WO2015087986A1

WO2015087986A1 - Method for producing dispersion, and dispersion

Info

Publication number: WO2015087986A1
Application number: PCT/JP2014/082901
Authority: WO
Inventors: 貴司芥川; 健一郎榎; 大輝松田; 理根布谷; 修一篠原; 金子　尚史; 太田　浩二; 泰治山下
Original assignee: 三洋化成工業株式会社
Priority date: 2013-12-11
Filing date: 2014-12-11
Publication date: 2015-06-18
Also published as: JPWO2015087986A1; JP6533467B2

Abstract

The purpose of the present invention is to provide a dispersion production method with which it is possible to obtain, quickly and with small power, a dispersion in which a dispersoid, such as solid particles, is dispersed in a dispersion solvent finely and stably. This method for producing a dispersion (L) is a method for producing a dispersion (L) in which particles (C), including a dispersoid (A), are dispersed in a solvent (S), the method comprising a step for expanding the volume of a mixture (X) including the dispersoid (A), the solvent (S), and a compressible fluid (F), the method being characterized in that: the volume of the mixture (X) is expanded at a temperature lower than or equal to the boiling point or the softening point of the dispersoid (A) in a state where the dispersoid (A) is dissolved in the solvent (S) and/or the compressible fluid (F) at a temperature lower than or equal to the boiling point or the softening point of the dispersoid (A); and the median diameter of the particles (C) is less than or equal to 3.0 µm.

Description

Dispersion production method and dispersion

The present invention relates to a method for producing a dispersion and a dispersion. Specifically, the present invention relates to a method for producing a dispersion in which various fine particles such as solid particles are dispersed in a solvent, and the dispersion.

In various manufacturing processes such as paints, inks, cosmetics, foods, pharmaceuticals, etc., the process includes the step of making materials such as solid particles fine and dispersing the fine particles in a dispersion solvent such as water or organic solvent to produce a dispersion. However, the conventional method and apparatus require a long time and a lot of power to disperse the fine particles such as solid particles in the solvent.
In order to improve the method as described above, after supplying a mixture of a dispersoid and a solvent to a supercritical container to be in a supercritical state, the mixture in the supercritical state is released into the atmosphere, and is put into a collision part. As a method of dispersing the dispersoid in a solvent by making it collide (for example, see Patent Document 1) or a method of turning the dispersoid into a fine particle by crystallization, a supercritical fluid in which the dispersoid is dissolved is ejected from a nozzle. The supercritical rapid expansion method for precipitating the dispersoid or the solution in which the dispersoid is dissolved is ejected from the nozzle into the supercritical fluid, or the supercritical fluid is ejected from the nozzle in the solution in which the solute is dissolved. Although a supercritical poor solvent method for precipitation has been proposed (see, for example, Patent Document 2), there is a problem that dispersibility of the dispersoid in the solvent is insufficient.
Furthermore, although a method has been proposed in which a mixture of a dispersoid and a compressive fluid is expanded under reduced pressure from a temperature equal to or higher than the melting point of the dispersoid (Patent Document 3), the stability of the dispersion after expansion under reduced pressure is insufficient. There is a problem that only a crystalline material having a melting point can be handled.

Japanese Patent Laid-Open No. 10-192670 JP 2006-181553 A JP 2011-115780 A

The problem to be solved by the present invention is to provide a method for producing a dispersion, in which a dispersoid such as solid particles is finely and stably dispersed in a dispersion solvent can be obtained quickly and with little power. It is.

According to the present invention, the particles (C) containing the dispersoid (A), including the step of expanding the volume of the mixture (X) containing the dispersoid (A), the solvent (S), and the compressive fluid (F). Is a process for producing a dispersion (L) in which the dispersoid (A) is dispersed in the solvent (S) at a temperature below the melting point or softening point of the dispersoid (A). In a state dissolved in the fluid (F), the mixture (X) is volume-expanded below the melting point or softening point of the dispersoid (A), and a dispersion liquid in which the median diameter of the particles (C) is 3.0 μm or less ( A method for producing L) is provided to solve the above problems.

According to the present invention, it is possible to effectively disperse the dispersoid, and it is possible to obtain a dispersion liquid in which the median diameter of the dispersoid is fine and stable quickly and with less power.

It is a flowchart of the experimental apparatus used for preparation of the dispersion liquid by the mixing method by line blend in this invention.

The present invention is described in detail below.
The dispersoid (A) used in the present invention is not particularly limited and may be an organic substance and / or an inorganic substance. For example, wax, resin (crystalline resin, amorphous resin), dye, pigment, filler, antistatic agent, charge control agent, ultraviolet absorber, antioxidant, antiblocking agent, heat stabilizer, and flame retardant In addition, two or more of the above may be used in combination.
When the dispersoid (A) has a melting point, a wax and a crystalline resin are preferable in that the effect of atomization is greater. When the dispersoid (A) is an amorphous material, it is preferable that the dispersoid (A) is dissolved in the solvent (S) and / or the compressive fluid (F) in a mixture of the compressive fluid (F) and the solvent (S). From the viewpoint that the dispersoid (A) is in a liquid state, an amorphous resin is preferable, for example, a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and the like, and combinations thereof.

Examples of the wax include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, fatty acid ester having 30 to 50 carbon atoms, and a mixture thereof.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers of maleic acid alkyl (number of carbon atoms in the alkyl 1-18) ester, etc.] or the like, and Sasol wax.
Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax.
Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid. Examples of the fatty acid ester having 30 to 50 carbon atoms include stearyl stearate.
The dispersoid (A) suitable for using the method for producing a dispersion of the present invention has a melting point or a softening point. The melting point or softening point of the dispersoid (A) is preferably 30 to 120 ° C, more preferably 40 to 110 ° C, still more preferably 50 ° C to 100 ° C, particularly preferably 55 ° C to 90 ° C, most preferably 60 to 80 ° C. ° C.
The melting point in the present invention is used when the dispersoid (A) is a crystalline material, and is determined from an endothermic peak in differential scanning calorimetry (hereinafter referred to as DSC).
The softening point in the present invention is obtained when the dispersoid (A) is an amorphous material, and is measured and determined using a descending flow tester.
In the present invention, the term “amorphous” means a material that does not exhibit the following crystal characteristics, and the crystallinity is defined below. “Crystallinity” means that in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a step-like endothermic change, and an absolute temperature ratio between the peak temperature and the softening temperature (softening temperature / (Endothermic peak temperature) is 0.93 to 1.07.
In addition, the softening point in the present invention is measured using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), while 1 g of a measurement sample is heated at a heating rate of 6 ° C./min. Apply a load of 1.96 MPa with a jar, push out from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger drop (flow value)” and “temperature”, and the maximum value of plunger drop The temperature corresponding to 1/2 of the sample is read from the graph, and this value (temperature when half of the measurement sample flows out) is taken as the softening point.

Resins include crystalline resins and amorphous resins.

The composition of the crystalline resin is not particularly limited, and examples thereof include crystalline resins such as polyester resins, polyurethane resins, polyurea resins, polyamide resins, polyether resins, polycarbonate resins, and vinyl resins, and composite resins thereof.
Amorphous resins include vinyl resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. And composite resins thereof.

Among the above crystalline resins, the polyester resin is preferably a polycondensed polyester resin synthesized from an alcohol (diol) component and an acid (dicarboxylic acid) component from the viewpoint of crystallinity. However, a tri- or higher functional alcohol (trivalent or higher polyol) component or an acid (trivalent or higher polycarboxylic acid) component may be used as necessary. Examples of the polyurethane resin include a polyurethane resin synthesized from an alcohol (diol) component and an isocyanate (diisocyanate) component. However, if necessary, a tri- or higher functional alcohol (trivalent or higher polyol) component or an isocyanate (trivalent or higher polyisocyanate) component may be used. Examples of the polyamide resin include a polyamide resin synthesized from an amine (diamine) component and an acid (dicarboxylic acid) component. However, a tri- or higher functional amine (trivalent or higher polyamine) component or an acid (trivalent or higher polycarboxylic acid) component may be used as necessary. Examples of the polyurea resin include a polyurea resin synthesized from an amine (diamine) component and an isocyanate (diisocyanate) component. However, a tri- or higher functional amine (trivalent or higher polyamine) component or an isocyanate (trivalent or higher polyisocyanate) component may be used as necessary. As the polyester resin, in addition to the polycondensation polyester resin, a lactone ring-opening polymer and polyhydroxycarboxylic acid are also preferable. Examples of the polycarbonate resin include a polycarbonate resin synthesized from a diol component and phosgene or dimethyl carbonate.

In the following description, first, a diol component, a trivalent or higher polyol component, a dicarboxylic acid component, a trivalent or higher valent component used in the crystalline polycondensation polyester resin, the crystalline polyurethane resin, the crystalline polyamide resin, and the crystalline polyurea resin. The polycarboxylic acid component, diisocyanate component, trivalent or higher polyol component, diamine component, and trivalent or higher polyamine component will be described.
-Diol component-
As the diol component, an aliphatic diol is preferable, and the chain carbon number is preferably in the range of 2 to 36. A linear aliphatic diol is more preferred.
When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting point is lowered. For example, toner blocking resistance, image storage stability, and low-temperature fixability of the resulting dispersion (L) are deteriorated. May end up. On the other hand, when the number of carbon atoms exceeds 36, it may be difficult to obtain practical materials.

The content of the linear aliphatic diol in the diol component is preferably 80 mol% or more of the diol component used, and more preferably 90 mol% or more. Other components may be included as necessary.
When the content of the linear aliphatic diol is 80 mol% or more, the crystallinity of the polyester resin is improved, so that the particle size can be easily reduced.

Specific examples of the linear aliphatic diol 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, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like, but are not limited thereto. Of these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

Other diols used as necessary include aliphatic diols other than those having 2 to 36 carbon atoms (1,2-propylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, Neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol) Alicyclic diol having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); 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.] Adducts (addition moles 1-30); Bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (addition moles 2-30); polylactone diols (poly ε-caprolactone diol, etc.); and polybutadiene diols.

Furthermore, as a diol used as necessary, a diol having another functional group may be used in addition to the diol having no functional group other than the above hydroxyl group. Examples of the diol having a functional group other than a hydroxyl group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [having 6 to 24 carbon atoms, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylol. Heptanoic acid, 2,2-dimethyloloctanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (the alkyl group has 1 to 6 carbon atoms) or an AO adduct thereof (EO as AO). Or PO, such as PO, such as N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; (2-hydroxyethyl) phosphate and the like.
Examples of the salt of the diol having a functional group other than the hydroxyl group include salts of the functional group with the tertiary amine having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metal (such as sodium). It is done.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of trihydric or higher polyols that are used as needed include trihydric to octahydric or higher polyols. Examples of the polyol having a valence of 3 to 8 or more include polyhydric aliphatic alcohols having a valence of 3 to 8 or more having 3 to 36 carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydration product thereof). For example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; sugars and derivatives thereof such as sucrose and methylglucoside); AO adducts of trisphenols (such as trisphenol PA) ( Addition 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. are mentioned.
Among these, preferred are trivalent to octavalent or higher valent polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

-Dicarboxylic acid and trivalent or higher polycarboxylic acid components-
Examples of the dicarboxylic acid component include various dicarboxylic acids, but aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and the aliphatic dicarboxylic acids are more preferably linear carboxylic acids. Examples of the trivalent or higher polycarboxylic acid component include polycarboxylic acids having a valence of 3 to 6 or higher.

Examples of the dicarboxylic acid include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); alicyclic dicarboxylic acids having 6 to 40 carbon atoms Acid [dimer acid (dimerized linoleic acid), etc.], alkene dicarboxylic acid having 4 to 36 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid) C8-36 aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.) Etc.
As the dicarboxylic acid or the polycarboxylic acid having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) can be used. It may be used.
Among these dicarboxylic acids, it is particularly preferable to use an aliphatic dicarboxylic acid (particularly a straight-chain carboxylic acid) alone, but an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid) together with the aliphatic dicarboxylic acid. Those obtained by copolymerizing acids and these lower alkyl esters are preferred as well. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.
Examples of the dicarboxylic acid component include, but are not limited to, the above carboxylic acids. Of these, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid are preferable in consideration of crystallinity and availability.

-Diisocyanate and tri- or higher polyisocyanate component-
Examples of the diisocyanate include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and 8 carbon atoms. ~ 15 araliphatic diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products) and the like The mixture of 2 or more types of these is mentioned. Moreover, you may use together polyisocyanate more than trivalence as needed.

Specific examples of the aromatic diisocyanate having 6 to 20 carbon atoms and the trivalent or higher aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate ( TDI), crude TDI, 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane] And a small amount (for example, 5 to 20% by weight) of a trifunctional or higher functional polyamine] phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -tri Phenylmethane triisocyanate, m- or p-isocyanatophenylsulfur Isocyanate, and the like.
Specific examples of the aliphatic diisocyanate having 2 to 18 carbon atoms 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- And isocyanatoethyl-2,6-diisocyanatohexanoate.
Specific examples of the alicyclic diisocyanate having 4 to 15 carbon atoms 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- or 2,6-norbornane diisocyanate, and the like.
Specific examples of the araliphatic diisocyanate having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like. It is done.
Examples of the modified products of diisocyanate and polyisocyanate having 3 or more valences include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product. 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).
Among these, 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 and HDI. , Hydrogenated MDI, and IPDI.

