JP5214558B2 - Resin particles and method for producing the same - Google Patents

Description

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

  As methods for forming resin particles having higher crystallinity than conventional methods, a method of depositing a crystalline resin from an organic solvent (for example, see Patent Document 1) and a method using a phase separation solvent (for example, see Patent Document 2). Are known.

Japanese Patent Laid-Open No. 2005-15589 JP-A-8-176310

However, the resin particles obtained by the above method are insufficient in terms of both heat-resistant storage stability and melting characteristics.
The subject of this invention is providing the manufacturing method which obtains the crystalline resin particle which can make heat resistant preservability and a fusion | melting characteristic unconventional.

As a result of intensive studies, the inventors have found that the heat resistant storage stability and melting characteristics of the resin particles can be achieved by treating with carbon dioxide in a liquid or supercritical state, and the present invention has been achieved.
That is, the present invention is the following three inventions.
(I) Resin particles (B) containing a resin (A) composed of a crystalline part (a) having a polyhydroxycarboxylic acid (p) as essential constituents and an amorphous part (b) are liquid or A process for producing resin particles (X) comprising a step of treating with carbon dioxide (C) in a supercritical state and then removing (C), and melting by differential scanning calorimetry (DSC) measurement of the obtained (X) A method for producing resin particles (X) in which heat satisfies the following relational expression (1) and the weight ratio of the crystalline part (a) in the resin (A) is 30 to 95%.
0 ≦ H2 / H1 ≦ 0.9 (1)
[In relational expression (1), H1 represents the heat of fusion (J / g) at the first temperature rise by DSC measurement; H2 represents the measurement value of the heat of fusion (J / g) at the second temperature rise by DSC measurement. ]
(II) Resin particles (X) obtained by the above production method.
(III) An electrophotographic toner containing the resin particles (X).

  The resin particles (X) of the present invention obtained by the production method of the present invention can achieve both heat resistant storage stability and melting characteristics.

It is a flowchart of the experimental apparatus used for preparation of the resin particle in this invention.

Hereinafter, the present invention will be described in detail.
1st invention of this application is invention regarding the manufacturing method of a resin particle, Comprising: The crystalline part (a) which uses polyhydroxycarboxylic acid (p) as an essential structural component, and an amorphous part (b) are comprised. The resin particles (B) containing the resin (A) may be described as liquid or supercritical carbon dioxide (C) [hereinafter referred to as carbon dioxide (C). ], After manufacturing, it is a manufacturing method including the process of obtaining resin particle (X) by removing a carbon dioxide (C).

In the present invention, it is necessary that the heat of fusion of the obtained resin particles (X) measured by differential scanning calorimetry (DSC) satisfies the following relational expression.
0 ≦ H2 / H1 ≦ 0.9 (1)
H1 represents the heat of fusion (J / g) at the first temperature rise by DSC measurement, and H2 represents the measured value of the heat of fusion (J / g) at the second temperature rise by DSC measurement.

Here, the heat of fusion is measured in accordance with JIS K7122 (1987) “Method of measuring the transition heat of plastic”.
Specifically, a sample (5 mg) is collected and placed in an aluminum pan, and a differential scanning calorimeter (DSC) (for example, “RDC220 manufactured by SII Nano Technology Co., Ltd.”, “DSC20 manufactured by Seiko Electronics Industry Co., Ltd.) The temperature of the endothermic peak due to melting [melting point (m)] (° C.) can be determined at a heating rate of 10 ° C. per minute. Further, the heat of fusion can be determined from the area of the endothermic peak. In addition, after the first temperature increase, the cooling before the second temperature increase is performed at a cooling rate of 90 ° C./min to 0 ° C.

As shown in the relational expression (1), H2 / H1 is 0 or more, preferably 0.01 or more, more preferably 0.1 or more.
Further, H2 / H1 is 0.9 or less, preferably 0.85 or less, and more preferably 0.8 or less. If it exceeds 0.9, the heat resistant storage stability deteriorates, which is not preferable.

The resin (A) contained in the resin particles (X) of the present invention is composed of a crystalline part (a) and a non-crystalline part (b) containing polyhydroxycarboxylic acid (p) as essential constituent components. Specifically, it is obtained by bonding a resin constituting the crystalline part (a) and a resin constituting the non-crystalline part (b).
Below, resin which comprises a crystalline part (a) is demonstrated in detail.
The resin constituting the crystalline part (a) is not particularly limited as long as it has polyhydroxycarboxylic acid (p) as an essential constituent and has crystallinity. From the viewpoint of heat-resistant storage stability, the melting point (m) is preferably in the range of 30 to 120 ° C, more preferably 40 to 100 ° C.
Here, melting | fusing point (m) was measured with the differential scanning calorimeter (DSC) based on JISK7122 (1987) "Plastic transition heat measuring method" similarly to the measuring method of the said heat of fusion, It means the temperature (° C) of the endothermic peak due to melting at the first temperature rise.

Polyhydroxycarboxylic acid (p) can also be obtained by directly dehydrating and condensing hydroxycarboxylic acids such as glycolic acid and lactic acid (L-form, D-form, racemic form). Ring-opening polymerization of a cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to an intermolecular dehydration condensate, with a polyol containing a diol as an initiator, and optionally in the presence of a catalyst Is preferable from the viewpoint of adjusting the molecular weight.
When a polyol is used as the initiator, a polyhydroxycarboxylic acid (p) having a hydroxyl group at the terminal can be obtained. In addition, (p) may be modified at its terminal so as to become, for example, a carboxyl group.
Examples of the polyol include diols (c) described later such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. These polyols may be used in combination.
Examples of the cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) include glycolide and lactide (L-form, D-form, racemate) and the like. Of these, L-lactide and D-lactide are preferable from the viewpoint of crystallinity.
Moreover, it can copolymerize using C3-C12 monolactones (one ester group in a ring), such as (gamma) -butyrolactone and (epsilon) -caprolactone, with a C4-C12 cyclic ester. The polyhydroxycarboxylic acid (p) may be a block copolymer, a random copolymer, or an alternating copolymer with the monolactone having 3 to 12 carbon atoms thus obtained. When monolactone is copolymerized, the proportion of monolactone in the constituent unit of the copolymer is preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 5 to 60% by weight.
As the catalyst, for example, commonly used catalysts such as acids such as inorganic acids and organic acids, metal chlorides, oxides and hydroxides, fatty acid metal salts, and organometallic compounds can be used.
Of these, organic tin compounds (dibutyltin oxide, methylphenyltin oxide, etc.), organic titanium compounds (tetra-n-propyl titanate, tetraisopropyl titanate, etc.), and organic halogenated tin compounds (monobutyltin trichloride, etc.) are preferred.
The addition amount of the catalyst is preferably 0.1 to 5000 ppm with respect to the entire reaction system. The polyhydroxycarboxylic acid (p) can be obtained by polymerization at a reaction temperature of 100 to 230 ° C., preferably in an inert atmosphere.
The ring-opening polymerization reaction may be performed without a solvent, or a reaction solvent may be used. As the reaction solvent, one or more known organic solvents such as toluene, benzene, ethylbenzene, hexane and pentane can be used.

  As for the molecular weight of polyhydroxycarboxylic acid (p), the thing whose weight average molecular weight (Mw) calculated | required by the gel permeation chromatography (GPC) is 2000-80000 is preferable. The glass transition temperature (Tg) is preferably -100 to 60 ° C, more preferably -80 to 40 ° C. The melting point (m) is preferably 40 to 100 ° C.

The resin constituting the crystalline part (a) has polyhydroxycarboxylic acid (p) as an essential component and is not particularly limited as long as it has crystallinity, and is a single resin of polyhydroxycarboxylic acid (p). Alternatively, it may be a composite resin with another resin having crystallinity. Moreover, a mixed resin with other resin which has crystallinity may be sufficient.
As other resins having crystallinity used in the composite resin, it is easy to introduce a block of polyhydroxycarboxylic acid (p), so that polyester resins other than polyhydroxycarboxylic acid, polyurethane resins, polyurea resins, and polyamide resins are used. One or more kinds of resins selected from the above are preferable, and polyester resins (particularly linear polyester resins) are more preferable.

