JP5138670B2 - 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 two inventions.
(I) Resin particles (B) containing a resin (A) composed of a crystalline part (a) containing polyurethane and / or polyurea (p) as essential constituents and an amorphous part (b) are liquid. Alternatively, a method for producing resin particles (X) comprising a step of treating with carbon dioxide (C) in a supercritical state and then removing (C), which is obtained by differential scanning calorimetry (DSC) measurement of (X) A method for producing resin particles (X) whose heat of fusion satisfies the following relational expression (1).
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.

  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.
The first invention is an invention relating to a method for producing resin particles, and comprises a crystalline part (a) having polyurethane and / or polyurea (p) as essential constituents and an amorphous part (b). 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 this process, the carbon dioxide (C) is removed to obtain the resin particles (X).

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 0.81 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 an amorphous part (b) containing polyurethane and / or polyurea (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 polyurethane and / or polyurea (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.

  The polyurethane and / or polyurea (p) means any one of polyurethane, polyurea, and polyurethane / polyurea. The polyol component containing the diol (c) and / or the polyamine component containing the diamine (d) and the diisocyanate (e ) -Containing polyisocyanate component and / or polyurethane and / or polyurea. However, if necessary, a trifunctional or higher functional polyol (f), a trifunctional or higher functional polyamine (g), or a trifunctional or higher functional polyisocyanate (h) may be used in combination.

As a polyol component which comprises a polyurethane and / or polyurea (p), aliphatic diol (c1) is preferable and it is preferable that it is C2-C36. More preferred is a linear aliphatic diol (c11). Also preferred are linear aliphatic polyester diol (c12) and linear aliphatic polyether diol (c13).
When the aliphatic diol, the aliphatic polyester diol, and the aliphatic polyether diol are branched, the crystallinity of the polyurethane and / or polyurea is lowered and the melting point is lowered, so that the heat-resistant storage stability may be deteriorated. In addition, when the aliphatic diol has more than 36 carbon atoms, it may be difficult to obtain a practical material.

Examples of the polyol component composed of the diol (c) and, if necessary, a trifunctional or higher functional (3- to 8- or higher valent) polyol (f) include linear aliphatic diol (c11) and linear aliphatic polyester diol The total content of (c12) and the linear aliphatic polyether diol (c13) is preferably 70 mol% or more, more preferably 80 mol% or more of the polyol component. Other diol (c2) may be included as necessary.
When the total content of the linear aliphatic diol, the linear aliphatic polyester diol, and the linear aliphatic polyether diol is less than 70 mol%, the crystallinity of the polyurethane and / or polyurea decreases, and the melting point decreases. Therefore, the heat resistant storage stability may be deteriorated.

Specific examples of the linear aliphatic diol (c11) include 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-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, Examples include, but are not limited to, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol.
Among these, considering availability, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1, 10-decanediol is preferred.

  Examples of the linear aliphatic polyester diol (c12) include the above linear aliphatic diols and linear aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid). And polyester diols composed of acids and the like.

  Examples of the linear aliphatic polyether diol (c13) include ethylene oxide (hereinafter abbreviated as EO), tetrahydrofuran (hereinafter abbreviated as THF), and the like of the above linear aliphatic diol] 300).

  In addition, aliphatic diols (c1) other than (c11) and other diols (c2) used in combination as needed include aliphatic diols other than those having 2 to 36 carbon atoms (1,2-propylene) Glycol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); other than (c13), C4-C36 alkylene ether glycol (dipropylene glycol, polypropylene glycol, etc.); C4-C36 Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxides of the above alicyclic diols (hereinafter abbreviated as AO) [EO, propylene oxide (hereinafter abbreviated as PO), butylene Oxide (hereinafter abbreviated as BO) etc.] Adduct (addition mole number 1 0); AO [EO, PO, BO, etc.] adducts of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (additional mole number 2-30); branched aliphatic polyester diol; aromatic polyester diol; Type aliphatic polyether diols; polylactone diols (such as poly ε-caprolactone diols); and polybutadiene diols.