-Diamine and triamine or higher polyamine component-
Examples of diamines and trivalent or higher polyamines include aliphatic diamines having 2 to 18 carbon atoms and aliphatic polyamines having 3 or more carbon atoms, aromatic diamines having 6 to 20 carbon atoms, and aromatic polyamines having 3 or more carbon atoms. Is mentioned.
Examples of the aliphatic diamines and trivalent or higher aliphatic polyamines (2 to 18 carbon atoms) include [1] aliphatic diamines and trivalent or higher aliphatic polyamines {C 2-6 alkylene diamines (ethylenediamine, Propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (2 to 6 carbon atoms) diamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine , Pentaethylenehexamine, etc.] ;; [2] These alkyl (carbon number 1 to 4) or hydroxyalkyl (carbon number 2 to 4) substitutes [dialkyl (carbon number 1 to 3) aminopropylamine, trimethylhexamethylenediamine Aminoethyl etano Lumin, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.]; [3] Aliphatic or heterocyclic containing aliphatic diamine and trivalent or higher alicyclic or heterocyclic containing aliphatic polyamine {Cycloaliphatic diamines (4 to 15 carbon atoms) [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, 1,4bis (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 (8 carbon atoms) To 15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), and the like.

Examples of aromatic diamines and trivalent or higher aromatic polyamines (6 to 20 carbon atoms) include [1] unsubstituted aromatic diamines and trivalent or higher unsubstituted aromatic polyamines [1,2-, 1,3. -Or 1,4-phenylenediamine, 2,4'- or 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) ) Sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine, etc.]; [2] nucleus-substituted alkyl groups (methyl, ethyl, n- Or an aromatic diamine having 1 to 4 carbon atoms such as i-propyl and butyl) and a trivalent or higher aromatic diamine. Group polyamines such as 2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o -Toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 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-2,2'-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, and the like, and mixtures of these isomers in various proportions; [3] Nuclear-substituted electron withdrawing groups (halogens such as Cl, Br, I, and F; alkoxy groups such as methoxy and ethoxy; Aromatic diamines having a nitro group and the like and trivalent or higher aromatic polyamines [methylene bis-o-chloroaniline, 4-chloro-o-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; 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′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic diamines having secondary amino groups and trivalent or higher aromatic polyamines [Aromatic diamines of [1] to [3] above and trivalent or higher Aromatic polyamines in which part or all of —NH ₂ is replaced by —NH—R ′ (where R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4′-di (methyl Amino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and the like.

In addition to these, diamine or triamine or higher polyamine components include polyamide polyamines [dicarboxylic acid (dimer acid, etc.) and excess polyamines (more than 2 mol per mol of acid) (the above alkylenediamine, polyalkylenepolyamine, etc.) Low-molecular-weight polyamide polyamines obtained by condensation with polyamines], polyether polyamines [hydrides of cyanoethylated polyether polyols (polyalkylene glycols, etc.)], and the like.

Among crystalline polyester resins, lactone ring-opening polymerization products are monolactones having 3 to 12 carbon atoms (number of ester groups in the ring) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Lactones such as one) can be obtained by ring-opening polymerization using a catalyst such as a metal oxide or an organometallic compound. Of these, a preferred lactone is ε-caprolactone from the viewpoint of crystallinity.
When glycol is used as the initiator, a lactone ring-opening polymer having a hydroxyl group at the terminal is obtained. Such a lactone ring-opening polymer can be obtained, for example, by reacting the lactone with the diol component such as ethylene glycol or diethylene glycol in the presence of a catalyst. As the catalyst, an organic tin compound, an organic titanium compound, an organic tin halide compound, or the like is generally used, and is added to the reaction solution at a rate of about 0.1 to 5000 ppm, and preferably at 100 to 230 ° C. By polymerizing in an active atmosphere, a lactone ring-opening polymer can be obtained. The lactone ring-opening polymer may be modified at its terminal so as to be, for example, a carboxyl group. The lactone ring-opening polymer is a thermoplastic aliphatic polyester resin having high crystallinity. As the lactone ring-opening polymer, commercially available products may be used, for example, H1P, H4, H5, H7, etc. of PLACEL series manufactured by Daicel Corporation (all of which melting point = about 60 ° C., Tg = about −60 ° C. Highly crystalline polycaprolactone).

Among crystalline polyester resins, polyhydroxycarboxylic acid can be obtained by directly dehydrating and condensing hydroxycarboxylic acid such as glycolic acid and lactic acid (L-form, D-form, racemic form), but glycolide, lactide (L-form, A cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to a dehydration condensate of two or three molecules of a hydroxycarboxylic acid such as D-form or racemate) as a metal oxide or organic Ring-opening polymerization using a catalyst such as a metal compound is preferred from the viewpoint of adjusting the molecular weight. Of these, preferred cyclic esters are L-lactide and D-lactide from the viewpoint of crystallinity.
When glycol is used as an initiator, a polyhydroxycarboxylic acid skeleton having a hydroxyl group at the terminal is obtained. Such a compound having a polyhydroxycarboxylic acid skeleton having a hydroxyl group at the terminal can be obtained, for example, by reacting the cyclic ester with the diol component such as ethylene glycol or diethylene glycol in the presence of a catalyst. As the catalyst, an organic tin compound, an organic titanium compound, an organic tin halide compound, or the like is generally used, and is added to the reaction solution at a rate of about 0.1 to 5000 ppm, and preferably at 100 to 230 ° C. A polyhydroxycarboxylic acid can be obtained by polymerization in an active atmosphere. The polyhydroxycarboxylic acid may have a terminal modified so as to be, for example, a carboxyl group.

Examples of the polyether resin include crystalline polyoxyalkylene polyols.
The method for producing the crystalline polyoxyalkylene polyol is not particularly limited, and any conventionally known method may be used.
For example, a method of ring-opening polymerization of a chiral AO with a catalyst usually used in the polymerization of AO (for example, Journal of the American Chemical Society, 1956, Vol. 18, No. 18, p. 4787-4792) And a method of ring-opening polymerization of inexpensive racemic AO using a sterically bulky complex having a special chemical structure as a catalyst.
As a method using a special complex, a method in which a compound obtained by contacting a lanthanoid complex and organoaluminum is used as a catalyst (for example, described in JP-A-11-12353), or bimetal μ-oxoalkoxide and a hydroxyl compound are previously used. A reaction method (for example, described in JP-T-2001-521957) is known.
Further, as a method for obtaining a polyoxyalkylene polyol having a very high isotacticity, a method using a salen complex as a catalyst (for example, Journal of the American Chemical Society, 2005, Vol. 127, No. 33, p. 11566-). 11567) is known.

For example, when a chiral AO is used and glycol or water is used as an initiator during the ring-opening polymerization, a polyoxyalkylene glycol having a hydroxyl group at the terminal and having an isotacticity of 50% or more can be obtained. The polyoxyalkylene glycol having an isotacticity of 50% or more may be modified such that its terminal is, for example, a carboxyl group. If the isotacticity is 50% or more, the crystallinity is usually obtained.
Examples of the glycol include the carboxylic acid used for carboxy modification of the diol component and the like, and the dicarboxylic acid component and the like.

Examples of AO used for the production of the crystalline polyoxyalkylene polyol include those having 3 to 9 carbon atoms, such as the following compounds.
C3 AO [PO, 1-chlorooxetane, 2-chlorooxetane, 1,2-dichlorooxetane, epichlorohydrin, epibromohydrin]; C4 AO [1,2-BO, methylglycidyl ether]; C5 AO [1,2-pentylene oxide, 2,3-pentylene oxide, 3-methyl-1,2-butylene oxide]; C6 AO [cyclohexene oxide, 1,2-hexylene oxide , 3-methyl-1,2-pentylene oxide, 2,3-hexylene oxide, 4-methyl-2,3-pentylene oxide, allyl glycidyl ether]; AO [1,2-heptyl having 7 carbon atoms] Ren oxide]; AO having 8 carbon atoms [styrene oxide]; AO having 9 carbon atoms [phenyl glycidyl ether] and the like.

Of these AOs, PO, 1,2-BO, styrene oxide and cyclohexene oxide are preferred. More preferred are PO, 1,2-BO and cyclohexene oxide. From the viewpoint of the polymerization rate, PO is most preferable.
These AOs can be used alone or in combination of two or more.

The isotacticity of the crystalline polyoxyalkylene polyol is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and most preferably from the viewpoint of high crystallinity of the obtained crystalline polyether resin. 95% or more.

Isotacticity is described in Macromolecules, vol. 35, no. 6, 2389-2392 (2002), and can be calculated as follows.
About 30 mg of a measurement sample is weighed into a 13 C-NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved to obtain an analysis sample. Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

Signals derived from three methine groups in 13C-NMR are syndiotactic (S) around 75.1 ppm, heterotactic (H) around 75.3 ppm, and isotactic (I) around 75.5 ppm, respectively. Observed at. Isotacticity is calculated by the following calculation formula (1).
Isotacticity (%) = [I / (I + S + H)] × 100 (1)
Where I is the integrated value of the isotactic signal; S is the integrated value of the syndiotactic signal; and H is the integrated value of the heterotactic signal.

The crystalline resin in the present invention may be a block polymer using the crystalline resin as the crystalline part (b), and using the crystalline part (b) and the amorphous part (c) described below. Examples of the resin used for forming the amorphous part (c) include polyester resin, polyurethane resin, polyurea resin, polyamide resin, polyether resin, acrylic resin (polystyrene, styrene acrylic polymer, etc.), and amorphous such as polyepoxy. However, this is not the case.
However, the resin used for forming the crystalline part (b) is preferably a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, or a polyether resin. The resin used for forming the crystalline part (c) is also preferably a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polyether resin, and a composite resin thereof. More preferred are polyurethane resins and polyester resins.

-Manufacturing method of amorphous resin-
As the amorphous resin used as the amorphous part (c), like the crystalline part (b), the polyester resin is a heavy resin synthesized from an alcohol (diol) component and an acid (dicarboxylic acid) component. A condensed polyester resin is preferred. However, a tri- or higher functional alcohol (trivalent or higher polyol) component or an acid (trivalent or higher polycarboxylic acid) component may be used as necessary. Examples of the polyurethane resin include a polyurethane resin synthesized from an alcohol (diol) component and an isocyanate (diisocyanate) component. However, a tri- or higher functional alcohol (trivalent or higher polyol) component or an isocyanate (trivalent or higher polyisocyanate) component may be used as necessary. Examples of the polyurea resin include a polyurea resin synthesized from an amine (diamine) component and an isocyanate (diisocyanate) component. However, a tri- or higher functional amine (trivalent or higher polyamine) component or an isocyanate (trivalent or higher polyisocyanate) component may be used as necessary. Examples of the polyamide resin include a polyamide resin synthesized from an amine (diamine) component and an acid (dicarboxylic acid) component. However, a tri- or higher functional amine (trivalent or higher polyamine) component or an acid (trivalent or higher polycarboxylic acid) component may be used as necessary. Examples of the polyether resin include polyoxyalkylene polyols obtained by adding AO to an alcohol (diol) component.
The monomers used in these amorphous polyester resin, amorphous polyurethane resin, amorphous polyamide resin, amorphous polyurea resin, and amorphous polyether resin are the diol component, the trivalent or higher polyol component, Specific examples include the dicarboxylic acid component, the trivalent or higher polycarboxylic acid component, the diisocyanate component, the trivalent or higher polyisocyanate component, the diamine component, the trivalent or higher polyamine component, and the AO. Any combination is possible as long as it is a crystalline resin.

-Manufacturing method of block polymer-
For the block polymer composed of the crystalline part (b) and the amorphous part (c), the use or non-use of the binder is selected in consideration of the reactivity of the respective terminal functional groups. Can select a binder type suitable for the terminal functional group and bond the crystalline part (b) and the amorphous part (c) to form a block polymer.
When the binder is not used, the reaction between the terminal functional group of the resin that forms the crystalline part (b) and the terminal functional group of the resin that forms the amorphous part (c) is advanced while heating and decompressing as necessary. In particular, in the case of a reaction between an acid and an alcohol or a reaction between an acid and an amine, the reaction proceeds smoothly when the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high. The reaction temperature is preferably 180 to 230 ° C.
When a binder is used, various binders can be used. A crystalline resin as a block polymer can be obtained by performing a dehydration reaction or an addition reaction using a polyvalent carboxylic acid, a polyhydric alcohol, a polyvalent isocyanate, a polyfunctional epoxy, an acid anhydride, or the like as a binder.
Examples of the polyvalent carboxylic acid and acid anhydride include the same dicarboxylic acid component and trivalent or higher polycarboxylic acid component. Examples of the polyhydric alcohol include the same diol component and trivalent or higher polyol component. Examples of the polyvalent isocyanate include the same diisocyanate components and trivalent or higher 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, bisphenol A or F AO adduct diglycidyl ether, hydrogenated Diglycidyl ethers of bisphenol A AO adducts, diols (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, etc.) diglycidyl ethers, trimethylolpropane di Or triglycidyl ether, pentaerythritol tri- or tetraglycidyl ether, sorbitol hepta or hexaglycidyl ether, Sol Shinji glycidyl ether, dicyclopentadiene-phenol addition type glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether, polybutadiene diglycidyl ether, and the like.