The crystalline polyester resin is preferably a polyester resin synthesized from a polyol component containing a diol and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyol or a trifunctional or higher functional polycarboxylic acid may be used in combination.
The crystalline polyurethane resin is preferably a polyurethane resin synthesized from a polyol component containing a diol and a polyisocyanate component containing a diisocyanate. However, if necessary, trifunctional or higher functional polyols or trifunctional or higher functional polyisocyanates may be used in combination.
The crystalline polyamide resin is preferably a polyamide resin synthesized from a polyamine containing a diamine and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polycarboxylic acid may be used in combination.
The crystalline polyurea resin is preferably a polyurea resin synthesized from a polyamine containing a diamine and a polyisocyanate component containing a diisocyanate. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polyisocyanate may be used in combination.

  Polyol component, polycarboxylic acid component, polyisocyanate component, and polyamine component (each including three or more functional groups) used for crystalline polyester resin, crystalline polyurethane resin, crystalline polyamide resin, crystalline polyurea resin are shown respectively. .

  Among the polyol components, examples of the diol include a diol that does not contain an aromatic ring, a diol that contains an aromatic ring, and a diol having a functional group other than a hydroxyl group.

  Among the diols that do not contain an aromatic ring, examples of the aliphatic diol include a linear aliphatic diol, an aliphatic diol having a secondary hydroxyl group, and a branched aliphatic diol.

The straight-chain aliphatic diol means a straight-chain aliphatic diol having a primary hydroxyl group at the molecular end, and a straight-chain aliphatic diol having 2 to 36 carbon atoms (for example, ethylene glycol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol). It is done.
Among these, considering availability, a linear aliphatic diol having 2 to 10 carbon atoms (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol) are preferred.

Examples of the aliphatic diol having a secondary hydroxyl group include aliphatic diols having a secondary hydroxyl group having 2 to 36 carbon atoms (for example, 1,2-propylene glycol).
Examples of the branched aliphatic diol include branched aliphatic diols having 2 to 36 carbon atoms (for example, neopentyl glycol and 2,2-diethyl-1,3-propanediol).

  Examples of diols containing no aromatic ring other than aliphatic diols include alkylene ether glycols having 4 to 36 carbon atoms (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol), carbon A alicyclic diol of 4 to 36 (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A), alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO) ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] addition products (number of added moles 1 to 30), polybutadiene diol, and the like.

  Examples of the diol containing an aromatic ring include AO (EO, PO, BO, etc.) addition products (addition mole number 2-30) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.).

Examples of the diol having another functional group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol having a carboxyl group include dialkylol alkanoic acids having 6 to 24 carbon atoms [for example, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid. 2,2-dimethyloloctanoic acid].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid di (ethylene glycol) ester, sulfamic acid diol [N, N-bis ( 2-hydroxyalkyl) sulfamic acid (alkyl group having 1 to 6 carbon atoms) or an AO adduct thereof (AO includes EO or PO, such as 1 to 6 added moles of AO): for example, N, N-bis (2- Hydroxyethyl) sulfamic acid, and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct], bis (2-hydroxyethyl) phosphate, and the like.
Examples of neutralizing bases for these diols include tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).

Examples of the trifunctional or higher (3 to 8 or higher) polyols include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof, for example, Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and their derivatives such as sucrose and methylglucoside); AO adducts (additions) of trisphenols (such as trisphenol PA) Mole number 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomers, etc. ]; Etc.
Among these, preferred are AO adducts of 3 to 8 or higher polyhydric aliphatic alcohols and novolak resins.

  As a polyol component, it is preferable that content of a linear aliphatic diol is 80 mol% or more of a polyol component, More preferably, it is 90 mol% or more. If it is 80 mol% or more, the crystallinity of the resin is improved and the melting point is increased, so that the heat resistant storage stability is good.

  Among the polycarboxylic acid components, dicarboxylic acids include aliphatic dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); 6-40 alicyclic dicarboxylic acids [dimer acid (dimerized linoleic acid), etc.], C4-C36 alkene dicarboxylic acid (dodecenyl succinic acid, pentadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.) ); Aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.) .

Examples of the tri- or higher functional (3- to 6-valent or higher) polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid and polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a C1-C4 lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The polycarboxylic acid component is preferably an aliphatic dicarboxylic acid (particularly linear carboxylic acid), an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid, and more preferably from the viewpoint of crystallinity and availability. Adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid.

  Among the polyisocyanate components, the diisocyanate includes an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, and an oil having 4 to 15 carbon atoms. Cyclic diisocyanate, C8-15 aromatic aliphatic diisocyanate, modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group And the like, and mixtures of two or more thereof. Moreover, you may use trifunctional or more (3-8 valence or more) polyisocyanate together as needed.

  Specific examples of aromatic diisocyanates and trivalent or higher aromatic polyisocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), Examples include crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, and the like. .

  Specific examples of the aliphatic diisocyanate and the trivalent or higher aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, lysine diisocyanate, 2 , 6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, and the like.

  Specific examples of the alicyclic diisocyanate and the trivalent or higher alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate ( Hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic diisocyanate and the tri- or higher valent araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate ( TMXDI).

  Among these polyisocyanate components, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

As an example of a polyamine component, as aliphatic diamines (C2-C18),
[1] Aliphatic diamine {C2-C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) diamine [diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]};
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substitutes [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2, 5-hexamethylenediamine, methyliminobispropylamine, etc.];
[3] Alicyclic or heterocyclic-containing aliphatic diamine {alicyclic diamine (C4 to C15) [1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene Dianiline), etc.], heterocyclic diamines (C4-C15) [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane etc.];
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.);

As aromatic diamines (C6-C20),
[1] Unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine) , Diaminodiphenylsulfone, benzidine, thiodianiline, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine, and the like;
[2] Aromatic diamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], such as 2,4- and 2,6-tolylenediamine, crude tri Rangeamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2, 4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 4,4′-diamino-3,3′-dimethyldiphenylmethane, etc.), and mixtures of these isomers in various proportions;
[3] Aromatic diamine [methylene bis-o-chloroaniline, 4-chloro-o] having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group, etc.) -Phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5- Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline, etc.];
[4] Aromatic diamine having a secondary amino group [partial or partial -NH ₂ of the aromatic diamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group such as methyl, ethyl Etc.] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].

  In addition to these, the polyamine component is obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamines (eg alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

The proportion of the polyhydroxycarboxylic acid (p) in the resin constituting the crystalline part (a) is preferably 10% by weight or more, more preferably 15 to 95% by weight, particularly preferably 20 to 90% by weight.
When a mixed resin of (p) and another resin is used as the crystalline part (a), the proportion of (p) in the mixed resin is preferably 10% by weight or more, more preferably 15 to 95% by weight. Particularly preferred is 20 to 90% by weight.

  The method of combining the polyhydroxycarboxylic acid (p) with the crystalline polyester resin, the crystalline polyurethane resin, the crystalline polyurea resin, and the crystalline polyamide resin is based on the reactivity of the functional group contained therein. Whether or not (coupling agent) is used is selected, and when it is used, a binder suitable for the functional group contained can be selected and bonded to form a composite resin.

When a binder is not used when preparing the composite resin, for example, in the presence of a crystalline polyester resin, a crystalline polyurethane resin, a crystalline polyurea resin, a crystalline polyamide resin, and a mixture thereof, A method of ring-opening polymerization of 12 cyclic esters.
Other examples include a method in which polyhydroxycarboxylic acid (p) is first prepared and the reaction between the functional group contained in (p) and the functional group contained in the other resin is advanced while heating and reducing pressure as necessary. The reaction temperature is preferably 180 ° C to 230 ° C.

When using a binder, various binders can be used according to the kind of the functional group at the terminal.
By using polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, acid anhydride, polyfunctional epoxy or the like as a binder, and performing a dehydration reaction or an addition reaction, the crystalline part (a) which is a composite resin is obtained. can get.
Examples of the polyvalent carboxylic acid and acid anhydride include those similar to the polycarboxylic acid component. Examples of the polyhydric alcohol include those similar to the polyol component. Examples of the polyvalent isocyanate include the same polyisocyanate components.
As the polyfunctional epoxy, bisphenol A type and -F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, diglycidyl ethers of AO adducts of bisphenol A or -F, Diglycidyl ether of AO adduct of hydrogenated bisphenol A, diol (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, etc.) diglycidyl ether, trimethylolpropane Di and / or triglycidyl ether, pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta And / or hexaglycidyl ether, resorcin diglycidyl ether, dicyclopentadiene / phenol-added glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, polybutadiene diglycidyl ether, etc. Is mentioned.