Furthermore, as the other diol (c2), a diol having another functional group may be used in addition to the diol having no terminal functional group other than the above hydroxyl group.
Examples of the diol having such a functional group include a diol having a carboxyl group (c21), a diol having a sulfonic acid group or a sulfamic acid group (c22), and salts thereof.
Examples of the diol (c21) having a carboxyl group include dialkyrol alkanoic acids [for C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dithiol. Methylol heptanoic acid, 2,2-dimethylol octanoic acid, etc.].

Examples of the diol (c22) 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 (C1-6 of the alkyl group) or an AO adduct thereof (EO is PO, such as EO or PO, 1-6 addition moles of AO): For example, N, N-bis (2 -Hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; 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).
Preferred as these aliphatic diols (c1) other than (c11) and other diols (c2) are AO adducts of bisphenols, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, and these It is a combined use.

The polyamine component constituting the polyurethane and / or polyurea (p) is preferably an aliphatic diamine (d1), and preferably having 2 to 36 carbon atoms. More preferably, it is a linear aliphatic diamine (d11).
When the aliphatic diamine (d1) is branched, the crystallinity of polyurethane and / or polyurea is lowered and the melting point is lowered, so that the heat resistant storage stability may be deteriorated. On the other hand, when the number of carbon atoms exceeds 36, it may be difficult to obtain practical materials.

As the polyamine component composed of the diamine (d) and, if necessary, a triamine or higher (3 to 8 or more valent) polyamine (g), the content of the linear aliphatic diamine (d11) is 70 of the polyamine component. It is preferably at least mol%, more preferably at least 80 mol%. Other diamine (d2) may be included as necessary.
When the content of the linear aliphatic diamine (d11) is less than 70 mol%, the crystallinity of polyurethane and / or polyurea is lowered and the melting point is lowered, so that the heat resistant storage stability may be deteriorated.

Specific examples of the linear aliphatic diamine (d11) include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1 , 7-heptanedidiamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1 , 14-tetradecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, and the like, but are not limited thereto.
Among these, considering availability, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 1,10- Decanediamine is preferred.

In addition, as aliphatic diamine (d1) other than (d11) and other diamine (d2) used in combination with linear aliphatic diamine (d11) as necessary, aliphatic polyamines other than the above (C2-C18) and aromatic polyamines (C6-C20).
As aliphatic polyamines (C2 to C18) other than the above, [1] branched aliphatic diamine {C2 to C6 alkylenediamine (1,2-propylenediamine, etc.), polyalkylene (C2 to C6) diamine [diethylenetriamine, imino Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] These alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substituents [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.]; [3] alicyclic or heterocyclic ring contained Aliphatic Jami {Alicyclic diamines (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, 1,4 bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) -2 , 4,8,10-tetraoxaspiro [5,5] undecane, etc.]; [4] Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.); etc. Is mentioned.

As aromatic polyamines (C6 to C20), [1] unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethane Diamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4 , 4 ', 4 "-triamine, naphthylenediamine, etc .; [2] aromatic diamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], for example 2 , 4- and 2,6-tolylenediamine, crude tolylenediamine, di Tiltlylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diamino Benzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diamino Benzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5 '-Tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3'-diethyl-2, '-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3 ', 5,5'- Tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylsulfone, etc.], and mixtures of these isomers in various proportions; [3] nucleus Aromatic diamines having substituted electron withdrawing groups (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2, -Dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo -Diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2) -Chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino) -3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-me Renbis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic diamine having a secondary amino group [1] To [3] wherein a part or all of —NH ₂ of the aromatic diamine is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [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.].

  As the diisocyanate (e) and a tri- or higher functional polyisocyanate (h) used in combination as necessary, an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter) and 2 carbon atoms. -18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, C8-15 araliphatic diisocyanate, modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette Group, uretdione group, uretoimine group, isocyanurate group, modified product containing oxazolidone group) and a mixture of two or more of these. Moreover, you may use together trifunctional or more (3-8 valence or more) polyisocyanate (h) if needed.