Among the methods for bonding the crystalline part (b) and the amorphous part (c), examples of the dehydration reaction include both the crystalline part (b) and the amorphous part (c) being alcohol resins at both ends. Reaction with a binder (for example, 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 resin.
Examples of the addition reaction include a resin having a hydroxyl group at both ends of the crystalline part (b) and the amorphous part (c), a reaction in which these are bonded with a binder (for example, a polyvalent isocyanate), and crystalline In the case where one of the part (b) and the amorphous part (c) 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, the crystalline part (b) and the amorphous part (c) are both dissolved in a soluble solvent, and if necessary, a binder is added and reacted at a reaction temperature of 80 ° C. to 150 ° C. A crystalline resin is obtained.

In addition, a crystalline vinyl resin is also preferable as the crystalline resin.
As a crystalline vinyl resin, what has a vinyl monomer (m) which has a crystalline group, and the vinyl monomer which does not have a crystalline group mentioned later as a structural unit if necessary is preferable.

Examples of the vinyl monomer (m) include linear alkyl (meth) acrylate (m1) having an alkyl group having 12 to 50 carbon atoms (the linear alkyl group having 12 to 50 carbon atoms is a crystalline group), and the crystal And vinyl monomer (m2) having a unit of the sex part (b).
As the crystalline vinyl resin, it is more preferable that the vinyl monomer (m) contains a linear alkyl (meth) acrylate (m1) having an alkyl group having 12 to 50 carbon atoms (preferably 16 to 30).
As the linear alkyl (meth) acrylate (m1) having 12 to 50 carbon atoms in the alkyl group, each alkyl group is linear, lauryl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meta) ) Acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate.
In the present invention, alkyl (meth) acrylate means alkyl acrylate and / or alkyl methacrylate, and the same description method is used hereinafter.

In the vinyl monomer (m2) having a unit of the crystalline part (b), the method of introducing the unit of the crystalline part (b) into the vinyl monomer takes into account the reactivity of each terminal functional group, and the binder ( (Coupling agent) is used or not, and when it is used, the binder suitable for the terminal functional group is selected, and the crystalline part (b) is bonded to the vinyl monomer, and the crystalline part (b ) Units of vinyl monomer (m2).

When a binder is not used in the production of the vinyl monomer (m2) having the unit of the crystalline part (b), the terminal functional group of the crystalline part (b) and the terminal functional group of the vinyl monomer are heated and decompressed as necessary. Advance the reaction. 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 to 230 ° C.

When using a binder, various binders can be used according to the kind of the functional group at the terminal.
Specific examples of the binder and a method for producing the vinyl monomer (m2) using the binder include the same methods as those for producing the block polymer.

Hereinafter, vinyl resin, polyester resin, polyurethane resin, and epoxy resin, which are preferable resins as the amorphous resin, will be described in detail.

The vinyl resin used as the amorphous resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer having no crystalline group. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbon:
Alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6 -Hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbon:
Mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene and limonene.
(1-3) Aromatic vinyl hydrocarbon:
Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexyl Styrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, etc .; indene and vinylnaphthalene.

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (C1-C24) esters such as (meth) acrylic acid, (meth) acrylic acid alkyl esters, (anhydrous ) Maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, cinnamic acid, etc. Carboxyl group-containing vinyl monomers; and metal salts thereof.

(3) Sulfone group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2-hi Roxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random, block may be) mono (meth) acrylate sulfate [Poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfate or sulfone represented by the following general formulas (1-1) to (1-3) Acid group-containing monomers; and salts thereof.

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 15 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and when n is plural, (AO) may be the same or different. If different, they may be random or block, Ar represents a benzene ring, m and n each independently represents an integer of 1 to 50, and R ′ represents the number of carbon atoms optionally substituted by a fluorine atom. Represents an alkyl group of 1 to 15.)

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (carbon number 1 to 24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (carbon number 1 to 24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid; and their salts.

The salts (organic acid salts) of (2) to (4) above include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K. Of these, alkali metal salts and amine salts are preferable, and sodium salts and tertiary monoamine salts having 3 to 20 carbon atoms are more preferable.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof and the like.
(6-2) Amide group-containing vinyl monomer:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like.
(6-3) Nitrile group-containing vinyl monomer:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(6-4) Quaternary ammonium cation group-containing vinyl monomer:
Quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine (methyl chloride, dimethyl sulfate) Quaternized with a quaternizing agent such as benzyl chloride or dimethyl carbonate).
(6-5) Nitro group-containing vinyl monomer:
Nitrostyrene etc.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 11 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.], dialkyl fumarate (the two alkyl groups are linear, branched, having 2 to 8 carbon atoms) Or an alicyclic group), a dialkyl maleate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxy Alkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol EO 10 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol Di (meth) acrylate, propylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(9-3) Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone.
(9-4) Vinyl sulfone such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(10) Other vinyl monomers:
(10-1) Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
(10-2) Monomer having a dimethylsiloxane group:
Methacryl-modified silicone is preferred, and examples thereof include those having a structure represented by the following formula.
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) _a Si (CH ₃ ) ₂ R (where a is an average value of 15 to 45, and R is an organically modified group containing a methacryl group)
An example of R includes C ₃ H ₆ OCOC (CH ₃ ) ═CH ₂ .

(10-3) Fluorine-containing monomer:
Perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE); perfluoro (alkyl vinyl ether) (PFAVE), perfluoro (1,3-dioxole), perfluoro ( 2,2-dimethyl-1,3-dioxole) (PFDD), perfluoro- (2-methylene-4-methyl-1,3-dioxolane) (MMD), perfluorobutenyl vinyl ether (PFBVE) and other perfluoro Vinyl ether; vinylidene fluoride (VdF), trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3,3,3-trifluoro-2-trifluoromethylpropene, 3,3,3- Trifluoropropene, Hydrogen atom-containing fluoroolefins such as fluoro (butyl) ethylene (PFBE); 1,1-dihydroperfluorooctyl acrylate (DPFOA), 1,1-dihydroperfluorooctyl methacrylate (DPFOMA), 2- (perfluorohexyl) ethyl Acrylate, 2- (perfluorooctyl) ethyl acrylate (PFOEA), 2- (perfluorooctyl) ethyl methacrylate (PFOEMA), 2- (perfluorohexyl) ethyl methacrylate (PFHEMA), 2- (perfluorobutyl) ethyl methacrylate Polyfluoroalkyl (meth) acrylates such as (PFBEMA); α-fluorostyrene, β-fluorostyrene, α, β-difluorostyrene, β, β-difluorostyrene, α, β, β- Trifluorostyrene, α-trifluoromethylstyrene, 2,4,6-tri (trifluoromethyl) styrene, 2,3,4,5,6-pentafluorostyrene, 2,3,4,5,6-penta Examples thereof include fluorostyrene such as fluoro-α-methylstyrene and 2,3,4,5,6-pentafluoro-β-methylstyrene.

When a vinyl resin containing a salt of an organic acid is used as the vinyl monomer, this resin may be, for example, Al, Ti, Cr, among the salts of the monomers (2) to (4) as at least a part of the vinyl monomer. It can be obtained by using one or more metal salts selected from Mn, Fe, Zn, Ba, and Zr. The amount of these organic acid salts used in all monomers used for the polymerization is preferably 5 to 60% by weight. The lower limit is more preferably 10% by weight, and the upper limit is more preferably 50% by weight.

Examples of the copolymer of vinyl monomers include polymers obtained by copolymerizing any of the above monomers (1) to (10) in a binary or higher number at an arbitrary ratio. (Meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-acrylonitrile- ( (Meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and Examples thereof include salts of these copolymers.

Examples of the polyester resin used as the amorphous resin include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol (12) having a valence of 3 to 8 or higher, and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) or 3 to 6 Examples thereof include polycarboxylic acids (14) having a valence of 1 or higher and acid anhydrides or lower alkyl esters thereof.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1 to the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/4, particularly preferably from 1 / 1.3 to 1/3.
In order to keep the carboxyl group content within the above preferred range, the polyester having an excess of hydroxyl groups may be treated with polycarboxylic acid.

Examples of the diol (11) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecandiol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) Polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Or alicyclic diol alkylene oxide (AO) [EO, PO, BO, etc.] adducts (addition mole number 1 to 120); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (added mole number 2-30); polylactone diols (poly ε-caprolactone diol, etc.); and polybutadiene diols.

As the diol (11), in addition to the diol having no functional group other than the above hydroxyl group, a diol (11a) having another functional group may be used. Examples of the diol (11a) having a functional group other than a hydroxyl group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [having 6 to 24 carbon atoms, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylol. Heptanoic acid, 2,2-dimethyloloctanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (alkyl group having 1 to 6 carbon atoms) or an AO adduct (EO as AO). Or PO, such as PO, such as N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; (2-hydroxyethyl) phosphate and the like.
Examples of the salt of the diol having a functional group other than the hydroxyl group include salts of the functional group with the tertiary amine having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metal (such as sodium). It is done.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the polyol (12) having a valence of 3 to 8 or higher include polyhydric aliphatic alcohols having a valence of 3 to 8 or more having 3 to 36 carbon atoms (alkane polyol and its intramolecular or intermolecular). Dehydrates such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; sugars and derivatives thereof such as sucrose and methylglucoside); AO adducts of polyhydric fatty alcohols (addition) AO adducts of trisphenols (trisphenol PA, etc.) (addition moles 2-30); AO adducts of novolak resins (phenol novolac, cresol novolac, etc.) (addition moles 2-30) ); Acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl Copolymerization products of Rumonoma]; and the like.
Among these, preferred are trivalent to octavalent or higher valent polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acids (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acid having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid) etc.), alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.
Examples of the polycarboxylic acid (14) having a valence of 3 to 6 or higher include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.).
Examples of the dicarboxylic acid (13) or the polycarboxylic acid (14) having a valence of 3 to 6 or higher include the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester). , Isopropyl ester, etc.) may be used.

When a polyester resin containing a structural unit of an organic acid salt is used, this resin is synthesized, for example, by synthesizing a polyester having an COOH residue (acid value is preferably 1 to 100, more preferably 5 to 50), The at least one COOH group can be obtained by converting it into a salt of at least one metal selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr.
As a method for forming a metal salt, for example, it is obtained by reacting a polyester having a COOH group with a hydroxide of the corresponding metal.

Examples of the polyurethane resin used as the amorphous resin include polyisocyanate (15) and active hydrogen-containing compound {water, polyol [including diol (11) [including diol (11a) having a functional group other than hydroxyl group]], and Polyhydric acid having a valence of 3 to 8 or higher (12)], polycarboxylic acid [dicarboxylic acid (13), and polycarboxylic acid having a valence of 3 to 6 or higher (14)], polyol and poly Polyester polyols obtained by polycondensation of carboxylic acids, ring-opening polymers of lactones having 6 to 12 carbon atoms, polyadditions of polyamines (16), polythiols (17), and combinations thereof}, and polyisocyanates (15 ) And an active hydrogen-containing compound, a terminal isocyanate group prepolymer, and an isocyanate of the prepolymer Obtained by reacting an equivalent amount of primary and / or secondary monoamines (18) to the base, and amino group-containing polyurethane resins.
The content of carboxyl groups in the polyurethane resin is preferably 0.1 to 10% by weight.

