2.53 g of calcium phosphate was added to 130 g of ion-exchanged water, and the mixture was stirred at 10,000 rpm using a homomixer to prepare an aqueous medium.

next,
・ Styrene 15.4g
・ N-butyl acrylate 3.8 g
・ Divinylbenzene 0.3g
・ Composite polymer 1 8.0g
・ Toluene 5.0g
・ 2,2′-azobis- (2,4-dimethylvaleronitrile) 0.7 g
・ Dispersing aid 1 1.3g
Were mixed to prepare a polymerizable composition. The polymerizable composition was mixed with the previously prepared aqueous medium and stirred at 10,000 rpm at room temperature to prepare a suspension of the polymerizable composition. This suspension was put into a 300 ml three-necked flask, and after bubbling with nitrogen for 30 minutes while stirring at 200 rpm, the dispersion of the resin composition was adjusted by holding at 70 ° C. for 8 hours. Finally, concentrated hydrochloric acid was added to the dispersion liquid of the resin composition, followed by filtration and drying under reduced pressure to obtain powdery resin particles 7. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 7.

[Comparative Example 2]
Resin particles 8 were obtained in the same manner except that the chain transfer agent 1 in Example 1 was omitted. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 8.

[Comparative Example 3]
Resin particles 9 were obtained in the same manner except that 0.80 g of chain transfer agent 3 was used instead of chain transfer agent 1 in Example 1. Table 1 summarizes the characterization of the polymerizable composition and the resin particles 9.

[Comparative Example 4]
Resin particles 10 were obtained in the same manner except that 0.40 g of chain transfer agent 2 was used instead of chain transfer agent 1 in Example 1. Table 1 summarizes the composition of the polymerizable composition and the characterization of the resin particles 10.

DESCRIPTION OF SYMBOLS 11 Radical polymerizable polymer 12 Crystalline polymer 13 Radical polymerizable functional group 14 Radical polymerizable monomer 15 Composite polymer 16 Amorphous polymer derived from composite polymer 17 Chemical bond of crystalline polymer and amorphous polymer which composite polymer has 18 Amorphous polymer not derived from composite polymer 19 Resin composition 20 Chain transfer agent 21 Growing polymer 22 Radical 23 Methyl methacrylate dimer 24 Vinylidene group 25 Tertiary carbo radical

Claims (10)

A method for producing a resin composition comprising synthesizing a resin composition by radical polymerization using a polymerizable composition containing a crystalline polymer, a radical polymerizable monomer, and a chain transfer agent,
The crystalline polymer is a radical polymerizable polymer having a radical polymerizable functional group,
The radical polymerizable functional group is a functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group;
The chain transfer agent has a number average molecular weight of less than 1000;
The manufacturing method of the resin composition characterized by the above-mentioned. The crystalline polymer is
(1) a crystalline polyester,
(2) It has an endothermic peak measured by differential scanning calorimetry, and the half-value width of the endothermic peak is 10 ° C. or less.
The manufacturing method of the resin composition of Claim 1.   The method for producing a resin composition according to claim 1 or 2, wherein a chain transfer constant of the chain transfer agent is 0.1 or more and 10 or less with respect to the radical polymerizable monomer.   The method for producing a resin composition according to any one of claims 1 to 3, wherein the chain transfer agent is a compound that undergoes β-cleavage by radical polymerization to form a vinylidene group. The manufacturing method of the resin composition of any one of Claims 1 thru | or 4 with which the said 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 method for producing a resin composition according to any one of claims 1 to 5, wherein the crystalline polymer has the radical polymerizable functional group at a main chain end. A polymerizable composition containing a crystalline polymer, a radical polymerizable monomer, and a chain transfer agent is dispersed in an aqueous medium to prepare a suspension having particles of the polymerizable composition, and a resin composition is obtained by radical polymerization. A method for producing resin particles for forming particles of a product,
The crystalline polymer is a radical polymerizable polymer having a radical polymerizable functional group,
The radical polymerizable functional group is a functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group;
The chain transfer agent has a number average molecular weight of less than 1000;
The manufacturing method of the resin particle characterized by the above-mentioned. A resin composition containing a composite polymer and an amorphous polymer,
The composite polymer is a branched polymer in which a crystalline polymer and an amorphous polymer are chemically bonded,
The resin composition having a vinylidene group. The crystalline polymer is
(1) a crystalline polyester,
(2) It has an endothermic peak measured by differential scanning calorimetry, and the half-value width of the endothermic peak is 10 ° C. or less.
The resin composition according to claim 8. The resin composition according to claim 8 or 9, 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.)

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