  Specific examples of the aromatic diisocyanate and the trivalent or higher aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI). , Crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixture thereof; diaminodiphenylmethane] And a small amount (for example, 5 to 20% by weight) of a trifunctional or higher polyamine]] phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -tri Phenylmethane triisocyanate, m- and p Such isocyanatophenyl sulfonyl isocyanate.

  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, 2,2 , 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2, Examples include 6-diisocyanatohexanoate.

  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, and 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 tri- or higher valent araliphatic polyisocyanates include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate. (TMXDI).

Examples of the modified products of the above diisocyanates and tri- or higher polyisocyanates include urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, and oxazolidone group-containing modified products. Can be mentioned.
Specifically, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), modified products of diisocyanates such as urethane modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane modified TDI ( In combination with an isocyanate-containing prepolymer)] and the like.

  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.

  The molecular weight of the polyurethane and / or polyurea (p) is preferably that having a weight average molecular weight (Mw) of 2000 to 80000 determined by gel permeation chromatography (GPC). The glass transition temperature (Tg) is preferably -100 to 40 ° C, more preferably -80 to 0 ° C. The melting point (m) is preferably 40 to 100 ° C.

The resin constituting the crystalline part (a) has polyurethane and / or polyurea (p) as an essential component, and is not particularly limited as long as it has crystallinity. A single resin of polyurethane and / or polyurea (p) Alternatively, it may be a composite resin with another resin having crystallinity.
As the other resin having crystallinity used for the composite resin, one or more resins selected from polyester resins and polyamide resins are preferable because a block of polyurethane and / or polyurea (p) is easily introduced.
The composite resin can be obtained, for example, by bonding a crystalline polyester resin, a crystalline polyamide resin, and a mixture thereof with polyurethane and / or polyurea (p).

The crystalline polyester resin is preferably a polyester resin synthesized from a polyol component containing the diol (c) and a polycarboxylic acid component containing the dicarboxylic acid (i). However, if necessary, a trifunctional or higher functional polyol (f) or a trifunctional or higher functional polycarboxylic acid (j) may be used in combination.
The crystalline polyamide resin is preferably a polyamide resin synthesized from a polyamine containing diamine (d) and a polycarboxylic acid component containing dicarboxylic acid (i). However, if necessary, a trifunctional or higher functional polyamine (g) or a trifunctional or higher functional polycarboxylic acid (j) may be used in combination.

  A polyol component, a polycarboxylic acid component, and a polyamine component (each including three or more functional groups) used for the crystalline polyester resin and the crystalline polyamide resin are respectively shown.

Among the polyol components, the diol (c) is preferably an aliphatic diol (c1), and preferably having 2 to 36 carbon atoms. Moreover, linear aliphatic diol (c11) is more preferable.
When the aliphatic diol (c1) is branched, the crystallinity of the resin is lowered and the melting point is lowered, so that the heat resistant storage stability may be deteriorated. On the other hand, when the number of carbon atoms exceeds 36, it may be difficult to obtain practical materials.

The polyol component composed of the diol (c) and, if necessary, a tri- or higher functional (3- to 8- or higher valent) polyol (f) has a linear aliphatic diol (c11) content of the polyol component of 80. It is preferably at least mol%, more preferably at least 90 mol%. Other diol (c2) may be included as necessary.
When the content of the linear aliphatic diol (c11) is less than 80 mol%, the crystallinity of the resin is lowered and the melting point is lowered, so that the heat resistant storage stability may be deteriorated.

Specific examples of the linear aliphatic diol (c11) include those described above, and preferred ones are also the same.
In addition, the aliphatic diol (c1) other than (c11) and the other diol (c2) used in combination with the linear aliphatic diol (c11) as necessary include those other than the above (c11) And aliphatic diol (c1) and other diol (c2), diol (c21) having a carboxyl group, diol (c22) having a sulfonic acid group or sulfamic acid group, and salts thereof are exemplified. The preferable ones are also the same.
Examples of the trifunctional or higher (3 to 8 valence or higher) polyol (f) used as necessary include those described above, and preferable ones are also the same.