Examples of the polyisocyanate (15) include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic rings having 4 to 15 carbon atoms. Formula polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- or 4, 4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; trifunctional or more of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)] A mixture of polyamine and polyamine]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl An isocyanate etc. are mentioned.
Specific examples of the 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-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Aliphatic polyisocyanates such as
Specific examples of the 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- or 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane-modified TDI). (Combined use with an isocyanate-containing prepolymer)] is included.
Among these, preferred are 6-15 aromatic polyisocyanates, aliphatic polyisocyanates having 4-12 carbon atoms, and alicyclic polyisocyanates having 4-15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of polyamine (16) include
Aliphatic polyamines (2 to 18 carbon atoms): [1] Aliphatic polyamine {2 to 6 carbon atoms alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (carbon 2-6) polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (1 to 4 carbon atoms) Or substituted with hydroxyalkyl (2 to 4 carbon atoms) [dialkyl (1 to 3 carbon atoms) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyl ester Nobispropylamine etc.]; [3] Alicyclic or heterocyclic aliphatic polyamines [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.] [4] Aromatic ring-containing aliphatic amines (C8-15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4-15): 1,3-diamino; Cyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.
Heterocyclic polyamines (4 to 15 carbon atoms): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Aromatic polyamines (6 to 20 carbon atoms): [1] unsubstituted aromatic polyamine 1,2-, 1,3- or 1,4-phenylenediamine, 2,4'- or 4,4'-diphenylmethanediamine , 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 polyamines having a nucleus-substituted alkyl group (C1-C4 alkyl group such as methyl, ethyl, n- or i-propyl, butyl, etc.), for example 2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, , 3-Dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2 , 3-Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetra Methyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodi Phenylmethane, 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, and the like, and mixtures of these isomers in various proportions; [3] Nuclear-substituted electron withdrawing groups Aromatic polyamines [Methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-, etc.] (Halogens such as Cl, Br, I, F; alkoxy groups such as methoxy, ethoxy, etc .; nitro groups, etc.) 1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phen Range amine, 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'-methylenebis (2-bromoaniline) ), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [the above [1] to [3] Aromatic polyamines in which part or all of —NH ₂ is replaced by —NH—R ′ (where R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4′-di (methyl Amino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (dimer acid, etc.) and excess (more than 2 moles per mole of acid) polyamines (the above alkylenediamine, Low molecular weight polyamide polyamines obtained by condensation with polyalkylene polyamines, etc., polyether polyamines: polyether polyols (polyalkylene glycols) Hydrides of cyanoethylation products of Lumpur, etc.).

Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.) and the like.

Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and active hydrogen group-containing compound (T) {water, polyol [the diol (11) and trivalent or higher polyol (12)], dicarboxylic acid) Acid (13), trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17), etc.} polyaddition product, or polyepoxide (19) and dicarboxylic acid (13) or trivalent or higher polyvalent Examples thereof include a cured product of the carboxylic acid (14) with an acid anhydride.
The polyepoxide (19) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. A preferable polyepoxide (19) is one having 2 to 6 epoxy groups in the molecule from the viewpoint of mechanical properties of the cured product. The epoxy equivalent of the polyepoxide (19) (molecular weight per epoxy group) is usually from 65 to 1,000, and preferably from 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65. is there.

Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylated products of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Glycidyl ether form of enol or cresol novolac resin, glycidyl ether form of limonene phenol novolak resin, diglycidyl ether form obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by a condensation reaction and polyglycidyl ethers of polyphenols obtained by a condensation reaction of resorcin and acetone. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Further, in the present invention, as the aromatic system, triglycidyl ether of p-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting a polyol with the above two reactants. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine. Examples of the alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy- 6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) butylamine, dimer acid diglycidyl ester and the like. The alicyclic polyepoxy compound also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic polyepoxy compound includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

The method for producing the crystalline resin and the amorphous resin is not particularly limited, and a desired resin having a melting point or a softening point can be produced by appropriately setting the kind and amount of the above-described monomer.

The method for producing the dispersion liquid (L) of the present invention includes a step of volume expansion of a mixture (X) containing the dispersoid (A), the solvent (S), and the compressive fluid (F). ) Containing particles (C) dispersed in a solvent (S), wherein the dispersoid (A) is a solvent (A) at a temperature below the melting point or softening point of the dispersoid (A). S) and / or the volume of the mixture (X) is expanded below the melting point or softening point of the dispersoid (A) in the state of being dissolved in the compressive fluid (F), and the median diameter of the particles (C) is 3. It is 0 μm or less.

In the present invention, the solvent (S) is, for example, a ketone solvent (such as acetone and methyl ethyl ketone), an ether solvent (such as tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and cyclic ether), an ester solvent ( Acetic acid esters such as ethyl acetate, pyruvate, 2-hydroxyisobutyric acid, and lactic acid esters), amide solvents (such as dimethylformamide), alcohol solvents (such as methanol, ethanol, isopropanol, and fluorine-containing alcohols), aromatic Examples include hydrocarbon solvents (toluene, xylene, etc.), aliphatic hydrocarbon solvents (octane, decane, etc.), water, etc., and mixed solvents thereof.

In the present invention, the particles (C) are particles containing the dispersoid (A).

In the present invention, the compressible fluid means a fluid compressed at a normal temperature or higher pressure at room temperature. The pressure of the compressive fluid (F) is preferably 1 MPa or more, more preferably 2 MPa or more, still more preferably 3 MPa or more, and particularly preferably 4 MPa or more.
In the present invention, the compressive fluid (F) may be methane, ethylene, chlorofluorocarbon alternative, etc., but is preferably carbon dioxide from the viewpoint of safety and ease of handling, and more preferably liquid carbon dioxide, Critical carbon dioxide or supercritical carbon dioxide is preferred.
In the present invention, 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 (temperature = −57 ° C.) on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. Supercritical carbon dioxide, which represents carbon dioxide, which is the temperature / pressure condition of the portion surrounded by the gas-liquid boundary line passing through (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and the solid-liquid boundary line Represents carbon dioxide which is a temperature / pressure condition above the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).

In the present invention, the mixture (X) is a mixture containing the dispersoid (A), the solvent (S), and the compressive fluid (F).
In the mixture (X) before volume expansion, the dispersoid (A) is liquid, and the dispersoid (A) is a solvent (S) and / or compressible at a temperature below the melting point or softening point of the dispersoid (A). Dissolved in fluid (F). In the present invention, the mixture (X) is volume-expanded below the melting point or softening point of the dispersoid (A).

When the dispersoid (A) has a melting point, the following condition 1 is preferably satisfied.
Condition 1
T3 <T1 <T2 <T0
T0: Melting point of dispersoid (A) T1: Exothermic peak temperature derived from dispersoid (A) when DSC temperature drop measurement of dispersion (L) T2: Temperature of mixture (X) immediately before volume expansion T3: Mixture Temperature of dispersion liquid (L) immediately after volume expansion of (X)

When the condition 1 is not satisfied, the temperature after volume expansion is high, and the dispersoid (A) is insufficiently precipitated, or the particles (C) formed by precipitation are unstable. Moreover, when the state of the dispersoid (A) before the volume expansion of the mixture (X) is not in a liquid state but in a precipitated state, it may be difficult to obtain a dispersion of fine particles (C).

Further, in the mixture (X) at the temperature T2, it is more preferable that the dispersoid (A) is dissolved in the solvent (S) and / or the compressible fluid (F).
As another form, in the mixture (X), the dispersoid (A) is preferably melted (in a liquid state) at a temperature not higher than the melting point of the dispersoid (A), and the dispersoid (A) It is preferable that at least one liquid selected from the group consisting of the solvent (S) and the compressive fluid (F) is subjected to liquid-liquid two-phase separation. Further, in the mixture (X) at the temperature T2, the dispersoid (A) is melted (in a liquid state), and the dispersoid (A) and the solvent (S) or the compressive fluid (F) are separated into two liquid-liquid phases. More preferably. As such a mixture (X), for example, in the mixture (X) having a temperature not higher than the melting point of the dispersoid (A) (preferably temperature T2), the dispersoid (A) is dissolved in the solvent (S), and the compressibility is reduced. Examples include a form in which the fluid (F) and liquid-liquid two-phase separation are performed, and a form in which the dispersoid (A) is dissolved in the compressive fluid (F) and the liquid (liquid-liquid two-phase separation) is performed. In the mixture (X), the dispersoid (A) is dissolved in the compressible fluid (F) at a temperature not higher than the melting point of the dispersoid (A) (preferably temperature T2), and the liquid (liquid / liquid) two-phase separation is performed. It is particularly preferable.
In the present invention, the state of the dispersoid (A) before volumetric expansion of the mixture (X) may be any of the above states, and other dispersants and physical properties (viscosity, diffusion coefficient, dielectric constant, solubility, interface, etc.) In order to adjust tension etc.), you may use together the inert gas etc. which are mentioned later.

In the mixture (X), it is particularly preferable that the following condition 2 is satisfied.
Condition 2
T3 + 10 <T1
T1: Exothermic peak temperature derived from the dispersoid (A) when the dispersion (L) was measured for DSC temperature drop T3: Temperature of the dispersion (L) immediately after volumetric expansion of the mixture (X) Perform under the following conditions.
Using a differential scanning calorimeter {for example, DSC210 manufactured by Seiko Denshi Kogyo Co., Ltd.], the measurement sample is heated to 200 ° C., and then cooled to 0 ° C. at a cooling rate of 10 ° C./min. T1 is the maximum peak temperature of exotherm derived from the dispersoid (A) appearing at this time.

When the dispersoid (A) contained in the mixture (X) is an amorphous material, in the mixture (X), the dispersoid (A) is a solvent (S) at a temperature below the softening point of the dispersoid (A). And / or dissolved in the compressible fluid (F). As another form, in the mixture (X), the dispersoid (A) is separated into at least one liquid selected from the group consisting of a solvent (S) and a compressive fluid (F) and a liquid-liquid two-phase separation. It is preferable that the dispersoid (A) and the solvent (S) or the compressive fluid (F) are more preferably liquid-liquid two-phase separated in the mixture (X). As such a mixture (X), for example, in the mixture (X) having a temperature equal to or lower than the softening point of the dispersoid (A), the dispersoid (A) is dissolved in the solvent (S), and the compressive fluid (F) A form in which liquid-liquid two-phase separation is performed, and a form in which the dispersoid (A) is dissolved in the compressive fluid (F) and liquid-liquid two-phase separation is performed with the solvent (S). In the mixture (X), the dispersoid (A) is dissolved in the compressible fluid (F) at a temperature equal to or lower than the softening point of the dispersoid (A), and the liquid (liquid and liquid) is separated into two phases. Particularly preferred.
In the present invention, the state of the dispersoid (A) before volumetric expansion of the mixture (X) may be any of the above states, and other dispersants and physical properties (viscosity, diffusion coefficient, dielectric constant, solubility, interface, etc.) An inert gas or the like may be used in combination for adjusting the tension.

The mixture (X) may contain a dispersant, and the dispersant is not particularly limited, and a known one can be used, and a unit having high compatibility with the dispersoid (A) And a polymer or oligomer in which a unit having high compatibility with the solvent (S) is present as a block body.
When the dispersoid (A) has a high hydrocarbon ratio such as wax, a polymer or oligomer in which one of the unit having high compatibility with the hydrocarbon and the unit having high compatibility with the resin is grafted on the other [for example, , Obtained by polymerizing vinyl monomer in the presence of wax), unsaturated hydrocarbon (ethylene, propylene, butene, styrene, α-methylstyrene, etc.) and α, β-unsaturated carboxylic acid or ester thereof Or a copolymer with an anhydride thereof (acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, esters thereof, itaconic anhydride, etc.), block or graft copolymer of vinyl resin and polyester resin, etc. Is mentioned.

Examples of inert gases include inert gases such as nitrogen, helium, argon, and air. When carbon dioxide is used as the compressive fluid (F), the weight fraction of carbon dioxide in the total of carbon dioxide and other inert gas is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably Is 90% by weight or more.

The median diameter of the particles (C) contained in the dispersion (L) obtained in the present invention is 3.0 μm or less, preferably 0.05 μm to 3.0 μm, more preferably 0.06 μm to 1. The thickness is 0 μm, more preferably 0.07 μm to 0.7 μm, and particularly preferably 0.08 μm to 0.4 μm. On the other hand, when the median diameter is larger than 3.0 μm, there arises a problem that the smoothness of the coated surface is impaired when, for example, the dispersion liquid (L) is blended and applied to the paint, and the particles (C) are contained in the particles. In the case of producing resin particles containing, the particle size distribution of the resin particles is deteriorated. The median diameter is a median diameter based on the volume distribution. The median diameter is measured by a laser type particle size distribution measuring device (LA-920: manufactured by Horiba, Ltd.). The coarse particle amount can also be measured using the same apparatus.

The amount of coarse particles (C) in the dispersion (L) obtained by the present invention is preferably 1.0% by volume or less, more preferably 0.5% by volume or less, and still more preferably 0.1% by volume. % Or less, particularly preferably 0.01% by volume or less. When the amount of coarse particles exceeds 1% by volume, for example, there is a problem that the smoothness of the coated surface is impaired when the dispersion liquid (L) is blended and applied to the paint, and the particles (C) in the particles. When the resin particles containing the resin are produced, the particle size distribution of the resin particles is deteriorated.
Coarse particles are particles of (median diameter × 3) μm or more. However, when (median diameter × 3) ≦ 1.0, particles of 1.0 μm or more are coarse particles.

In the dispersion liquid (L) obtained by the present invention, the stability during storage of the particles (C) in the dispersion liquid (L) is good.
Good stability means that there is no change in the median diameter of the particles during storage and there is no increase in the amount of coarse particles.

The rate of change of the median diameter during storage of the particles (C) in the dispersion (L) obtained by the present invention is 100% or less, preferably 50% or less, more preferably 25, within a range not exceeding 3 μm. % Or less, particularly preferably 10% or less. When the rate of change exceeds 100%, when producing resin particles containing particles (C) in the particles, the production becomes unstable and the particle size distribution deteriorates.