  Among the methods for producing the composite resin, as an example of the dehydration reaction, when the polyhydroxycarboxylic acid (p) and the other resin forming the composite resin both have a hydroxyl group, these hydroxyl groups are bonded to a binder (for example, a polyhydric acid). Reaction with a divalent carboxylic acid). In this case, for example, the reaction is performed at a reaction temperature of 180 ° C. to 230 ° C. in the absence of a solvent to obtain a crystalline part (a) which is a composite resin.

  Examples of the addition reaction include a case in which the polyhydroxycarboxylic acid (p) and other resins forming the composite resin both have a hydroxyl group at the terminal, and a reaction in which these are bonded with a binder (for example, a polyvalent isocyanate), In addition, when one of the polyhydroxycarboxylic acid (p) and the other resin forming the composite resin has a hydroxyl group at the terminal and the other is a resin having an isocyanate group at the terminal, these are bonded without using a binder. Reaction. In this case, for example, both the polyhydroxycarboxylic acid (p) and the other resin forming the composite resin are dissolved in a soluble solvent, and if necessary, a binder is added and the reaction temperature is 80 ° C. to 150 ° C. It reacts and the crystalline part (a) which is a composite resin is obtained.

Examples of the resin constituting the amorphous part (b) include polyester resins (including polyhydroxycarboxylic acid), polyurethane resins, polyurea resins, polyamide resins, polystyrene resins, styrene acrylic polymers, and the like.
Of these, polyester resins (including polyhydroxycarboxylic acid), polyurethane resins, polyurea resins, polyamide resins, and composite resins thereof are preferable, and polyurethane resins and polyester resins are more preferable.

Similar to the crystalline part (a), the polyester resin is preferably a polyester resin synthesized from a polyol component containing a diol and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyol or a trifunctional or higher functional polycarboxylic acid can be used in combination.
The polyurethane resin is preferably a polyurethane resin synthesized from a polyol component containing a diol and a polyisocyanate component containing a diisocyanate. However, if necessary, a trifunctional or higher functional polyol or a trifunctional or higher functional polyisocyanate can be used in combination.
The polyurea resin is preferably a polyurea resin synthesized from a polyamine containing a diamine and a polyisocyanate component containing a diisocyanate. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polyisocyanate can be used in combination.
The polyamide resin is preferably a polyamide resin synthesized from a polyamine containing a diamine and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polycarboxylic acid can be used in combination.
Monomers constituting the non-crystalline polyester resin, non-crystalline polyurethane resin, non-crystalline polyamide resin, and non-crystalline polyurea resin include the polyol component, the polycarboxylic acid component, the polyisocyanate component, and the polyamine component. The thing similar to what was shown as a specific example is mentioned, What kind of combination may be sufficient if it becomes non-crystalline resin.

The glass transition temperature (Tg) of the resin constituting the non-crystalline part (b) is preferably 40 to 250 ° C., more preferably 50 to 240 ° C., and particularly preferably 60 to 230 ° C. from the viewpoint of heat-resistant storage stability. .
Here, the glass transition temperature is a differential scanning calorimeter (DSC20 manufactured by Seiko Denshi Kogyo Co., Ltd., RDC220 manufactured by SII Nano Technology Co., Ltd.) in accordance with JIS K7122 (1987) “Method for measuring the transition heat of plastic”. Etc.).

The bond between the resin constituting the crystalline part (a) and the resin constituting the non-crystalline part (b) takes into account the reactivity of the respective terminal functional groups of the resin constituting (a) and (b). Whether to use a binder (coupling agent) or not, and if so, select a binder suitable for the terminal functional group, bond (a) and (b), and block polymer It can be set as resin (A) which is.
In addition, when a mixture of the resin (A) and the unreacted (a) and / or (b) [preferably a mixture of (A) and (a)] is obtained by the above method, the mixture is used as it is. You may use for the manufacturing method of particle | grains.

When the binder is not used, the reaction between the terminal functional group of the resin forming (a) and the terminal functional group of the resin forming (b) is advanced while heating and reducing pressure as necessary. Especially when the terminal functional group is a reaction between a carboxyl group and a hydroxyl group, or a reaction between a carboxyl group and an amino group, if the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high, Progresses smoothly. The reaction temperature is preferably 180 ° C to 230 ° C.
When using a binder, various binders can be used according to the kind of the functional group at the terminal.
By using polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, acid anhydride, polyfunctional epoxy or the like as a binder, dehydration reaction or addition reaction is performed, so that crystalline part (a) and non-crystalline part By combining (b), the resin (A) is obtained.
Specific examples of these binders and bonding methods include those described above.

  The resin (A) composed of the crystalline part (a) and the amorphous part (b) is preferably a crystalline resin, and the melting point (m) is preferably 40 ° C. from the viewpoint of heat-resistant storage stability. Above, more preferably 50 ° C. or higher, particularly preferably 55 ° C. or higher. Moreover, from a viewpoint of a melt characteristic, 110 degrees C or less is preferable, More preferably, it is 100 degrees C or less, Most preferably, it is 90 degrees C or less. Here, the melting point (m) is measured by the method described above.

The ratio (s / m) of the softening point (s) [° C.] to the melting point (m) [° C.] of the resin (A) is preferably 0.8 to 1.55, more preferably 0.8 to 1.2, particularly preferably 0.85 to 1.15. Within this range, image degradation is less likely to occur when used as toner particles. The softening point (s) is a value measured as follows.
<Softening point>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount And this value (temperature when half of the measurement sample flows out) is taken as the softening point.

In the viscoelastic properties of the resin (A), it is preferable to satisfy the following [Condition 1], and it is more preferable to satisfy the following [Condition 1-2].
[Condition 1] G ′ (m + 20) = 50 to 1 × 10 ⁶ [Pa]
[Condition 1-2] G ′ (m + 20) = 100 to ⁵ × 10 ⁵ [Pa]
When G ′ at (m + 20) ° C. is 50 Pa or more, hot offset hardly occurs even at low temperature fixing, and the fixing temperature range is widened. Further, if it is 1 × 10 ⁶ [Pa] or less, the viscosity is liable to be fixed on the low temperature side, and the fixing property at low temperature is improved.
The measured dynamic viscoelasticity (storage elastic modulus G ′, loss elastic modulus G ″) is measured using a dynamic viscoelasticity measuring device RDS-2 manufactured by Rheometric Scientific, under a frequency of 1 Hz. The measurement temperature range is 30. By measuring the melt viscoelasticity between these temperatures at a temperature between 200 ° C. and 200 ° C., it can be obtained as a curve of temperature-G ′ and temperature-G ″.
The resin (A) satisfying [Condition 1] can be obtained by adjusting the ratio of the crystalline component in the composition constituting (A), adjusting the resin molecular weight, or the like. For example, when the ratio of the crystalline part (a) or the ratio of the crystalline component is increased, the value of G ′ (m + 20) decreases. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like. Also, the value of G ′ (m + 20) is decreased by decreasing the resin molecular weight.

The melting start temperature (x) of the resin (A) is preferably within the temperature range of (m ± 20) ° C. (m is the melting point), more preferably within the temperature range of (m ± 15) ° C., particularly preferably It is within the temperature range of (m ± 10) ° C. Specifically, (x) is preferably 30 to 100 ° C, more preferably 40 to 80 ° C. The melting start temperature (x) is a value measured as follows.
<Melting start temperature>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. After extruding from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”. Is read from the graph, and this value is taken as the melting start temperature.

The resin (A) preferably satisfies the following [Condition 2], more preferably satisfies [Condition 2-2] with respect to the loss elastic modulus G ″ and the melting start temperature (x), and [Condition 2]. −3] is particularly preferable, and [Condition 2-4] is most preferably satisfied.
[Condition 2] | LogG ″ (x + 20) −LogG ″ (x) |> 2.0
[G ′: storage elastic modulus [Pa], G ″: loss elastic modulus [Pa]]
[Condition 2-2] | LogG ″ (x + 20) −LogG ″ (x) |> 2.5
[Condition 2-3] | LogG ″ (x + 15) −LogG ″ (x) |> 2.5
[Condition 2-4] | LogG ″ (x + 10) −LogG ″ (x) |> 2.5
When the melting start temperature (x) of the resin (A) is within the above range and [Condition 2] is satisfied, the resin has a low viscosity reduction speed. The same image quality can be obtained on the side. Moreover, the process from the start of melting to the fixable viscosity is fast, which is advantageous for obtaining excellent low-temperature fixability. [Condition 2] is an index of the sharp melt property of the resin, which indicates how fast it can be fixed with less heat, and is obtained experimentally.
The resin (A) satisfying the preferable range of the melting start temperature (x) and [Condition 2] can be obtained by adjusting the ratio of the crystalline component in the constituent components of (A). For example, when the ratio of the crystalline component is increased, the temperature difference between (m) and (x) is decreased.