Among the polycarboxylic acid components, as the dicarboxylic acid (i), an alkanedicarboxylic acid having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.), C6-C40 alicyclic dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.], C4-C36 alkene dicarboxylic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.) Alkenyl 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 and the like).
Moreover, you may use together polycarboxylic acid (j) more than trifunctional (3-6 valence or more) as needed.
Examples of the tri- or higher functional polycarboxylic acid (j) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and aliphatic or alicyclic polycarboxylic acids having 6 to 36 carbon atoms. An acid (hexane tricarboxylic acid etc.) etc. are mentioned.
The dicarboxylic acid (i) and the tri- or higher functional polycarboxylic acid (j) include the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.). It may be used.
In view of crystallinity and availability, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid are particularly preferable.

Among the polyamine components, the diamine (d) is preferably an aliphatic diamine (d1), and preferably having 2 to 36 carbon atoms. Moreover, linear aliphatic diamine (d11) is more preferable.
When the aliphatic diamine (d1) is a branched type, the crystallinity of the resin is lowered and the melting point is lowered, so that the heat resistant storage stability may be deteriorated. On the other hand, when the number of carbon atoms exceeds 36, it may be difficult to obtain practical materials.

The polyamine component composed of the diamine (d) and, if necessary, a triamine or higher (3 to 8 or more valent) polyamine (g), the content of the linear aliphatic diamine (d11) is 80% of the polyamine component. It is preferably at least mol%, more preferably at least 90 mol%. Other diamine (d2) may be included as necessary.
If the content of the linear aliphatic diamine (d11) is less than 80 mol%, the crystallinity of the resin is lowered and the melting point is lowered, so that the heat resistant storage stability may be deteriorated.

  Examples of the polyamine component include those described above.

  The proportion of polyurethane and / or polyurea (p) in the resin constituting the crystalline part (a) is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40 to 95% by weight.

  In the method of bonding polyurethane and / or polyurea (p) to a crystalline polyester resin and a crystalline polyamide resin, is a binder (coupling agent) used in consideration of the reactivity of the functional group contained in each? In the case of using the resin, it is possible to select a binder suitable for the functional group to be contained and bond it to form a composite resin.

  When a binder is not used when producing a composite resin, there is a method of proceeding the reaction between the functional group contained in the polyurethane and / or polyurea (p) and the functional group contained in the other resin while heating and reducing pressure as necessary. Can be mentioned. 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 a composite resin, as an example of a dehydration reaction, when both polyurethane and / or polyurea (p) and other resins forming the composite resin have a hydroxyl group, these hydroxyl groups are bonded to a binder (for example, Reaction with polyvalent 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.

  An example of the addition reaction is a case where both polyurethane and / or polyurea (p) and other resins forming the composite resin have a hydroxyl group at the terminal, and a reaction in which these are bonded with a binder (for example, polyvalent isocyanate) In addition, when one of the polyurethane and / or polyurea (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 used without using a binder. The reaction which couple | bonds is mentioned. In this case, for example, polyurethane and / or polyurea (p) and other resins forming the composite resin are dissolved in a solvent that can be dissolved, and if necessary, a binder is added, and the reaction temperature is 80 ° C. to 150 ° C. The crystalline part (a) which is a composite resin is obtained.

Examples of the resin constituting the amorphous part (b) include polyester resins (including lactone ring-opening polymers), polyurethane resins, polyurea resins, polyamide resins, polystyrene resins, and styrene acrylic polymers.
Of these, polyester resins, polyurethane resins, polyurea resins, polyamide resins, and composite resins thereof are preferred, and polyurethane resins and polyester resins are more preferred.