In addition, the amount of increase in the amount of coarse particles in the dispersion liquid (L) of the present invention is 0.5% by volume or less, more preferably 0.1% by volume within a range where the absolute value of the amount of coarse particles does not exceed 1% by volume. Hereinafter, it is more preferably 0.01% by volume or less. The smaller the increase, the more stable the dispersion during storage. When the increase exceeds 0.5% by volume, when the resin particles containing particles (C) are produced, the resin particles are produced. It becomes unstable and the particle size distribution deteriorates.

As the stability of the particles during storage, the dispersion was allowed to stand at 10 ° C. for 24 hours, and the median diameter and the amount of coarse particles before and after standing were measured by the above-mentioned methods, and the median diameter change rate and coarse particles were measured. The amount of increase is calculated.

The change rate of the median diameter is obtained by the following calculation.
Formula 1 B / A × 100-100 = Change rate of median diameter (%)
Measured value A: median diameter of dispersion liquid left to stand at 10 ° C. for 24 hours Measured value B: median diameter in dispersion liquid within one hour after production

The rate of increase in the amount of coarse particles is determined by the following calculation.
Calculation formula 2 CD = Increase rate of coarse particle amount (%)
Measured value C: Coarse particle amount in dispersion at 10 ° C. for 24 hours Measured value D: Coarse particle amount in dispersion within 1 hour after production According to the method for producing the dispersion (L) of the present invention. When the dispersion is allowed to stand at 10 ° C. for 24 hours, the median diameter and the amount of coarse particles before and after standing are measured by the above method, and the median diameter change rate and the amount of increase in coarse particles are calculated, A dispersion in which the rate of change in the median diameter of the particles (C) contained in the dispersion and the amount of increase in coarse particles are in the above-described ranges can be produced.

In the method for producing a dispersion of the present invention, the dispersion (L) can be obtained by volume expansion of the mixture (X) of the dispersoid (A), the solvent (S), and the compressive fluid (F). .
In the method for producing a dispersion of the present invention, the dispersoid (A) is dissolved in the solvent (S) and / or the compressible fluid (F) at a temperature below the melting point or softening point of the dispersoid (A). The mixture (X) is volume-expanded below the melting point or softening point of the dispersoid (A).
In the method for producing a dispersion of the present invention, the mixture (X) having a temperature below the melting point or softening point of the dispersoid (A) is volume-expanded. In the mixture (X) having a temperature equal to or lower than the melting point or softening point of the dispersoid (A), the dispersoid (A) is in a state dissolved in the solvent (S) and / or the compressible fluid (F).

When carbon dioxide is used as the compressible fluid (F), the dispersoid (A) contains at least one selected from the group consisting of fluorine, silicone group, ether group, carbonyl group and hydrocarbon chain. It is preferable.

The volume ratio of the dispersoid (A), the compressive fluid (F), and the solvent (S) in the mixture (X) is any ratio as long as the dispersion liquid (L) after volume expansion reaches the target temperature. However, the higher the ratio of the compressible fluid (F), the lower the temperature after volume expansion, and the smaller the particle size of the particles (C), the more easily a stable dispersion (L) can be obtained. If the compressible fluid (F) is a good solvent for the dispersoid (A), the higher the ratio of the compressible fluid (F), the lower the viscosity, and the smaller the particle size of the particles (C), and the more stable dispersion. (L) is easily obtained. *

Mixing of the dispersoid (A), the compressible fluid (F) and the solvent (S) in the mixture (X) is sufficient if the dispersoid (A) is in a liquid state and is uniformly dissolved or uniformly dispersed by stirring. It is. However, if it is not uniform, a temperature distribution is generated in the dispersion liquid (L), and the particle size distribution of the particles (C) is deteriorated.

A method for producing the dispersion liquid (L) when the dispersoid (A) has a melting point will be described in detail.
In the method for producing a dispersion of the present invention, the mixture (X) is volume-expanded at a temperature not higher than the melting point of the dispersoid (A) so that the particles (C) of the dispersoid (A) are contained in the solvent (S). A dispersed dispersion (L) is obtained. The method of the present invention may comprise a step of preparing the mixture (X). The preparation method of mixture (X) is not specifically limited, For example, it can prepare by mixing a dispersoid (A), a solvent (S), and a compressive fluid (F).
Further, as a preferred form, the solvent (S), the dispersoid (A), and the compressive fluid (F) are mixed at a temperature equal to or higher than the melting point (T0) of the dispersoid (A) (at a temperature that can maintain the liquid state). To prepare a mixture (X). When carbon dioxide is used as the compressive fluid (F), it is preferable to use carbon dioxide having a pressure of 0.5 MPa or more.
Thereafter, the mixture (X) is adjusted to a temperature (T2) below the melting point of the dispersoid (A), and then the volume is expanded to vaporize and remove the compressible fluid (F). By cooling (T3) below the precipitation temperature (T1), a dispersion (L) in which the dispersoid (A) is dispersed as particles (C) in the solvent (S) is obtained.

When the dispersoid (A) does not have a melting point, the mixture (X) is volume-expanded at a temperature below the softening point of the dispersoid (A) so that the particles (C) of the dispersoid (A) A dispersion liquid (L) dispersed in (S) is obtained.
The mixture (X) in the case of using a dispersoid (A) that does not have a melting point (amorphous material) is not particularly limited. For example, the temperature above the softening point of the dispersoid (A) (maintains a liquid state). It is preferable to mix the solvent (S), the dispersoid (A), and the compressive fluid (F) at a temperature higher than or equal to a temperature where the mixture (X) can be produced. When carbon dioxide is used as the compressive fluid (F), it is preferable to use carbon dioxide having a pressure of 0.5 MPa or more.
Thereafter, the mixture (X) is temperature-controlled to a temperature below the softening point of the dispersoid (A), and then volume-expanded to vaporize and remove the compressible fluid (F), thereby precipitating the dispersoid (A). The dispersion (L) in which the dispersoid (A) is dispersed as particles (C) in the solvent (S) can be obtained by cooling below the temperature.

As described above, it is preferable that the dispersoid (A) and the solvent (S) are mixed with the solvent in advance from the viewpoint of ease of handling. The amount of the solvent (S) is preferably 1 to 100% by weight based on the dispersoid (A), more preferably 5 to 80% by weight, particularly preferably 10 to 60% by weight. Within this range, the dispersion can be obtained with a viscosity that is easy to handle.
There is no particular limitation on the procedure for mixing the dispersoid (A) and the solvent (S) and making the mixture at a temperature higher than the temperature at which the dispersoid (A) does not precipitate [preferably the solvent (S) solution of the dispersoid (A)]. The mixture may be heated after mixing the normal temperature dispersoid (A) and the solvent (S), or the other may be introduced into the heated dispersoid (A) or the solvent (S). In addition, when using additives, such as said dispersing agent, adding to this mixture is preferable.

In the method for producing a dispersion according to the present invention, when the primary particles of the particles (C) containing the dispersoid (A) are already the target size and only have secondary aggregation, the dispersoid (A) Therefore, in this case, in addition to the above method, for example, when carbon dioxide is used as the compressive fluid (F), the compressive fluid (F) having a pressure of 0.5 MPa or more is used. Dispersed in which the dispersoid (A) is dispersed in the solvent (S) by mixing and then rapidly expanding under reduced pressure, vaporizing the compressive fluid (F) and mixing with the solvent (S). A liquid (L) is obtained.
The solvent (S) may be mixed at any stage of the above process, or may be previously mixed with the dispersoid (A).

As means for expanding the volume, there are heating operation of the compressive fluid and decompression operation, but volume expansion by the decompression operation is preferable for efficient pulverization and pulverization.
The pressure immediately before volumetric expansion of the mixture (X) is preferably 2 to 15 MPa, more preferably 2.5 to 12 MPa, particularly preferably from the viewpoint of obtaining a dispersion having a small particle size and few coarse particles. Is 3.5 to 10 MPa. Further, the pressure after volume expansion of the mixture (X) is preferably −0.1 to 2 MPa, more preferably 0 to 1 MPa from the viewpoint of obtaining a dispersion having a small particle size and few coarse particles. Particularly preferred is 0.1 to 0.5 MPa.

A method of mixing a mixture of a dispersoid (A) and a solvent (S) (hereinafter referred to as (A) -containing mixture) and a compressible fluid (F) such as carbon dioxide having a pressure of 0.5 MPa or more, for example, Although not particularly limited, as a preferred specific method, when mixing the (A) containing mixture and the compressive fluid (F) in a pressure resistant container, the (A) containing mixture is charged into the pressure resistant container, ( A) When the temperature of the containing mixture is low and the dispersoid (A) is precipitated, the dispersoid (A) is liquefied by heating. The dispersoid (A) can be melted at a temperature equal to or higher than the melting point of the dispersoid (A). After the dispersoid (A) is completely melted, a compressive fluid (until the desired pressure is reached by a pressurizing means such as a pump provided in the pressure vessel while adjusting to a temperature below the melting point of the dispersoid (A). F) is introduced into the container and mixed with the mixture containing (A). Since the volume of the (A) -containing mixture expands by introducing the compressive fluid (F), the initial charge amount of the (A) -containing mixture is preferably 5 to 70% by volume with respect to the volume of the container.

The pressure vessel used in the method for producing a dispersion of the present invention can withstand a maximum pressure of 0.5 MPa or more when, for example, carbon dioxide or the like is used as the compressive fluid (F). It is preferable to equip the equipment which can stir and mix the mixture and the compressive fluid (F) with a nozzle for taking out the mixture (A) at the bottom of the container. The nozzle may be any nozzle that allows liquid substances to pass through, for example, opening and closing a needle valve or a ball valve having a diameter of about 0.1 to 5.0 mm (A) after mixing of compressive fluid (F) (A ) The mixed liquid can be ejected from the high pressure state into the atmosphere at once.

After introducing the compressive fluid (F), the mixture is sufficiently stirred to allow the compressive fluid (F) to sufficiently permeate the mixture containing (A). The stirring time may be the minimum time that the mixture (A) is sufficiently mixed with the entire compressive fluid (F), and is preferably stirred for about 10 to 30 minutes. By sufficiently mixing the compressive fluid (F), the viscosity of the (A) -containing mixture can be lowered, and the dispersoid (A) can be effectively made into fine particles by decompression expansion in the next step.
In addition, the temperature during the stirring and mixing of the (A) -containing mixture and the compressive fluid (F) is preferably from the viewpoint of preventing aggregation of dispersoids due to excessive temperature rise, adjusting the temperature of the (A) -containing mixture during discharge, and the like. Is 20 to 180 ° C, more preferably 30 to 120 ° C, still more preferably 35 to 100 ° C, and particularly preferably 40 to 85 ° C.

After stirring, the valve is opened from the nozzle at the bottom of the container and the mixture (A) is expanded under reduced pressure to atmospheric pressure all at once. As a result, the temperature of the (A) -containing mixture is drastically decreased, and the dissolved dispersoid (A) is deposited below the temperature at which the dispersoid (A) is precipitated. Further, by removing the compressible fluid (F) by vaporization, a dispersion (L) in which the dispersoid (A) is dispersed in the solvent (S) is obtained. In order to sufficiently lower the temperature of the (A) -containing mixture by this decompression and to sufficiently precipitate the dispersoid (A), the temperature and pressure of the (A) -containing mixture before decompression are set to appropriate conditions. Should be set from the enthalpy diagram. Moreover, as a method of decompressing and expanding the (A) containing mixture at once, it is preferable to discharge from a high pressure by opening and closing a needle valve or a ball valve attached to the nozzle.

(A) Mixing of the mixture and the compressive fluid (F) may be performed continuously by a line blend (in-line mixing) method, in addition to the method in the pressure vessel described above, to improve productivity and to make the quality constant. This is preferable from the standpoints of manufacturing and reduction of manufacturing space. Specific examples of the apparatus used for the line blending method include static in-line mixers such as static mixers, in-line mixers, ramond super mixers, and sulzer mixers, and stirring-type in-line mixers such as vibrator mixers and turbo mixers. It is done. There is no limitation on the length and pipe diameter of the mixer part of the device, and the number of mixing devices (elements). For example, when carbon dioxide is used as the compressible fluid (F), it can withstand a maximum pressure of 0.5 MPa or more. It must be obtained.
The outlet of the apparatus used for the line blending method is preferably provided with a nozzle for taking out the mixture, similar to the pressure vessel.

(A) As a mixing method of the containing mixture and the compressive fluid (F), first, the compressive fluid (F) is introduced into an apparatus for performing line blending and adjusted so that the pressure becomes 0.5 MPa or more, and then (A) It is preferable to introduce the containing mixture into the compressive fluid (F). The pressure of the compressive fluid (F) is preferably the same pressure as that used in the pressure vessel.
The temperature at which line blending is performed is the same as in the case of mixing using the above-described pressure vessel. The residence time in the apparatus is not particularly limited as long as the mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.
Dispersion liquid in which particles (C) containing dispersoid (A) are dispersed in solvent (S) by expanding the mixture after line blending under reduced pressure to atmospheric pressure and vaporizing and removing compressive fluid (F) (L) is obtained.