Further, in the viscoelastic property of the resin (A), the ratio of the loss elastic modulus G ″ at (m + 30) ° C. to the loss elastic modulus G ″ at (m + 70) ° C. [G ″ (m + 30) / G ″ (m + 70)] is 0. It is preferably 0.05 to 50, more preferably 0.1 to 10 [m: melting point of (A)].
By maintaining the ratio of the loss elastic modulus within the above range, when the toner particles are used, a more stable image quality can be obtained in the fixing temperature region.
The resin (A) satisfying the above G ″ ratio can be obtained by adjusting the ratio of the crystalline component in the composition constituting (A) and the molecular weight of the crystalline part (a). For example, when the ratio of the crystalline part (a) or the ratio of the crystalline component is increased, the value of [G ″ (m + 30) / G ″ (m + 70)] decreases. The molecular weight of the crystalline part (a) is decreased. Increasing the value decreases the value of [G ″ (m + 30) / G ″ (m + 70)]. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like.

The weight average molecular weight (Mw) of the resin (A) is preferably 5000 to 100,000, more preferably 6000 to 80000, and particularly preferably 8000 to 50000 from the viewpoint of melting characteristics.
As for Mw of the crystalline part (a) which comprises (A), 2000-80000 are preferable, More preferably, it is 3000-60000, Most preferably, it is 4000-30000.
Further, the Mw of the non-crystalline part (b) constituting (A) is preferably 500 to 50,000, more preferably 750 to 20,000, and particularly preferably 1000 to 10,000.
The Mw of the crystalline part (a) and the non-crystalline part (b) is determined by measuring the weight average molecular weight (Mw) of the resin constituting (a) and the resin constituting (b) before bonding. can get. In the present invention, the weight average molecular weight (Mw) of the resin is measured using gel permeation chromatography (GPC) under the following conditions.

Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLY made by Tosoh Corporation)
STYRENE) 12 points (Molecular weight 500 1050 2800
5970 9100 18100 37900 96400
190000 355000 1090000 2890000)

  The proportion of the crystalline part (a) in the resin (A) is preferably 30 to 95% by weight, more preferably 40 to 90% by weight, and particularly preferably 50 to 85% by weight. Within this range, the crystallinity of the resin (A) is not impaired, and the heat resistant storage stability is good.

Resin (A) is a block resin composed of a crystalline part (a) and an amorphous part (b), and (a) and (b) are linearly bonded in the following format. It is preferable that both ends are resins of (a), and the average value n of the number of repeating units of {-(b)-(a)} is 0.5 to 3.5, more preferably n = 0. 0.7 to 2.0, particularly preferably n = 0.9 to 1.5.
(A) {-(b)-(a)} n
Specifically, the above formula shows that the crystalline part (a) and the non-crystalline part (b)
(A) [n = 0],
(A)-(b)-(a) [n = 1],
(A)-(b)-(a)-(b)-(a) [n = 2],
(A)-(b)-(a)-(b)-(a)-(b)-(a) [n = 3]
And the like, and mixtures thereof (except for those consisting only of n = 0). In addition, containing that whose n is 0 means containing resin which comprises a crystalline part (a) with resin (A).
When n is 3.5 or less, the crystallinity of the resin (A) is not impaired. Further, when n is 0.5 or more, the elasticity after melting of (A) is good, and when used for toner, hot offset hardly occurs at the time of fixing, and the fixing temperature region becomes wider. Note that n is a calculated value obtained from the amount of raw material used [molar ratio of (a) and (b)]. Further, from the viewpoint of the crystallinity of the resin (A), it is preferable that both ends of (A) are crystalline parts (a).
In addition, when both ends are non-crystalline parts (b), the crystallinity is lowered, so that the ratio of the crystalline parts (a) in (A) is used in order to give the resin (A) crystallinity. Is preferably 75% by weight or more.

In the present invention, the desired resin particles (X) are obtained by treating the resin particles (B) in carbon dioxide (C) in a liquid or supercritical state and then removing the carbon dioxide (C). Can do. Here, the treatment means that the resin particles (B) are dispersed in (C), brought into contact with (C) for a certain time, and (B) is swollen. By performing this treatment, even resin particles (B) having a ratio of H2 / H1 of 1 or 1 or more can be modified to target resin particles (X) of 0.9 or less.
The predetermined time [including the time required for forming the resin particles (B). ] Is usually 10 seconds to 180 minutes, preferably 30 seconds to 60 minutes.
Swelling occurs when carbon dioxide permeates into resin particles (B) by bringing resin particles (B) into contact with carbon dioxide (C) for a certain period of time. Therefore, the degree of swelling can be adjusted by the contact time with (C), the pressure and temperature of (C).

Examples of the method for dispersing the resin particles (B) in (C) include the following (1) to (4).
(1) A method in which a solution (L) in which a resin (A) is dissolved in a solvent (S) is dispersed in (C) to obtain a resin particle (B) dispersion [in this case, the resin particles (B) are (A ) And (S). ]
(2) Dispersing molten resin (A) in (C) to obtain resin particles (B) dispersion (3) Resin particles (B) are prepared by another method, and (B) is stirred (4) Disperse the resin particles (B) prepared by another method in the solvent (T) and introduce the dispersion into (C). In addition, it is preferable to use the fine particles for dispersion (D) in the dispersion methods (1) and (2). By dispersing (D) in (C), (D) can be adsorbed on the surface of (B), and (B) can be stably dispersed in (C).
Among these methods, (1) is preferable because the particle diameter of the resin particles can be easily adjusted and the particle size distribution (ratio Dv / Dn of volume average particle diameter Dv to number average particle diameter Dn) can be reduced. .

Examples of the solvent (S) include ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, cyclic ether, etc.), ester solvents (acetate ester, pyrubin). Acid esters, 2-hydroxyisobutyric acid esters, lactic acid esters, etc.), amide solvents (dimethylformamide, etc.), alcohols (methanol, ethanol, fluorine-containing alcohols, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), and fats Group hydrocarbon solvents (octane, decane, etc.). A mixed solvent of two or more of these solvents or a mixed solvent of these organic solvents and water can also be used.
From the viewpoint of solvent removal, a mixed solvent (particularly, a mixed solvent of acetone, methanol and water, a mixed solvent of acetone and methanol, a mixed solvent of acetone and ethanol, and a mixed solvent of acetone and water) is preferable.

The viscosity of the solution (L) at 40 ° C. is preferably 10 to 1 million mPa · s, more preferably 500 to 500,000 mPa · s, and particularly preferably 100 to 200,000 mPa · s. . If it is this range, the dispersibility of the resin particle (B) will improve.
The weight ratio of the resin (A) in the solution (L) is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and particularly preferably 15 to 85% by weight. . If it is this range, a resin particle (B) can be formed efficiently.

The fine particles for dispersion (D) used as necessary are not particularly limited as long as the resin particles (B) can be dispersed, and include inorganic fine particles (silica, titania, etc.), organic fine particles (acrylic resin, polyester resin, etc.) and the like.
The volume average particle diameter of the fine particles (D) is not particularly limited as long as the resin particles (B) can be dispersed, but is preferably 30 to 1000 nm, and more preferably 50 to 500 nm. If it is this range, the dispersibility of the resin particle (B) in (C) will improve.
The weight ratio (% by weight) of the fine particles (D) and the resin particles (B) is not particularly limited, but is preferably 0.1 to 20%, more preferably 0.5% with respect to the resin particles (B). ~ 15%. If it is this range, the dispersibility of the resin particle (B) will improve.
The fine particles (D) are preferably those that do not dissolve in (C) and are stably dispersed in (C).

  In the present invention, any method may be used to disperse the fine particles (D) in carbon dioxide (C). For example, (D) and (C) are charged in a container, and (D ) Directly in (C), and a method in which a dispersion in which fine particles (D) are dispersed in a solvent is introduced into (C).

  As said solvent, the thing similar to a solvent (S) is mentioned. From the viewpoint of dispersibility of the fine particles (D), an aliphatic hydrocarbon solvent (decane, hexane, heptane, etc.) and an ester solvent (ethyl acetate, butyl acetate, etc.) are preferable.