Similar to the crystalline part (a), the polyester resin is preferably a polyester resin synthesized from a polyol component containing the diol (c) and a polycarboxylic acid component containing the dicarboxylic acid (i). However, if necessary, a trifunctional or higher functional polyol (f) or a trifunctional or higher functional polycarboxylic acid (j) can be used in combination.
The polyurethane resin is preferably a polyurethane resin synthesized from a polyol component containing the diol (c) and a polyisocyanate component containing the diisocyanate (e). However, if necessary, a trifunctional or higher functional polyol (f) or a trifunctional or higher functional polyisocyanate (h) can be used in combination.
The polyurea resin is preferably a polyurea resin synthesized from a polyamine containing diamine (d) and a polyisocyanate component containing diisocyanate (e). However, a trifunctional or higher functional polyamine (g) or a trifunctional or higher functional polyisocyanate (h) can be used in combination as required.
The polyamide resin is preferably a polyamide resin synthesized from a polyamine containing diamine (d) and a polycarboxylic acid component containing dicarboxylic acid (i). However, a trifunctional or higher functional polyamine (g) or a trifunctional or higher functional polycarboxylic acid (j) can be used in combination as necessary.
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. is there.
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).
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 include those described above.

Among the methods for bonding (a) and (b), examples of dehydration reactions include those in which the crystalline part (a) and the non-crystalline part (b) are resins having a hydroxyl group at their terminals. Examples of the reaction include binding with a binder (for example, a polyvalent carboxylic acid). In this case, for example, the resin (A) is obtained by reaction at a reaction temperature of 180 ° C. to 230 ° C. in the absence of a solvent.
Examples of the addition reaction include a resin having a hydroxyl group at both ends of the crystalline part (a) and the non-crystalline part (b), a reaction in which these are bonded with a binder (for example, a polyvalent isocyanate), and crystallinity. In the case where one of the part (a) and the non-crystalline part (b) is a resin having a hydroxyl group at the terminal and the other is a resin having an isocyanate group at the terminal, there is a reaction of bonding them without using a binder. . In this case, for example, both the crystalline part (a) and the non-crystalline part (b) are dissolved in a soluble solvent, and if necessary, a binder is added and reacted at a reaction temperature of 80 ° C. to 150 ° C. Resin (A) is obtained.

  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, the resin particles are hardly deteriorated. 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]
[G ′: storage elastic modulus [Pa]]
When G ′ at (m + 20) ° C. is 50 Pa or more, when the resin particles are electrostatically coated, they can be uniformly applied even at low temperature application, and the application temperature range is widened. Further, if it is 1 × 10 ⁶ [Pa] or less, the meltability at a 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”, and after a slight increase of the piston due to thermal expansion of the sample, the piston again Is read from the graph, and this value is taken as the melting start temperature.

The resin (A) preferably satisfies the following [Condition 2] with respect to the loss elastic modulus G ″ [Pa] and the melting start temperature (x) [° C.], and satisfies [Condition 2-2]. It is more preferable to satisfy [Condition 2-3], and it is most preferable to satisfy [Condition 2-4].
[Condition 2] | LogG ″ (x + 20) −LogG ″ (x) |> 2.0
[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 surface smoothness can be obtained on the side and the high temperature side. In addition, the process from the start of melting to the applicable viscosity is fast, which is advantageous for obtaining excellent low-temperature meltability. [Condition 2] is an index of the sharp melt property of the resin, which indicates how fast it can be melted with little 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 modulus in the above range, when the resin particles are electrostatically coated, more stable surface smoothness can be obtained in the coating 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) can be obtained by measuring the Mw of the resin constituting (a) and the resin constituting (b) before bonding.
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 the resin particles are used for electrostatic coating, the temperature range where application is possible 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 of dispersing a resin (A) dissolved in a solvent (S) in (C) to obtain a resin particle (B) dispersion (2) A molten resin (A) in (C) Method of dispersing and obtaining resin particle (B) dispersion (3) Method of preparing resin particle (B) by another method and dispersing (B) directly in (C) by stirring, ultrasonic irradiation or the like ( 4) Method of dispersing resin particles (B) prepared by another method in solvent (T) and introducing the dispersion into (C) In addition, in the dispersion method of (1) and (2), It is preferable to use fine particles for dispersion (D). 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 solution (L) of the resin (A) is produced by dissolving the resin (A) in the solvent (S).
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). .

  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.).