An example of an apparatus used for such a line blending method will be described with reference to the drawings.
FIG. 1 is a flowchart of an experimental apparatus used for producing a dispersion in the mixing method by line blending in the present invention. In the following, the case where carbon dioxide is used as the compressive fluid (F) is taken as an example, but the compressive fluid (F) in the present invention is not limited to this.
As a method of mixing the dispersoid (A), the solvent (S), and the compressive fluid (F), for example, first, the compressive fluid (F) is line blended from the carbon dioxide cylinder B1 through the carbon dioxide pump P2. Introduced into the apparatus (static mixer M1), for example, adjusted so that carbon dioxide is in a liquid or supercritical state pressure (0.5 MPa or more) and temperature, then dispersoid (A) and solvent (S) The solution to be contained is preferably introduced into the liquid or supercritical carbon dioxide from the dissolution tank T1 through the solution pump P1. Subsequently, the dispersoid (A), the solvent (S), and the compressive fluid (F) are line-blended with the static mixer M1 while maintaining the pressure and temperature to obtain a mixture (X). The solution containing the dispersoid (A) and the solvent (S) can be prepared by charging the dispersoid (A) and the solvent (S) in the dissolution tank T1, and sealingly mixing them. In this mixing, it is preferable to perform stirring and heating.
Next, by opening the valve V1 leading to the dispersion liquid receiving tank T2, the mixture (X) after the line blending is expanded under reduced pressure to atmospheric pressure, and the compressive fluid (F) is vaporized and removed, whereby the dispersoid (A ) Containing particles (C) are dispersed in the solvent (S).

Further, the method for producing a dispersion of the present invention is preferably a method including a step of mixing the dispersoid (A) and the compressible fluid (F) by line blending.

In addition, when the mixture (X) is transferred from the pressure resistant container in which the mixture (X) is prepared to another receiving container prepared at the target pressure, the nozzle having the same diameter that can transfer the mixture (X) and the receiving container are the same. A regulator that keeps the pressure is needed. However, in the latter case, a regulator is not required if the pressure in the receiving container is atmospheric pressure.

The dispersion (L) produced by the method for producing a dispersion of the present invention is also included in the present invention.
In the dispersion of the present invention, particles (C) containing the dispersoid (A) are dispersed in a solvent (S), and the median diameter of the particles (C) is 3.0 μm or less.
The application of the dispersion liquid of the present invention is not particularly limited, and can be used for various applications depending on the types of the dispersoid (A) and the solvent (S). For example, it can be suitably used for various applications such as paints, inks, cosmetics, foods, pharmaceuticals and the like.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by weight.

<Production Example 1> Production of Dispersant 454 parts of xylene and 150 parts of low molecular weight polyethylene [Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd., softening point 128 ° C.] 150 parts were charged into a pressure-resistant reaction vessel equipped with a stir bar and a thermometer. After the nitrogen substitution, the temperature was raised to 170 ° C. and dissolved sufficiently, and a mixed solution of 716 parts of styrene, 46 parts of butyl acrylate, 88 parts of acrylonitrile, 34 parts of di-t-butylperoxyhexahydroterephthalate, and 119 parts of xylene was obtained. The solution was dropped at 170 ° C. for 3 hours to polymerize, and further kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [Dispersant 1]. The weight average molecular weight of [Dispersant 1] was 5200. The weight average molecular weight is measured by gel permeation chromatography (GPC) and hereinafter abbreviated as Mw. The measurement conditions for GPC are shown below. It measured similarly about the subsequent manufacture examples.
(GPC measurement 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: 12 standard polystyrene (TSK standard POLY STYRENE) manufactured by Tosoh (molecular weight 500, 1050, 2800, 9100, 18100, 37900, 96400, 190000, 355000, 900000, 2890000)

<Production Example 2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 16 parts of 1,6-hexanediol, 16 parts of sebacic acid, and 0.05 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst are placed. The reaction was carried out for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 4 hours while distilling off the generated water and 1,6-hexanediol under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg. [Crystalline Resin 1] was obtained. [Crystalline resin 1] had a melting point of 65 ° C.

<Production Example 3>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 159 parts of 1,6-hexanediol, 286 parts of dodecanedioic acid, and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added. The reaction was carried out for 8 hours at 170 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction was further carried out under reduced pressure of 5 to 20 mmHg. Removal [Crystalline Resin 2] was obtained. [Crystalline resin 2] had a melting point of 65 ° C. and Mw of 10,000.

<Production Example 4>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 100 parts of 1,6-hexanediol, 30 parts of isophthalic acid, 70 parts of terephthalic acid, and titanium dihydroxybis (triethanolaminate) 1 as a condensation catalyst The reaction was allowed to proceed for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction was further carried out under reduced pressure of 5 to 20 mmHg. The taken-out resin was cooled to room temperature, and then pulverized and granulated to obtain a dispersoid [crystalline resin 3]. [Crystalline resin 3] had a melting point of 99 ° C. and Mw of 6000.

<Production Example 5>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 100 parts of isophthalic acid, 100 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed at 170 ° C. The reaction was carried out for 8 hours while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction was further carried out under reduced pressure of 5 to 20 mmHg. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain [Crystalline Resin 4]. [Crystalline resin 4] had a melting point of 77 ° C. and Mw of 5430.

<Production Example 6>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 15 parts of sebacic acid, 2 parts of adipic acid, 16 parts of 1,4-butanediol, and titanium dihydroxybis (triethanolaminate) 0 as a condensation catalyst .05 parts was added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off generated water. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 4 hours while distilling off the generated water and 1,6-hexanediol under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg. Resin 5] was obtained. [Crystalline resin 5] had a melting point of 58 ° C. and Mw of about 6000.

<Production Example 7>
A reaction vessel equipped with a stir bar and a thermometer was charged with 66 parts of 1,4-butanediol, 86 parts of 1,6-hexanediol, and 40 parts of methyl ethyl ketone (MEK). This solution was charged with 248 parts of hexamethylene diisocyanate (HDI) and reacted at 80 ° C. for 5 hours to obtain a MEK solution of [crystalline resin 6]. After removing the solvent, [Crystalline Resin 6] had a melting point of 57 ° C. and Mw of 9700.

<Production Example 8>
Into a reaction vessel equipped with a stirrer and a desolventizer, 1000 parts of methyl ethyl ketone, 430 parts of 1,6-hexanediol and 570 parts of hexamethylene diisocyanate are added and reacted at 80 ° C. for 7 hours, followed by desorption at 80 ° C. and 20 kPa. Solvent was used to obtain [Crystalline Resin 7]. [Crystalline resin 7] had an Mw of 7,500 and a melting point of 75 ° C.

<Production Example 9>
In a reaction vessel equipped with a stirrer and a solvent removal apparatus, 1000 parts of methyl ethyl ketone, 210 parts of 1,6-hexanediol, polyester diol composed of 1,6-hexanediol and sebacic acid (manufactured by Toyokuni Oil Co., Ltd., trade name “ HS 2H-200S ”, hydroxyl value 56) 500 parts and hexamethylene diisocyanate 290 parts were added, reacted at 80 ° C. for 7 hours, and desolventized at 80 ° C. and 20 kPa to obtain [Crystalline Resin 8]. [Crystalline resin 8] had an Mw of 9,000 and a melting point of 60 ° C.

<Production Example 10>
50 parts of 1,9-nonanediol and 38 parts of diethylene glycol were placed in a reaction vessel, 0.1 part of a 25 wt% methanol solution of sodium methoxide was added with stirring, and the temperature was raised to 160 ° C. After completion of the temperature elevation, 51 parts of dimethyl carbonate was added dropwise, and after 5 hours from the end of the addition, the mixture was cooled to 80 ° C. In order to remove the catalyst, an adsorbent was added and stirred for 1 hour, followed by filtration. The obtained product was returned to the reaction vessel, heated to 240 ° C., depressurized to 0.5 kPa, and unreacted substances and the solvent were distilled off to obtain [Crystalline Resin 9] composed of polycarbonate. [Crystalline resin 9] had an Mw of 6200 and a melting point of 54 ° C.

<Production Example 11>
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 crystallinity containing 1,6-hexanediol as a component. 340 parts of polycarbonate (made by Asahi Kasei Chemicals Corporation, trade name “PCDL T6002”, hydroxyl value 56) was added, reacted at 80 ° C. for 7 hours, desolvated at 80 ° C. and 20 kPa, and composite of polycarbonate and polyurethane [Crystalline resin 10] made of resin was obtained. [Crystalline resin 10] had an Mw of 11000 and a melting point of 61 ° C.

<Production Example 12>
200 parts of xylene and 2 parts of di-t-butylperoxyhexahydroterephthalate are charged into a pressure-resistant reaction vessel equipped with a stir bar and a thermometer. After purging with nitrogen, the temperature is raised to 170 ° C. and dissolved sufficiently. (Perfluorohexyl) ethyl acrylate (cheminox FAAC-6, manufactured by Unimatex) 60 parts, methyl methacrylate 20 parts, styrene 20 parts, and xylene 100 parts mixed solution was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [Amorphous Resin 1]. [Amorphous resin 1] had a weight average molecular weight of 5,200. The softening point measured by the following method with a descent type flow tester (manufactured by Shimadzu Corporation, CFT-500D) was 75 ° C.
While heating 1 g of [Amorphous Resin 1] at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger and extruded from a nozzle having a diameter of 1 mm and a length of 1 mm. (Flow value) ”and“ Temperature ”are drawn, and the temperature corresponding to 1/2 of the maximum value of the plunger drop is read from the graph. This value (temperature when half of the measured sample flows out) Was the softening point.

In the following examples and comparative examples, “T1” is derived from the dispersoid (crystalline material such as crystalline resin) contained in the dispersion when the obtained dispersion is subjected to DSC temperature drop measurement under the following conditions. Exothermic peak temperature.
DSC measurement conditions Using a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, and then heated. The temperature was increased at a rate of 20 ° C./min, and the endothermic change was measured.

The median diameter was measured with a laser particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd., hereinafter simply referred to as “LA-920”).
The change rate of the median diameter was obtained by the following calculation.
Formula 1 B / A × 100-100 = Change rate of median diameter (%)
Measured value A: median diameter of dispersion liquid left to stand at 10 ° C. for 24 hours Measured value B: median diameter in dispersion liquid within one hour after production

The amount of increase in coarse particles was determined by the following calculation.
Formula 2 CD = Coarse particle increase (%)
Measured value C: Coarse particle amount in the dispersion that was allowed to stand for 24 hours at 10 ° C. Measured value D: Coarse particle amount in the dispersion within one hour after production. Note that (median diameter × 3) particles larger than μm are coarse. Particles were used. However, when (median diameter × 3) ≦ 1.0, particles of 1.0 μm or more were coarse particles.

<Example 1>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 1] (T0 (melting point): 65 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 40 ° C. (T2) while maintaining 6 MPa, the nozzle attached to the bottom of the container was fully opened, and the atmosphere (0.1 MPa) The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-1) in which particles (C-1) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-1) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-1) by LA-920 is 0.52 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-1) after standing at 10 ° C. for 24 hours was 0.54 μm, and the amount of coarse particles was 0.0% by volume. The change rate of the median type was 3.8%, and the increase amount of coarse particles was 0.0% by volume. T1 was 20 degreeC from the measurement by DSC.

<Example 2>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 2] (T0 (melting point): 65 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 40 ° C. (T2) while maintaining 6 MPa, the nozzle attached to the bottom of the container was fully opened, and the atmosphere (0.1 MPa) The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-2) in which particles (C-2) containing [crystalline resin 2] were dispersed. . The temperature (T3) of the dispersion (L-2) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-2) by LA-920 is 0.50 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-2) after standing at 10 ° C. for 24 hours was 0.54 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 8.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 3>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 3] (T0 (melting point): 99 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 99 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the internal temperature was lowered to 75 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-3) in which particles (C-3) containing [crystalline resin 3] were dispersed. . The temperature (T3) of the dispersion (L-3) immediately after volume expansion is 38 ° C., the median diameter of the particles (C-3) by LA-920 is 0.45 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-3) after standing at 10 ° C. for 24 hours was 0.47 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 4.4%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 54 degreeC from the measurement by DSC.

<Example 4>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 4] (T0 (melting point): 77 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 77 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 45 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-4) in which particles (C-4) containing [crystalline resin 4] were dispersed. . The temperature (T3) of the dispersion liquid (L-4) immediately after volume expansion is 10 ° C., the median diameter of the particles (C-4) by LA-920 is 0.72 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of particles (C-4) after standing at 10 ° C. for 24 hours was 0.75 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 4.2%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 30 degreeC from the measurement by DSC.