The weight ratio (% by weight) between the fine particles (D) and the solvent is not particularly limited, but the fine particles (D) are preferably 50 or less, more preferably 30 or less, and particularly preferably 20 or less with respect to the solvent. is there. Within this range, the fine particles (D) can be efficiently introduced into (C).
The method for dispersing the fine particles (D) in the solvent is not particularly limited, but the fine particles (D) are charged into the solvent and directly dispersed by stirring, ultrasonic irradiation, or the like, or the fine particles are dissolved in the solvent at a high temperature. And a method of crystallization.

In the method (1) of dispersing the resin particles (B) in carbon dioxide (C), since the solution (L) of the resin (A) is dispersed in (C), the temperature at which the resin particles (B) are mixed with (C) The viscosity is preferably moderate, and is preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, from the viewpoint of particle size distribution. The solubility of the resin (A) in (C) is preferably 3% or less, more preferably 1% or less.
The SP value of the resin (A) is preferably 8 to 16, and more preferably 9 to 14. The SP value is expressed by the square root of the ratio between the cohesive energy density and the molecular volume, as shown below.
SP = (△ E / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

In the present invention, other additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, antioxidants) in the resin particles (B) and resin particles (X), An anti-blocking agent, a heat-resistant stabilizer, a flame retardant, etc.) may be contained. As a method for incorporating other additives in the resin particles (B) and (X), it is preferable to mix the resin (A) and the additive in advance and then add and disperse the mixture in (C). .
The electrophotographic toner of the present invention is obtained by adding a pigment or a colorant and, if necessary, a release agent and / or a charge control agent to the resin particles.

  In the method (1), any method may be used as a method of dispersing the solution (L) of the resin (A) in carbon dioxide (C). Specific examples include a method of dispersing the resin (A) solution (L) with a stirrer, a disperser, or the like, and spraying the resin (A) solution (L) into carbon dioxide (C) via a spray nozzle. A method of forming droplets, causing the resin in the droplets to be supersaturated, and precipitating resin particles (known as ASES: Aerosol Solvent Extraction System), coaxial multiple tubes (double tubes, triple tubes, etc.) A solution (L) is obtained by simultaneously ejecting a solution (L) from a separate tube together with a high-pressure gas, an entrainer, etc., and applying external stress to the droplets to promote breakup to obtain particles (known as SEDS: Solution Enhanced Dispersion Fluids). And a method of irradiating ultrasonic waves.

The resin (A) and the solvent (S) are contained by dispersing the solution (L) of the resin (A) in carbon dioxide (C) and adsorbing the fine particles (D) on the surface as necessary. A dispersion in which the resin particles (B) are dispersed in (C) is formed. In the case where the fine particles (D) are used, the surface of the resin particles (B) has a fine particle (D) fixed thereto or a film in which (D) is formed into a film.
The dispersion is preferably a single phase. That is, it is not preferable that the solvent (S) phase is separated in addition to the phase containing carbon dioxide (C) in which (B) is dispersed. Therefore, it is preferable to set the amount of the solution (L) of (A) relative to (C) so that the solvent phase does not separate. The amount of the solution (L) is preferably 90% by weight or less, more preferably 5 to 80% by weight, and particularly preferably 10 to 70% by weight with respect to (C).
In addition, the amount of (S) contained in the resin particles (B) containing the resin (A) and the solvent (S) is preferably 10 to 90% by weight, more preferably 20 to 70% by weight.
The weight ratio of the resin (A) to carbon dioxide (C) is preferably (A) :( C), 1: (0.1-100), more preferably 1: (0.5-50). Especially preferably, it is 1: (1-20).

  The method (2) is the same as the method (1) except that the molten resin (A) is used instead of the solution (L) obtained by dissolving the resin (A) in the solvent (S). A dispersion in which resin particles (B) containing the resin (A) are dispersed in carbon dioxide (C) is formed.

In the above methods (3) and (4), the following methods may be mentioned as methods for preparing the resin particles (B) from the liquid, lump, granule, pellet, or coarse powder resin (A).
(5) A method in which the liquid resin (A) is dispersed in an aqueous medium and taken out.
(6) A method of crushing or pulverizing the solid resin (A).

The method (5) will be described.
Even if it is a solid resin, it can be liquefied by heating the resin (A) to the melting point or higher, or by dissolving the resin (A) in an organic solvent.
As the organic solvent, the above solvent (S) or the like can be used.
As an aqueous medium, if it is a liquid which has water as an essential component, it can be used without a restriction | limiting, Water, the aqueous solution containing surfactant, etc. can be used.
As the surfactant, a known surfactant (for example, a surfactant described in JP-A No. 2004-124059) can be used.
The dispersion apparatus is not particularly limited as long as it is generally used as an emulsifier or a disperser, and a known dispersion apparatus (for example, a dispersion apparatus described in JP-A No. 2002-284881) or the like is used. Can do.
As a method for taking out the resin particles (B) that have been made into particles from the aqueous medium, the resin particles (B) are separated by a solid-liquid separation method (such as a centrifuge, a spacula filter, and / or a filter press) and then washed with water. Etc. are applicable.
The obtained resin particles (B) are dried if necessary. Drying is preferably performed at a temperature lower than the melting point of the resin particles, and is performed under reduced pressure as necessary. As the dryer, a known drying device (for example, a fluidized bed dryer, a vacuum dryer, and a circulating dryer) is used.

Next, the method (6) will be described.
As a crusher that can be used for crushing or crushing, a known crusher {for example, 80-86 pages of the theory and practice of emulsification dispersion (manufactured by Special Machine Co., Ltd., issued on April 17, 1997)}, etc. Can be used.

  The resin particles (B) thus obtained are classified using an air classifier or a sieve, if necessary, and the volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter are adjusted. be able to.

  In the method (4), the solvent (T) is not particularly limited as long as the resin particles (B) can be dispersed. However, a single solvent (for example, acetone, ethanol, dimethylformamide, isopropanol, etc.) or a mixed solvent [ For example, water, alcohol solvents (methanol, ethanol, etc.), amide solvents (dimethylformamide, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ether solvents (tetrahydrofuran, diethyl ether, etc.), 2 or more mixed solvents such as an aromatic hydrocarbon solvent (toluene, xylene, etc.) and an aliphatic hydrocarbon solvent (decane, hexane, heptane, etc.).

The weight ratio of the resin particles (B) and the solvent (T) is not particularly limited, but the resin particles (B) are preferably 55% by weight or less, more preferably 50% by weight or less, with respect to the solvent (T). It is particularly preferably 20 to 45% by weight. Within this range, the resin particles (B) can be efficiently introduced into (C).
Here, the weight ratio of carbon dioxide (C) to solvent (T) is not particularly limited, but (T) is preferably 1 to 50% by weight, more preferably 5%, based on carbon dioxide (C). -40% by weight. If it is this range, the dispersibility of the resin particle (B) will improve.

  In the methods (3) and (4), the weight ratio of the resin particles (B) to the weight of carbon dioxide (C) is preferably 60% by weight or less, more preferably 55% by weight or less, and particularly preferably 20%. ~ 50% by weight. If it is this range, it can process efficiently and can manufacture resin particle (X).

In the present invention, the carbon dioxide (C) used for the treatment of the resin particles (B) can be liquid or supercritical, but is preferably supercritical.
Here, liquid carbon dioxide refers to a triple point of carbon dioxide (temperature = −57 ° C., pressure = 0.5 MPa) and a critical point of carbon dioxide on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. The gas-liquid boundary line passing through (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and carbon dioxide, which is the temperature / pressure condition of the portion surrounded by the solid-liquid boundary line. On the other hand, carbon dioxide in a supercritical state represents carbon dioxide that is at a temperature / pressure condition higher than the critical temperature. The pressure in the present invention indicates the total pressure in the case of a mixed gas of two or more components.

Carbon dioxide (C) may contain other substances as appropriate in order to adjust physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. For example, nitrogen, helium Inert gas such as argon and air.
The weight fraction of (C) in the sum of (C) and other substances is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

When processing the resin particle (B) in (C), it is preferable to carry out at the following temperature.
In order to prevent carbon dioxide from undergoing a phase transition in the pipe during decompression and block the flow path, it is preferably 30 ° C. or higher, and 200 ° C. or lower to prevent thermal degradation of the resin particles (B). Is preferred. Furthermore, 30-150 degreeC is preferable, More preferably, it is 34-130 degreeC, Especially preferably, it is 35-100 degreeC, Most preferably, it is 40-80 degreeC.