  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
Into a reaction vessel, 1000 parts of methyl ethyl ketone, 430 parts of 1,6-hexanediol and 570 parts of hexamethylene diisocyanate were added, reacted at 80 ° C. for 7 hours, desolvated at 80 ° C. and 20 kPa, and polyurethane resin [crystalline part (A-1)] was obtained. [Crystalline part (a-1)] was Mw 7500, melting point (m) 75 ° C., and hydroxyl value 34.

Production Example 2
1000 parts of methyl ethyl ketone, 210 parts of 1,6-hexanediol, 500 parts of a polyester diol composed of 1,6-hexanediol having a hydroxyl value of 56 and sebacic acid (product name “HS 2H-200S” manufactured by Toyokuni Oil Co., Ltd.), A polyurethane resin [crystalline part (a-2)] was obtained in the same manner as in Production Example 1, except that 290 parts of hexamethylene diisocyanate was used. [Crystalline part (a-2)] was Mw 9000, melting point (m) 60 ° C., and hydroxyl value 26.

Production Example 3
Except for using 1000 parts of methyl ethyl ketone, 350 parts of 1,6-hexanediol, 90 parts of 1,6-hexanediamine, and 560 parts of hexamethylene diisocyanate, the same procedure as in Production Example 1 was carried out to obtain a polyurethane urea resin [crystalline part (a -3)]. [Crystalline part (a-3)] was Mw 6000, melting point (m) 80 ° C., and hydroxyl value 44.

Production Example 4
A polyurethane resin [amorphous part (b-1)] was obtained in the same manner as in Production Example 1 except that 500 parts of tetrahydrofuran, 360 parts of 1,2-propylene glycol and 640 parts of toluene diisocyanate were used. [Amorphous part (b-1)] was Mw3000.

Production Example 5
A polyurethane resin [amorphous part (b-2)] was obtained in the same manner as in Production Example 1 except that 500 parts of methyl ethyl ketone, 210 parts of 1,4-cyclohexanedimethanol and 290 parts of toluene diisocyanate were used. [Amorphous part (b-2)] was Mw5000.

Production Example 6
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-3)]. [Amorphous part (b-3)] was Mw5000 and hydroxyl value 55.

Production Example 7
Into a reaction vessel, 1150 parts of methyl ethyl ketone, 200 parts of the above [non-crystalline part (b-1)] and 50 parts of toluene diisocyanate were added and reacted at 80 ° C. for 5 hours, and then the above-mentioned [crystalline part (a -1)] 900 parts were 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 a resin (A-1). (A-1) was Mw18000, softening point (s) 75 ° C., melting point (m) 72 ° C., softening point (s) to melting point (m) ratio (s / m) 1.04.
G ′ (m + 20) was 7 × 10 ³ Pa, the melting start temperature (x) was 70 ° C., and the value of | LogG ″ (x + 20) −LogG ″ (x) | was 3.4.
The ratio of loss elastic modulus G ″ at (m + 30) ° C. to loss elastic modulus G ″ at (m + 70) ° C. [G ″ (m + 30) / G ″ (m + 70)] was 2.7.
It was n = 1.08 in the type | formula of the coupling | bonding type 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 8
After 700 parts of methyl ethyl ketone, 100 parts of the above [non-crystalline part (b-1)] and 25 parts of toluene diisocyanate are reacted, 575 parts of the above [crystalline part (a-2)] are introduced. Except that, Resin (A-2) was obtained in the same manner as in Production Example 7. 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 9
After adding 1030 parts of methyl ethyl ketone, 200 parts of the above [noncrystalline part (b-1)], and 50 parts of toluene diisocyanate, 780 parts of the above [crystalline part (a-3)] are introduced. Except that, Resin (A-3) was obtained in the same manner as in Production Example 7. 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 10
Into a reaction vessel, 780 parts of methyl ethyl ketone, 200 parts of the above [non-crystalline part (b-2)], and 580 parts of the above [crystalline part (a-1)] are charged and reacted at 80 ° C. for 5 hours. The solvent was removed at 80 ° C. and 20 kPa to obtain a resin (A-4). 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 11
In a reaction vessel, 500 parts of tetrahydrofuran, 200 parts of the above [noncrystalline part (b-3)] and 38 parts of m-xylylene diisocyanate were added and reacted, and then the above [crystalline part (a-1 )] Resin (A-5) was obtained in the same manner as in Production Example 7 except that 600 parts were added. 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).