<Example 5>
Into a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 196.8 parts of acetone and 43.2 parts of [crystalline resin 5] (T0 (melting point): 58 ° C.) are charged to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring to raise the temperature in the system to 58 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the internal temperature was lowered to 30 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-5) in which particles (C-5) containing [crystalline resin 5] were dispersed. . The temperature (T3) of the dispersion (L-5) immediately after volume expansion is 0 ° C., the median diameter of the particles (C-5) by LA-920 is 0.66 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-5) after standing at 10 ° C. for 24 hours was 0.66 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 16 degreeC from the measurement by DSC.

<Example 6>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer is charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 6] (T0 (melting point): 57 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 57 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the internal temperature was lowered to 30 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-6) in which particles (C-6) containing [crystalline resin 6] were dispersed. . The temperature (T3) of the dispersion (L-6) immediately after volume expansion is -1 ° C., the median diameter of the particles (C-6) by LA-920 is 0.42 μm, and the amount of coarse particles is 0.0 % By volume. The amount of coarse particles was 0.0% by volume. The median diameter of the particles (C-6) after standing at 10 ° C. for 24 hours was 0.45 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 7.1%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 15 degreeC from the measurement by DSC.

<Example 7>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 7] (T0 (melting point): 75 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 75 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 45 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-7) in which particles (C-7) containing [crystalline resin 7] were dispersed. . The temperature (T3) of the dispersion (L-7) immediately after volume expansion is 0 ° C., the median diameter of the particles (C-7) by LA-920 is 0.53 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-7) after standing at 10 ° C. for 24 hours was 0.54 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 1.9%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 8>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 8] (T0 (melting point): 60 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 60 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the internal temperature was lowered to 30 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-8) in which particles (C-8) containing [crystalline resin 8] were dispersed. . The temperature (T3) of the dispersion (L-8) immediately after the volume expansion is -5 ° C., the median diameter of the particles (C-8) by LA-920 is 0.62 μm, and the amount of coarse particles is 0.0 % By volume. The median diameter of the particles (C-8) after standing at 10 ° C. for 24 hours was 0.65 μm, and the amount of coarse particles was 0.0% by volume. The change rate of the median type was 4.8%, and the increase amount of coarse particles was 0.0% by volume. Moreover, T1 was 17 degreeC from the measurement by DSC.

<Example 9>
A pressure-resistant reaction vessel equipped with a stirring bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [Crystalline Resin 9] (T0 (melting point): 54 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 54 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the internal temperature was lowered to 30 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-9) in which particles (C-9) containing [crystalline resin 9] were dispersed. . The temperature (T3) of the dispersion (L-9) immediately after volume expansion was −2 ° C., the median diameter of the particles (C-9) by LA-920 was 0.41 μm, and the amount of coarse particles was 0.0 % By volume. The median diameter of the particles (C-9) after standing at 10 ° C. for 24 hours was 0.44 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 7.3%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 10>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [Crystalline Resin 10] (T0 (melting point): 61 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring to raise the temperature in the system to 61 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the internal temperature was lowered to 30 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-10) in which particles (C-10) containing [crystalline resin 10] were dispersed. . The temperature (T3) of the dispersion (L-10) immediately after the volume expansion is -1 ° C., the median diameter of the particles (C-10) by LA-920 is 0.52 μm, and the amount of coarse particles is 0.0 % By volume. The median diameter of the particles (C-10) after standing at 10 ° C. for 24 hours was 0.52 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 16 degreeC from the measurement by DSC.

<Example 11>
In a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer, 196.8 parts of acetone and 43.2 parts of [Amorphous Resin 1] (T0 (softening point): 75 ° C.) were added to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 75 ° C. After the temperature rise, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the temperature inside the system was lowered to 45 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). Is released to precipitate a crystalline resin and vaporize and remove carbon dioxide to obtain a dispersion liquid (L-11) in which particles (C-11) containing [amorphous resin 1] are dispersed. It was. The temperature (T3) of the dispersion (L-11) immediately after volume expansion is 10 ° C., the median diameter of the particles (C-11) by LA-920 is 0.39 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of particles (C-11) after standing at 10 ° C. for 24 hours was 0.40 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 2.6%, and the increase in coarse particles was 0.0% by volume.

<Example 12>
In a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer, 196.8 parts of ethyl acetate and 43.2 parts of [crystalline resin 1] (T0 (melting point): 65 ° C.) are added to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed, heated and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 40 ° C. (T2) while maintaining 6 MPa, the nozzle attached to the bottom of the container was fully opened, and the atmosphere (0.1 MPa) The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-12) in which particles (C-12) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-12) immediately after the volume expansion is 4 ° C., the median diameter of the particles (C-12) by LA-920 is 0.50 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-12) after standing at 10 ° C. for 24 hours was 0.52 μm, and the amount of coarse particles was 0.0 vol%. The rate of change in median diameter was 4.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 13>
Into a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer, 196.8 parts of methyl ethyl ketone and 43.2 parts of [crystalline resin 1] (T0 (melting point): 65 ° C.) are charged to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 40 ° C. (T2) while maintaining 6 MPa, the nozzle attached to the bottom of the container was fully opened, and the atmosphere (0.1 MPa) The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-13) in which particles (C-13) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-13) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-13) by LA-920 is 0.51 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-13) after standing at 10 ° C. for 24 hours was 0.51 μm, and the amount of coarse particles was 0.0% by volume. The rate of change in median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 14>
Into a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 196.8 parts of water and 43.2 parts of [Crystalline Resin 1] (T0 (melting point): 65 ° C.) are charged to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. Further, after maintaining the temperature at 65 ° C. to supply carbon dioxide to 6 MPa, the inside of the kettle was observed again from the observation window. The crystalline resin 1 dissolved in carbon dioxide, but separated from water, It was confirmed that two phases were formed. Further, stirring is performed to suspend the crystal resin carbon dioxide solution in water, the temperature inside the system is lowered to 40 ° C. (T2) while maintaining 6 MPa, the nozzle attached to the lower part of the container is fully opened, and the atmosphere (0.1 MPa) The crystalline resin was precipitated, and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-14) in which particles (C-14) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-14) immediately after the volume expansion is 7 ° C., the median diameter of the particles (C-14) by LA-920 is 0.53 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of particles (C-14) after standing at 10 ° C. for 24 hours was 0.54 μm, and the amount of coarse particles was 0.0 vol%. The rate of change in median diameter was 1.9%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 15>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 1] (T0 (melting point): 65 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After raising the temperature, carbon dioxide was supplied to 10 MPa, and the mixture was stirred for 10 minutes. The system temperature was lowered to 40 ° C. (T2) while maintaining 10 MPa, and the nozzle attached to the bottom of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-15) in which particles (C-15) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-15) immediately after volume expansion is 0 ° C., the median diameter of the particles (C-15) by LA-920 is 0.45 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-15) after standing at 10 ° C. for 24 hours was 0.46 μm, and the amount of coarse particles was 0.0 vol%. The rate of change in median diameter was 2.2%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 16>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [crystalline resin 1] (T0 (melting point): 65 ° C.) to 40% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa, and the mixture was stirred for 10 minutes. Then, the system temperature was lowered to 25 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-16) in which particles (C-16) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-16) immediately after the volume expansion was −10 ° C., the median diameter of the particles (C-16) by LA-920 was 0.41 μm, and the amount of coarse particles was 0.0 % By volume. Further, the median diameter of the particles (C-16) after standing at 10 ° C. for 24 hours was 0.41 μm, the change rate of the median diameter was 0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 17>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 196.8 parts of acetone and 43.2 parts of [Crystalline Resin 1] (T0 (melting point): 65 ° C.) to 30% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa, and the mixture was stirred for 10 minutes. Then, the internal temperature was lowered to 40 ° C. (T2) while maintaining 6 MPa, and the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). The crystalline resin was precipitated and the carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-17) in which particles (C-17) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-17) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-17) by LA-920 is 0.50 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of particles (C-17) after standing at 10 ° C. for 24 hours was 0.51 μm, the change rate of the median diameter was 2.0%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 18>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 175.0 parts of acetone and 75.0 parts of [crystalline resin 1] (T0 (melting point): 65 ° C.) to 30% of the volume of the pressure-resistant reaction vessel. The mixture was sealed and heated with stirring, and the system temperature was raised to 65 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes. Then, the system temperature was lowered to 40 ° C. (T2) while maintaining 6 MPa, the nozzle attached to the bottom of the container was fully opened, and the atmosphere (0.1 MPa) The crystalline resin was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-18) in which particles (C-18) containing [crystalline resin 1] were dispersed. . The temperature (T3) of the dispersion (L-18) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-18) by LA-920 is 0.57 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-18) after standing at 10 ° C. for 24 hours was 0.58 μm, the change rate of the median diameter was 1.8%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 19>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 196.8 parts of acetone and 43.2 parts of [Crystalline resin 1] (T0 (melting point): 65 ° C.) were charged, sealed and heated with stirring, and the system temperature was raised to 65 ° C. A solution of was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, the solution of the crystalline resin 1 is introduced at a flow rate of 0.5 L / h from the dissolution tank (tank) T1 and the pump P1, and the mixed solution is line-blended with M1 while maintaining 6 MPa and 40 ° C. (T2). Is released from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), thereby precipitating the crystalline resin 1, vaporizing and removing carbon dioxide, and particles (C-19) containing the crystalline resin 1 are obtained. A dispersed dispersion (L-19) was obtained. The temperature (T3) of the dispersion (L-19) immediately after volume expansion was 4 ° C., the median diameter of the particles (C-19) by LA-920 was 0.39 μm, and the amount of coarse particles was 0.0 volume. %Met. Further, the median diameter of the particles (C-19) after standing at 10 ° C. for 24 hours was 0.39 μm, the change rate of the median diameter was 0%, and the increase amount of coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 20>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 196.8 parts of acetone and 43.2 parts of [Crystalline Resin 10] (T0 (melting point): 61 ° C.) were charged, sealed and heated with stirring, and the system temperature was raised to 61 ° C. A solution of was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, a solution of crystalline resin 10 is introduced at a flow rate of 0.5 L / h from a dissolution tank (tank) and pump P1, and mixed by line blending with a static mixer M1 while maintaining 6 MPa and 30 ° C. (T2). By opening the liquid from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), the crystalline resin 10 is precipitated, and the carbon dioxide is vaporized and removed to obtain particles (C-20) containing the crystalline resin 10 A dispersion liquid (L-20) was obtained. The temperature (T3) of the dispersion (L-20) immediately after volume expansion is -1 ° C., the median diameter of the particles (C-20) by LA-920 is 0.35 μm, and the amount of coarse particles is 0.0 % By volume. Further, the median diameter of the particles (C-20) after standing at 10 ° C. for 24 hours was 0.36 μm, the change rate of the median diameter was 2.9%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 16 degreeC from the measurement by DSC.