The treatment is preferably performed at the following pressure.
In order to satisfactorily disperse the resin particles (B) in (C), it is preferably 3 MPa or more, and preferably 40 MPa or less from the viewpoint of equipment cost and operation cost. More preferably, it is 3.5-35 MPa, More preferably, it is 4-30 MPa, Most preferably, it is 4.5-25 MPa, Most preferably, it is 5-20 MPa.

  The temperature and pressure when treating in carbon dioxide (C) are set within a range in which the resin particles (B) do not dissolve in (C) and carbon dioxide (C) can penetrate into (B). It is preferable. Usually, (B) tends not to dissolve in (C) at lower temperatures and lower pressures, and carbon dioxide (C) tends to penetrate into the resin particles (B) at higher temperatures and pressures.

Carbon dioxide (C) is usually removed under reduced pressure from the dispersion in which the resin particles (B) are dispersed to obtain the resin particles (X) of the present invention. At that time, the pressure may be reduced stepwise by providing independent pressure-controlled containers in multiple stages, or may be reduced to normal temperature and normal pressure at a stretch.
The method for collecting the resin particles (X) is not particularly limited, and examples thereof include a method of filtering with a filter and a method of centrifuging with a cyclone or the like.
The resin particles (X) may be collected after depressurization, or may be collected under high pressure before depressurization and then depressurized. As a method of taking out the resin particles (X) from under high pressure when collecting under high pressure and then depressurizing, the collection container may be depressurized by batch operation, or continuously using a rotary valve. An operation may be performed.

Using the method (1) of dispersing the resin particles (B) in carbon dioxide (C), the resin particles (B) containing the resin (A) and the solvent (S) are dispersed in (C). When a dispersion is obtained, it is necessary to remove or reduce the solvent (S) after forming and treating the resin particles (B).
As a method for removing or reducing the solvent (S), there is a method in which the container is decompressed as it is, but the solvent dissolved in (B) is condensed and the resin particles (B) are redissolved, or the resin particles When collecting (X), there may be a problem that the resin particles (X) are united with each other.
As a preferable method, for example, carbon dioxide (C) is further mixed with the dispersion in which the resin particles (B) are dispersed in (C), and the solvent (S) is converted from the resin particles (B) to the carbon dioxide phase. A method of extracting and then substituting carbon dioxide containing the solvent (S) with carbon dioxide (C) not containing the solvent (S) and then reducing the pressure can be mentioned.

  In the mixing method of carbon dioxide, carbon dioxide having a pressure higher than that of the dispersion may be added, or the dispersion may be added to carbon dioxide having a pressure lower than that of the dispersion. However, from the viewpoint of ease of continuous operation. The latter is more preferable. The amount of carbon dioxide mixed with the dispersion is preferably 1 to 50 times, more preferably 1 to 40 times, most preferably 1 to 1 times the volume of the dispersion from the viewpoint of preventing coalescence of the resin particles (B). 30 times. By removing or reducing the solvent contained in the resin particles (B) as described above, and then removing carbon dioxide, it is possible to prevent the resin particles (B) from being united.

  As a method of replacing carbon dioxide containing the solvent (S) with carbon dioxide not containing the solvent (S), the resin particles (B) are once supplemented with a filter or cyclone, and then the solvent (S) is maintained while maintaining the pressure. A method of circulating carbon dioxide until it is completely removed can be mentioned. The amount of carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 70 times, and most preferably 1 to 50 times the volume of the dispersion from the viewpoint of removing the solvent from the dispersion. .

  The resin particles (X) of the present invention obtained by the above production method are improved in crystallinity by treatment with carbon dioxide (C) in a liquid or supercritical state, and the melting heat of melting increases.

  The volume average particle diameter of the resin particles (X) of the present invention obtained by the production method of the present invention is preferably 1 to 12 μm, more preferably 2 to 10 μm, and further preferably 3 to 8 μm. When it is 1 μm or more, the handling property as a powder is improved. When it is 12 μm or less, the melting characteristics are improved.

  The ratio Dv / Dn of the volume average particle diameter Dv of the resin particles (X) and the number average particle diameter Dn of the resin particles (X) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4. More preferably, it is 1.0 to 1.3. When it is 1.5 or less, the handling property and melting characteristics as powder are remarkably improved.

The volume average particle diameter of the resin particles (X) and the ratio (Dv / Dn) of the volume average particle diameter Dv and the number average particle diameter Dn of the resin particles (X) are the same as those in the resin particles (B) in (C). In the case of using the method (3) or (4) for dispersing in the resin particle, it is adjusted at the production stage of the resin particles (B). In the case of the method (1), the stirring speed when dispersing the resin (A) dissolved in the solvent (S) and, if necessary, the fine particles (D) in (C), and the fine particles (D) relative to the resin (A) The ratio can be adjusted. When the stirring speed is increased, the volume average particle diameter is decreased, and when the ratio of the fine particles (D) to the resin (A) is increased, the volume average particle diameter is decreased.
The same applies to Dv / Dn of resin particles (X). If the stirring speed is increased, Dv / Dn decreases, and if the ratio of fine particles (D) to resin (A) is increased, Dv / Dn decreases.
The resin particles (X) thus obtained are classified using an air classifier or a sieve, if necessary, and the volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter are further adjusted. can do.

  The volume average particle size and the number average particle size are determined by laser type particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) or Multisizer III (manufactured by Coulter), ELS-800 (Otsuka using laser Doppler method as an optical system). Etc.).

The electrophotographic toner of the present invention preferably has an external additive added.
In general, electrophotographic toners are used by mixing resin particles for toner and inorganic powders such as various metal oxides in order to impart flow characteristics. These inorganic powders are called external additives. Yes.
As external additives, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide and the like are known. In particular, silica particles obtained by reacting silica or titanium oxide fine particles with an organosilicon compound such as dimethyldichlorosilane, hexamethyldisilazane, or silicone oil and replacing the silanol groups on the surface of the silica fine particles with organic groups are preferably used. .
The amount (% by weight) of the external additive is not particularly limited, but is 0.01 to 5 with respect to the weight of the electrophotographic toner to which no external additive is added, from the viewpoint of compatibility between fixability and fluidity. More preferably, it is 0.1-4, Most preferably, it is 0.5-3.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1
In a reaction vessel, 2 parts of ethylene glycol, 400 parts of L-lactide, 150 parts of glycolide, and 2 parts of dibutyltin oxide were charged and reacted at 150 ° C. for 10 hours under normal pressure and nitrogen atmosphere. Furthermore, it cooled to 100 degreeC and obtained polyhydroxycarboxylic acid [crystalline part (a-1)]. [Crystalline part (a-1)] was Mw 4500, melting point (m) 60 ° C., and hydroxyl value 54.

Production Example 2
A reaction vessel was charged with 42 parts of terephthalic acid, 18 parts of isophthalic acid, 40 parts of 1,5-pentanediol, and 2 parts of dibutyltin oxide, and after dehydration reaction at normal pressure and 230 ° C. for 5 hours, 0.5 kPa The dehydration reaction was performed for 5 hours under reduced pressure.
Further, 350 parts of L-lactide and 150 parts of glycolide were added, and reacted at 150 ° C. for 10 hours under normal pressure and nitrogen atmosphere to give a composite resin of polyhydroxycarboxylic acid and polyester resin [crystalline part (a-2)]. Got. [Crystalline part (a-2)] was Mw 10,000, melting point (m) 65 ° C., and hydroxyl value 12.

Production Example 3
A reaction vessel equipped with a stirrer and a dehydrator is charged with 18 parts of 1,6-hexanediol, 400 parts of L-lactide, 150 parts of ε-caprolactone and 2 parts of dibutyltin oxide. The reaction was carried out at 10 ° C for 10 hours. Furthermore, it cooled to 100 degreeC and obtained polyhydroxycarboxylic acid [crystalline part (a-3)] which is a random copolymer of L-lactide and (epsilon) -caprolactone. [Crystalline part (a-3)] was Mw 9000, melting point (m) 75 ° C., and hydroxyl value 27.

Production Example 4
Into a reaction vessel, 1000 parts of methyl ethyl ketone, 19 parts of 1,4-butanediol and 54 parts of hexamethylene diisocyanate were added and reacted at 80 ° C. for 7 hours, and then the above-mentioned [crystalline part (a-1)] 329. Then, the reaction was carried out at 80 ° C. for 7 hours and the solvent was removed at 80 ° C. and 20 kPa to obtain a composite resin [crystalline part (a-4)] of polyhydroxycarboxylic acid and polyurethane resin. [Crystalline part (a-4)] was Mw 11000, melting point (m) 54 ° C., and hydroxyl value 22.