<Preparation of fine particle dispersion for dispersion>
Production Example 12
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 13
In the preparation of the acrylic crystalline resin fine particle (D-1) dispersion in Production Example 12, except that 700 parts of hexane was changed to 700 parts of ion-exchanged water, fine particles for dispersion (D ′ 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. Further, the resin solution (L-1) obtained in Production Example 7 was charged in the resin solution tank T1, and the hexane dispersion of the dispersion fine particles (D-1) prepared in Production Example 12 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 2-5
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-5) obtained in Production Examples 8 to 11. 2) to (X-5) were obtained.

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 13, 1 part of sodium carboxymethyl cellulose, 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 7 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.
Then, at 25 ° C., 75 parts of the resin solution (L-1) obtained in Production Example 7 was added and stirred for 2 minutes while stirring the TK homomixer at 12,000 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-2) for a comparison was obtained. Thereafter, physical properties were evaluated without performing supercritical carbon dioxide treatment.

<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 were 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 meltability>
The melting temperature was evaluated by the following method.
Using a commercially available corona charging spray gun on a standard zinc phosphate-treated steel plate made by Nippon Test Panel, resin particles are electrostatically coated so that the film pressure is 20 to 40 μm, and the baking temperature is changed for evaluation. The minimum temperature at which the surface smoothness by visual confirmation after baking for 5 minutes was good was measured.

  Resin particles (X-1) to (X-5) of the present invention prepared in Examples 1 to 5 and resin particles (R-1) for comparison prepared in Comparative Examples 1 and 2 (R-2) The evaluation results are shown in Table 2.

  The resin particles of Examples 1 to 5 were excellent in heat-resistant storage stability and low-temperature meltability, whereas the resin particles of Comparative Example 1 were significantly deteriorated in low-temperature meltability and heat-resistant storage stability. Moreover, although the resin particle of the comparative example 2 has favorable low-temperature meltability, the heat-resistant storage property deteriorated remarkably.

  Since the resin particles obtained by the production method of the present invention are excellent in heat-resistant storage stability and low-temperature melting property, the base particles of electrophotographic toner, paint additives, cosmetic additives, paper coating additives, slash It is useful as a molding resin, powder coating, electronic component manufacturing spacer, standard particles for electronic measuring instruments, electronic paper particles, medical diagnostic carriers, electroviscous 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 polyurethane and / or polyurea (p) as essential constituents and an amorphous part (b) are liquid or supercritical. A process for producing resin particles (X) comprising a step of treating with carbon dioxide (C) in a state and then removing (C), wherein the obtained (X) has a heat of fusion measured by differential scanning calorimetry (DSC). Resin particles (X) satisfying the following relational expression (1) and performing DSC measurement under the condition of cooling to 0 ° C. at the cooling rate of 90 ° C./min after the first temperature rise and before the second temperature rise. Manufacturing method.
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). Resin (A) has a melting point (m) of 40 to 110 ° C., and a ratio (s / m) of a softening point (s) [° C.] to a melting point (m) [° C.] of 0.8 to 1.2 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 −2 ] | LogG ″ (x + 20) −LogG ″ (x) |> 2.5
[G ′: storage elastic modulus [Pa], G ″: loss elastic modulus [Pa]]   Ratio of loss elastic modulus G ″ at (m + 30) ° C. and loss elastic modulus G ″ at (m + 70) ° C. of resin (A) [G ″ (m + 30) / G ″ (m + 70)] [m is resin (A) The melting point of] is 0.05-50, The 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 0.5 to 3.5. The manufacturing method in any one of -4.
(A) {-(b)-(a)} n The weight ratio of the crystalline part (a) in the resin (A) is 30 to 95%.
The manufacturing method in any one of.   Resin particles (X) obtained by the production method according to claim 1.

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