Production Example 5
In a mixing container, 150 parts of the above [crystalline part (a-1)] and crystalline polyester diol composed of 1,6-hexanediol having a hydroxyl value of 22 and sebacic acid (made by Toyokuni Oil Co., Ltd., trade name “ HS2H-500S ") 350 parts was added and mixed at 100 ° C for 1 hour to obtain a mixed resin of polyhydroxycarboxylic acid and polyester resin [crystalline part (a-5)]. [Crystalline part (a-5)] was Mw 12000, melting point (m) 64 ° C., and hydroxyl value 32.

Production Example 6
Into a reaction vessel, 500 parts of tetrahydrofuran, 360 parts of 1,2-propylene glycol and 640 parts of toluene diisocyanate are charged, reacted at 80 ° C. for 5 hours, desolvated at 80 ° C. and 20 kPa, and polyurethane resin [non-crystalline part (B-1)] was obtained. [Amorphous part (b-1)] was Mw 3000 and the NCO content was 1.2%.

Production Example 7
A reaction vessel was charged with 270 parts of terephthalic acid, 730 parts of a PO2 molar adduct of bisphenol A, and 5 parts of dibutyltin oxide. After dehydration reaction at normal pressure and 230 ° C. for 5 hours, under a reduced pressure of 0.5 kPa. A dehydration reaction was performed for 5 hours to obtain a polyester resin [amorphous part (b-2)]. [Amorphous part (b-2)] was Mw5000 and hydroxyl value 55.

Production Example 8
Into a reaction vessel, 500 parts of tetrahydrofuran, 200 parts of the above [non-crystalline part (b-1)] and 1000 parts of the above [crystalline part (a-1)] are charged, and the reaction is carried out at 80 ° C. for 5 hours. The solvent was removed at 80 ° C. and 20 kPa to obtain Resin (A-1). (A-1) was Mw 11000, softening point (s) 72 ° C., melting point (m) 67 ° C., softening point (s) to melting point (m) ratio (s / m) 1.07.
G ′ (m + 20) was 7 × 10 ³ Pa, the melting start temperature (x) was 59 ° C., and the value of | LogG ″ (x + 20) −LogG ″ (x) | was 3.2.
The ratio [G ″ (m + 30) / G ″ (m + 70)] of the loss elastic modulus G ″ (m + 30) at (m + 30) ° C. to the loss elastic modulus G ″ (m + 70) at (m + 70) ° C. was 1.3.
It was n = 1.20 in the formula of the combined form of (b) and (a). The physical property values are listed in Table 1.
To the reaction vessel, 300 parts of this resin (A-1), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-1).

Production Example 9
Except for using 500 parts of tetrahydrofuran, 200 parts of the above [noncrystalline part (b-1)] and 1000 parts of the above [crystalline part (a-2)], the same procedure as in Production Example 8 was carried out to obtain a resin ( A-2) was obtained. The physical property values of the resin (A-2) are shown in Table 1.
To the reaction vessel, 300 parts of this resin (A-2), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-2).

Production Example 10
Into a reaction vessel, 500 parts of tetrahydrofuran, 200 parts of the above-mentioned [non-crystalline part (b-2)] and 38 parts of m-xylylene diisocyanate were added and reacted at 80 ° C. for 5 hours. Sex part (a-1)] 270 parts was added, the reaction was carried out at 80 ° C. for 5 hours, and the solvent was removed at 80 ° C. and 20 kPa to obtain resin (A-3). The physical property values of the resin (A-3) are shown in Table 1.
In a reaction vessel, 300 parts of this resin (A-3), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-3).

Production Example 11
Except for using 500 parts of tetrahydrofuran, 200 parts of the above [noncrystalline part (b-1)], and 900 parts of the above [crystalline part (a-3)], the same procedure as in Production Example 8 was carried out. A-4) was obtained. The physical property values of the resin (A-4) are shown in Table 1.
To the reaction vessel, 300 parts of this resin (A-4), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-4).

Production Example 12
Except for using 500 parts of tetrahydrofuran, 200 parts of the above [noncrystalline part (b-1)], and 850 parts of the above [crystalline part (a-4)], the same procedure as in Production Example 8 was carried out to obtain a resin ( A-5) was obtained. The physical property values of the resin (A-5) are shown in Table 1.
In a reaction vessel, 300 parts of this resin (A-5), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-5).

Production Example 13
Except that 500 parts of tetrahydrofuran, 200 parts of the above [non-crystalline part (b-1)] and 1050 parts of the above [crystalline part (a-5)] are used, the same procedure as in Production Example 8 is carried out. A-6) was obtained. The physical property values of the resin (A-6) are shown in Table 1.
In a reaction vessel, 300 parts of this resin (A-6), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-6).

Production Example 14
Resin (A-7) was prepared in the same manner as in Production Example 10 except that 250 parts of [Crystalline part (a-5)] was used instead of 270 parts of [Crystalline part (a-1)]. Got. The physical property values of the resin (A-7) are shown in Table 1.
In a reaction vessel, 300 parts of this resin (A-7), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-7).

<Preparation of fine particle dispersion for dispersion>
Production Example 15
In a reaction vessel equipped with a dropping funnel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, behenyl acrylate (an acrylate of an alcohol having a linear alkyl group with 22 carbon atoms: Bremer VA (manufactured by NOF Corporation) )) 150 parts and 7.5 parts of azobisisobutyronitrile (AIBN) were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours from the end of the addition, toluene was added at 130 ° C. for 3 hours. Removal under reduced pressure gave an acrylic crystalline resin. The melting point of this resin was 65 ° C. and the number average molecular weight was 50000.
After mixing 700 parts of normal hexane and 300 parts of the above-mentioned acrylic crystalline resin, the mixture is pulverized with zirconia beads having a particle diameter of 0.3 mm in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). A hexane dispersion in which fine particles for dispersion (D-1) were dispersed was obtained. The volume average particle diameter of this dispersion was 0.3 μm.

Production Example 16
In the preparation of the acrylic crystalline resin fine particle (D-1) dispersion in Production Example 15, the dispersion fine particles (D ′ for Comparative Example) were similarly prepared except that 700 parts of hexane was changed to 700 parts of ion-exchanged water. An aqueous dispersion of -1) was obtained. The volume average particle diameter of this aqueous dispersion was 0.3 μm.

Example 1
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, and carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from the cylinder B2 using the pump P4, and the pressure was adjusted to 14 MPa and 40 ° C. In addition, the resin solution (L-1) obtained in Production Example 8 was charged in the resin solution tank T1, and the hexane dispersion of the dispersion fine particles (D-1) prepared in Production Example 15 was charged in the fine particle dispersion tank T2. .
Next, liquid carbon dioxide is charged into the dispersion tank T3 from the liquid carbon dioxide cylinder B1 using the pump P3, adjusted to a supercritical state (9 MPa, 40 ° C.), and further from the tank T2 using the pump P2. Then, a fine particle (D-1) hexane dispersion was introduced.
Next, while stirring the inside of the dispersion tank T3 at 2000 rpm, the resin solution (L-1) was introduced into the dispersion tank T3 from the tank T1 using the pump P1. After the introduction, the pressure inside T3 was 14 MPa.

In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (L-1) 270 parts Dispersion fine particles (D-1) in hexane dispersion 45 parts Carbon dioxide 550 parts

The weight of the introduced carbon dioxide is calculated by calculating the density of carbon dioxide from the temperature of carbon dioxide (40 ° C.) and the pressure (15 MPa) according to the state equation described in the following document, and the volume of the dispersion tank T3. It was calculated by multiplying.
Literature: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596

After introducing the resin solution (L-1), the mixture was stirred for 1 minute to obtain a dispersion in which resin particles (B-1) were dispersed in supercritical carbon dioxide.
Next, the valve V1 was opened, and the dispersion of (B-1) was transferred from T3 to T4 by introducing supercritical carbon dioxide into T3 and T4 using B1 to P3. While the dispersion of (B-1) was transferred from T3 to T4, the opening degree of V2 was adjusted so that the pressure was kept constant. This operation was performed for 30 seconds, and V1 was closed.
Next, by adjusting the opening degree of the pressure adjusting valve V2, carbon dioxide was introduced from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4 while maintaining the pressure at 14 MPa.
By this operation, carbon dioxide containing the solvent was discharged into the solvent trap tank T5, and the resin particles (B-1) were captured by the filter F1. The operation of introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4 was stopped when 5 times the amount of carbon dioxide introduced into the dispersion tank T3 was introduced into the particle recovery tank T4. . At the time of this stop, the operation of replacing the carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the resin particles (B-1) in the filter F1 was completed. Furthermore, the pressure control valve V2 was opened little by little, and the inside of the particle recovery tank was depressurized to atmospheric pressure, whereby the resin particles (X-1) of the present invention supplemented by the filter F1 were obtained.

Examples 2-7
Resin particles (X-) of the present invention were prepared in the same manner as in Example 1 except that the resin solution (L-1) was changed to the resin solutions (L-2) to (L-7) obtained in Production Examples 9 to 14. 2) to (X-7) were obtained.

Examples 8-14
In place of the resin solutions (L-1) to (L-7), 270 parts of (L-1) to (L-7) were added to each of 270 parts of carbon black processed pigment (“MICROLITH Black C-” manufactured by Ciba Japan). Electrophotographic toners (X′-1) to (X′-7) of the present invention were obtained in the same manner as in Examples 1 to 7, except that a colored resin solution mixed with 5 parts of K ″) was used.

Comparative Example 1
In a beaker, 97 parts of ion-exchanged water, 15.4 parts of an aqueous dispersion of fine particles for dispersion (D′-1) obtained in Production Example 16, 1 part of sodium carboxymethylcellulose, and 48.5 of sodium dodecyl diphenyl ether disulfonate 10 parts of a% aqueous solution (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) was added and dissolved uniformly. Then, at 25 ° C., 75 parts of the resin solution (L-1) obtained in Production Example 8 was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. until the concentration became 0.5% or less to obtain an aqueous resin dispersion of resin particles.
Subsequently, it filtered and dried at 40 degreeC * 18 hours, the volatile matter was made into 0.5% or less, and the resin particle (R-1) for a comparison was obtained. Thereafter, physical properties were evaluated without performing supercritical carbon dioxide treatment.

Comparative Example 2
In a beaker, 97 parts of ion-exchanged water, 1 part of sodium carboxymethyl cellulose, and 15 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) were uniformly dissolved.
Next, at 25 ° C., while stirring the TK homomixer at 12,000 rpm, 75 parts of the resin solution (L-1) obtained in Production Example 8 was added and stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. until the concentration became 0.5% or less to obtain an aqueous resin dispersion of resin particles.
Subsequently, it filtered and dried at 40 degreeC * 18 hours, the volatile matter was made into 0.5% or less, and the resin particle (R-2) for a comparison was obtained. Thereafter, physical properties were evaluated without performing supercritical carbon dioxide treatment.

Comparative Examples 3-4
Instead of resin solution (L-1), a colored resin solution in which 1.4 parts of carbon black processed pigment (“MICROLITH Black C-K” manufactured by Ciba Japan) is mixed as a colorant with 75 parts of (L-1) Except that was used, electrophotographic toners (R′-1) and (R′-2) for comparison were obtained in the same manner as in Comparative Examples 1 and 2.

<Measuring method of melting point (m) and heat of fusion>
A sample (5 mg) is collected and placed in an aluminum pan, and the DSC (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.) is used to determine the temperature (° C) of the endothermic peak due to melting at a heating rate of 10 ° C per minute. This was determined as the melting point (m).
The heat of fusion was determined from the area of the endothermic peak. Using the obtained heat of fusion, the ratio of heat of fusion was obtained from the following formula.
Ratio of heat of fusion = H2 / H1

<Evaluation of volume average particle diameter>
The resin particles were dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1%), and the volume average particle size was measured with a Coulter counter [Multisizer III (manufactured by Beckman Coulter)].

<Evaluation of heat-resistant storage stability>
The heat resistant storage stability of the resin particles was evaluated by the following method.
10 g of resin particles are collected in a 30 ml glass screw tube having a diameter of about 3 cm. The glass screw tube containing the resin particles was allowed to stand for 15 hours in a thermostat controlled at 50 ° C., and evaluated according to the following criteria depending on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied with a finger or the like.
X: Blocking occurs, and even if force is easily applied with a finger or the like, it does not disperse.

<Evaluation of low-temperature fixability>
The fixing temperature was evaluated by the following method.
1.0% of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) is added to the electrophotographic toner of the present invention or the electrophotographic toner for comparison, and mixed well using a mixer, so that Aerosil R972 adheres uniformly to the toner surface. Toner was made.
The toner for evaluation obtained above was uniformly placed on the paper so as to be 0.6 mg / cm ² .
At this time, as a method of placing the powder on the paper surface, a printer from which the heat fixing machine is removed is used (other methods may be used as long as the powder can be uniformly placed at the above-mentioned weight density). When this paper was passed through a pressure roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² , the temperature at which a cold offset was generated was measured.

Resin particles (X-1) to (X-7) of the present invention prepared in Examples 1 to 7, and resin particles (R-1) for comparison prepared in Comparative Examples 1 and 2 (R-2) ) Melting point, heat of fusion, volume average particle diameter, and heat resistant storage stability were measured by the above methods.
The electrophotographic toners (X′-1) to (X′-7) of the present invention prepared in Examples 8 to 14 and the electrophotographic toner for comparison (R′-1) prepared in Comparative Examples 3 and 4 , (R′-2) was measured by the above method. The results are shown in Table 2.

  The resin particles and electrophotographic toners of Examples 1 to 14 were excellent in heat-resistant storage stability and low-temperature fixability, whereas the resin particles and electrophotographic toners of Comparative Examples 1 and 3 were significantly deteriorated in low-temperature fixability. Further, the resin particles and the electrophotographic toners of Comparative Examples 2 and 4 were excellent in low-temperature fixability, but the heat-resistant storage stability was significantly deteriorated.

  The resin particles obtained by the production method of the present invention are extremely useful as base particles for an electrophotographic toner because they are excellent in heat-resistant storage stability and low-temperature fixability. In addition, paint additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, electronic component manufacturing spacers, electronic measuring instrument standard particles, electronic paper particles, medical diagnostic carriers It is also useful as electrorheological particles and other molding resin particles.

T1: Resin solution tank T2: Solution tank T3: Dispersion tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C.)
T5: Solvent trap F1: Ceramic filter (mesh: 0.5 μm)
B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1: Valve V2: Pressure adjustment valve

Claims (7)

Resin particles (B) containing a resin (A) composed of a crystalline part (a) having a polyhydroxycarboxylic acid (p) as essential constituents and an amorphous part (b) are in a liquid or supercritical state. Is a method for producing resin particles (X) comprising the steps of treating with carbon dioxide (C) and then removing (C), and the heat of fusion by differential scanning calorimetry (DSC) measurement of the obtained (X) is as follows: A method for producing resin particles (X) that satisfies the relational expression (1) and has a weight ratio of the crystalline part (a) in the resin (A) of 30 to 95%.
0 ≦ H2 / H1 ≦ 0.9 (1)
[In relational expression (1), H1 represents the heat of fusion (J / g) at the first temperature rise by DSC measurement; H2 represents the measurement value of the heat of fusion (J / g) at the second temperature rise by DSC measurement. ]   The manufacturing method according to claim 1, wherein the resin particles (B) contain a resin (A) and a solvent (S), and include a step of removing (C) and (S). The resin (A) has a melting point (m) of 40 to 110 ° C., and the ratio (s / m) of the softening point (s) [° C.] to the melting point (m) [° C.] of 0.8 to 1.55 The manufacturing method according to claim 1, wherein the resin has a melting start temperature (x) within a temperature range of (m ± 20) ° C. and satisfies the following conditions.
[Condition 1] G ′ (m + 20) = 50 to 1 × 10 ⁶ [Pa]
[Condition 2] | LogG ″ (x + 20) −LogG ″ (x) |> 2.0
[G ′: storage elastic modulus [Pa], G ″: loss elastic modulus [Pa]]   Ratio of loss elastic modulus G ″ (m + 30) at (m + 30) ° C. and loss elastic modulus G ″ (m + 70) at (m + 70) ° C. of resin (A) [G ″ (m + 30) / G ″ (m + 70)] [ The melting point of resin (A)] is 0.05-50, m is a manufacturing method in any one of Claims 1-3. The resin (A) is a resin in which a crystalline part (a) and an amorphous part (b) are linearly bonded in the following format, and n is 0.9 to 3.5. The manufacturing method in any one of -4.
(A) {-(b)-(a)} n   Resin particle (X) obtained by the manufacturing method in any one of Claims 1-5.   An electrophotographic toner containing the resin particles (X) according to claim 6.