<Example 21>
In an experimental apparatus using the line blending method shown in FIG. 1 (as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used), first, in a dissolution tank (tank) T1 196.8 parts of ethyl acetate and 43.2 parts of [Crystalline Resin 1] (T0 (melting point): 65 ° C.) were charged, sealed and heated with stirring, and the system temperature was raised to 65 ° C. 1 solution was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, the solution of the crystalline resin 1 is introduced at a flow rate of 0.5 L / h from the dissolution tank (tank) T1 and the pump P1, and the mixed solution is line-blended with M1 while maintaining 6 MPa and 40 ° C. (T2). Is released from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), thereby precipitating the crystalline resin 1, vaporizing and removing carbon dioxide, and particles (C-21) containing the crystalline resin 1 are obtained. A dispersed dispersion (L-21) was obtained. The temperature (T3) of the dispersion (L-21) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-21) by LA-920 is 0.31 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-21) after standing at 10 ° C. for 24 hours was 0.32 μm, the change rate of the median diameter was 3.2%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 22>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] , 196.8 parts of water and 43.2 parts of [Crystalline resin 1] (T0 (melting point): 65 ° C.) were sealed, heated with stirring, and the system temperature was raised to 65 ° C. 1 solution was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, the solution of the crystalline resin 1 is introduced from the tank T1 and the pump P1 at a flow rate of 0.5 L / h, and while maintaining 6 MPa and 40 ° C. (T2), the mixed liquid line-blended with M1 is dispersed from the nozzle. Dispersion in which particles (C-22) containing the crystalline resin 1 are dispersed by opening the liquid receiving tank T2 (0.1 MPa) to precipitate the crystalline resin 1 and vaporizing and removing carbon dioxide. A liquid (L-22) was obtained. The temperature (T3) of the dispersion (L-22) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-22) by LA-920 is 0.39 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-22) after standing at 10 ° C. for 24 hours was 0.39 μm, the change rate of the median diameter was 0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 23>
In an experimental apparatus using the line blending method shown in FIG. 1 (as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used), first, in a dissolution tank (tank) T1 196.8 parts of acetone and 43.2 parts of [Crystalline Resin 1] (T0 (melting point): 65 ° C.) were charged, sealed and heated with stirring, and the system temperature was raised to 65 ° C. 1 solution was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.7 L / h, and the valve V1 was adjusted to 10 MPa. Next, the solution of the crystalline resin 1 is introduced from the dissolution tank (tank) T1 and the pump P1 at a flow rate of 0.83 L / h, and the liquid mixture is line-blended with M1 while maintaining 10 MPa and 40 ° C. (T2). Is released from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), thereby precipitating the crystalline resin 1, vaporizing and removing carbon dioxide, and particles (C-23) containing the crystalline resin 1 are obtained. A dispersed dispersion (L-23) was obtained. The temperature (T3) of the dispersion (L-23) immediately after volume expansion is 0 ° C., the median diameter of the particles (C-23) by LA-920 is 0.30 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of particles (C-23) after standing at 10 ° C. for 24 hours was 0.31 μm, the change rate of the median diameter was 3.3%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 24>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 196.8 parts of acetone and 43.2 parts of [Crystalline resin 1] (T0 (melting point): 65 ° C.) were charged, sealed and heated with stirring, and the system temperature was raised to 65 ° C. A solution of was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, the solution of the crystalline resin 1 is introduced at a flow rate of 0.5 L / h from the dissolution tank (tank) T1 and the pump P1, and the mixed solution is line-blended with M1 while maintaining 6 MPa and 25 ° C. (T2). Is released from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), thereby precipitating the crystalline resin 1, vaporizing and removing carbon dioxide, and particles (C-24) containing the crystalline resin 1 are obtained. A dispersed dispersion (L-24) was obtained. The temperature (T3) of the dispersion (L-24) immediately after volume expansion is −10 ° C., the median diameter of the particles (C-24) by LA-920 is 0.35 μm, and the amount of coarse particles is 0.0 % By volume. Further, the median diameter of the particles (C-24) after standing at 10 ° C. for 24 hours was 0.36 μm, the change rate of the median diameter was 2.9%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 25>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 175.0 parts of acetone and 75.0 parts of [Crystalline resin 1] (T0 (melting point): 65 ° C.) were charged, sealed and heated with stirring, and the system temperature was raised to 65 ° C. A solution of was prepared. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, the solution of the crystalline resin 1 is introduced at a flow rate of 0.5 L / h from the dissolution tank (tank) T1 and the pump P1, and the mixed solution is line-blended with M1 while maintaining 6 MPa and 40 ° C. (T2). Is released from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), thereby precipitating the crystalline resin 1, vaporizing and removing carbon dioxide, and particles (C-25) containing the crystalline resin 1 are obtained. A dispersed dispersion (L-25) was obtained. The temperature (T3) of the dispersion (L-25) immediately after volume expansion is 4 ° C., the median diameter of the particles (C-25) by LA-920 is 0.37 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of particles (C-25) after standing at 10 ° C. for 24 hours was 0.39 μm, the change rate of the median diameter was 5.4%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 20 degreeC from the measurement by DSC.

<Example 26>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, 168 parts of acetone, and 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature rise, carbon dioxide was supplied to 8 MPa. While maintaining 8 MPa, the temperature was lowered to 70 ° C. (T2), stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). By opening, paraffin wax was precipitated and carbon dioxide was vaporized and removed to obtain dispersion liquid (L-26) in which particles (C-26) containing paraffin wax were dispersed. The temperature (T3) of the dispersion (L-26) immediately after the volume expansion was 13 ° C., the median diameter of the particles (C-26) by LA-920 was 0.52 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of the particles (C-26) after standing at 10 ° C. for 24 hours was 0.53 μm, the change rate of the median diameter was 1.9%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 27>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 24.0 parts of [Dispersant 1] obtained in Production Example 1, carnauba wax (H1-100, T0 (melting point): 83 ° C., manufactured by Dainichi Chemical Co., Ltd.) 48.0 parts, 168 parts of acetone, 40% of the volume of the pressure-resistant reaction vessel were charged, sealed and heated with stirring, and the system temperature was raised to 83 ° C. After the temperature rise, carbon dioxide was supplied to 8 MPa, the temperature was lowered to 75 ° C. while maintaining 8 MPa (T2), and stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa) By opening, carnauba wax was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-27) in which particles (C-27) containing carnauba wax were dispersed. The temperature (T3) of the dispersion (L-27) immediately after the volume expansion was 21 ° C., the median diameter of the particles (C-27) by LA-920 was 0.63 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of particles (C-27) after standing at 10 ° C. for 24 hours was 0.65 μm, the rate of change of the median diameter was 3.2%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 37 degreeC from the measurement by DSC.

<Example 28>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 24.0 parts of [Dispersant 1] obtained in Production Example 1, polyolefin wax (ACCUM ELT100, T0 (melting point): 102 ° C.) 48.0 parts, acetone 168 parts, charged to 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 102 ° C. After the temperature rise, carbon dioxide was supplied to 8 MPa. While maintaining 8 MPa, the temperature was lowered to 90 ° C. (T2), stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). By releasing, the polyolefin wax was precipitated, and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-28) in which particles (C-28) containing the polyolefin wax were dispersed. The temperature (T3) of the dispersion (L-28) immediately after the volume expansion was 32 ° C., the median diameter of the particles (C-28) by LA-920 was 0.66 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. The median diameter of the particles (C-28) after standing at 10 ° C. for 24 hours was 0.68 μm, the change rate of the median diameter was 3.0%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 62 degreeC from the measurement by DSC.

<Example 29>
[Dispersant 1] obtained in Production Example 1 24.0 parts, stearyl stearate (Exepal SS, T0 (melting point): 56 ° C.) 48.0 parts, The mixture was charged to 168 parts of acetone and 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 56 ° C. After the temperature rise, carbon dioxide was supplied to 8 MPa. While maintaining 8 MPa, the temperature was lowered to 40 ° C. (T2), stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened to the atmosphere (0.1 MPa). By releasing, stearyl stearate was precipitated and carbon dioxide was vaporized and removed to obtain dispersion liquid (L-29) in which particles (C-29) containing stearyl stearate were dispersed. The temperature (T3) of the dispersion liquid (L-29) immediately after volume expansion is −7 ° C., the median diameter of the particles (C-29) by LA-920 is 0.54 μm, and the ratio of the coarse particle amount is 0. 0.0% by volume. The median diameter of the particles (C-29) after standing at 10 ° C. for 24 hours was 0.56 μm, the change rate of the median diameter was 3.7%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 19 degreeC from the measurement by DSC.

<Example 30>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, ethyl acetate 168 parts, and 40% of the pressure-resistant reaction vessel volume, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature rise, carbon dioxide was supplied to 8 MPa. Further, while maintaining 8 MPa, the temperature was lowered to 70 ° C. (T2) and stirred for 10 minutes. The paraffin wax was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-30) in which particles (C-30) containing paraffin wax were dispersed. The temperature (T3) of the dispersion (L-30) immediately after the volume expansion was 13 ° C., the median diameter of the particles (C-30) by LA-920 was 0.52 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of the particles (C-30) after standing at 10 ° C. for 24 hours was 0.52 μm, the change rate of the median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 31>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, methyl ethyl ketone 168 parts, and 40% of the pressure-resistant reaction vessel volume, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature rise, carbon dioxide was supplied to 8 MPa. While maintaining 8 MPa, the temperature was lowered to 70 ° C. (T2) and stirred for 10 minutes. By opening, paraffin wax was precipitated and carbon dioxide was vaporized and removed to obtain dispersion liquid (L-31) in which particles (C-31) containing paraffin wax were dispersed. The temperature (T3) of the dispersion (L-31) immediately after the volume expansion was 13 ° C., the median diameter of the particles (C-31) by LA-920 was 0.55 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of particles (C-31) after standing at 10 ° C. for 24 hours was 0.56 μm, the change rate of the median diameter was 1.8%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 32>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, 168 parts of water and 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature increase, carbon dioxide was supplied to 8 MPa. At this time, it was confirmed that the paraffin wax was not dissolved in water but was dissolved only in carbon dioxide, and liquid-liquid two-phase separation was performed. The temperature was lowered to 70 ° C. (T2) while maintaining 8 MPa, and after stirring for 10 minutes, it was confirmed from the observation window that the paraffin wax carbon dioxide container was dispersed in water. By fully opening the nozzle attached to the bottom of the container and opening it to the atmosphere (0.1 MPa), paraffin wax is precipitated, carbon dioxide is vaporized and removed, and particles (C-32) containing paraffin wax are dispersed. A dispersion (L-32) was obtained. The temperature (T3) of the dispersion (L-32) immediately after the volume expansion was 13 ° C., the median diameter of the particles (C-31) by LA-920 was 0.58 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of the particles (C-32) after standing at 10 ° C. for 24 hours was 0.59 μm, the change rate of the median diameter was 1.7%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 33>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, 168 parts of acetone, and 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature increase, carbon dioxide was supplied to 10 MPa. The temperature was lowered to 70 ° C. (T2) while maintaining 10 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the lower part of the container was fully opened and opened to the atmosphere (0.1 MPa) to precipitate paraffin wax, and carbon dioxide. Carbon was vaporized and removed to obtain a dispersion liquid (L-33) in which particles (C-33) containing paraffin wax were dispersed. The temperature (T3) of the dispersion (L-33) immediately after the volume expansion was 6 ° C., the median diameter of the particles (C-33) by LA-920 was 0.36 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of the particles (C-33) after standing at 10 ° C. for 24 hours was 0.37 μm, the change rate of the median diameter was 2.8%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 34>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, 168 parts of acetone, and 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature increase, carbon dioxide was supplied to 8 MPa. The temperature was further lowered to 60 ° C. (T2) while maintaining 8 MPa, and after stirring for 10 minutes, the nozzle attached to the bottom of the container was fully opened and opened to the atmosphere (0.1 MPa), thereby precipitating paraffin wax. Carbon dioxide was evaporated and removed to obtain a dispersion liquid (L-34) in which particles (C-34) containing paraffin wax were dispersed. The temperature (T3) of the dispersion (L-34) immediately after the volume expansion was 0 ° C., the median diameter of the particles (C-34) by LA-920 was 0.39 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of the particles (C-34) after standing at 10 ° C. for 24 hours was 0.41 μm, the change rate of the median diameter was 5.1%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 35>
[Dispersant 1] 24.0 parts obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) The mixture was charged to 48.0 parts, 168 parts of acetone, and 30% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After the temperature increase, carbon dioxide was supplied to 8 MPa. The temperature was lowered to 70 ° C. (T2) while maintaining 8 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the lower part of the container was fully opened and opened to the atmosphere (0.1 MPa) to precipitate paraffin wax, and carbon dioxide. Carbon was vaporized and removed to obtain a dispersion liquid (L-35) in which particles (C-35) containing paraffin wax were dispersed. The temperature (T3) of the dispersion (L-35) immediately after the volume expansion was 13 ° C., the median diameter of the particles (C-35) by LA-920 was 0.43 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. Further, the median diameter of the particles (C-35) after standing at 10 ° C. for 24 hours was 0.45 μm, the change rate of the median diameter was 4.7%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 36>
32.0 parts of [Dispersant 1] obtained in Production Example 1, paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa) in a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer The mixture was charged to 64.0 parts, 168 parts of acetone, and 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 76 ° C. After raising the temperature, carbon dioxide was supplied to 8 MPa, and the temperature was further lowered to 70 ° C. (T2). After stirring for 10 minutes, the nozzle attached to the bottom of the container was fully opened and opened to the atmosphere (0.1 MPa). Then, paraffin wax was precipitated and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-36) in which particles (C-36) containing paraffin wax were dispersed. The temperature (T3) of the dispersion liquid (L-36) immediately after the volume expansion was 13 ° C., the median diameter of the particles (C-36) by LA-920 was 0.53 μm, and the ratio of the coarse particle amount was 0.00. It was 0% by volume. The median diameter of the particles (C-36) after standing at 10 ° C. for 24 hours was 0.54 μm, the change rate of the median diameter was 1.9%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 37>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 168.0 parts of acetone, 24.0 parts of [Dispersant 1] obtained in Production Example 1, and 48.0 parts of paraffin wax (HNP-9, T0 (melting point): 76 ° C., Nippon Seiwa) were charged and sealed. Then, the mixture was heated with stirring, and the temperature in the system was raised to 76 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, the paraffin wax solution was introduced at a flow rate of 0.65 L / h from the dissolution tank (tank) T1 and the pump P1, and the liquid mixture line-blended with M1 was maintained at 8 MPa at 70 ° C. (T2). To the dispersion liquid receiving tank T2 (0.1 MPa) to precipitate paraffin wax, vaporize and remove carbon dioxide, and disperse liquid in which particles (C-37) containing paraffin wax are dispersed ( L-37) was obtained. The temperature (T3) of the dispersion (L-37) immediately after volume expansion is 13 ° C., the median diameter of the particles (C-37) by LA-920 is 0.45 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-37) after standing at 10 ° C. for 24 hours was 0.46 μm, the change rate of the median diameter was 2.2%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 38>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 168.0 parts of acetone, 24.0 parts of [Dispersant 1] obtained in Production Example 1 and 48.0 parts of stearyl stearate (Exepal SS, T0 (melting point): 56 ° C.) were charged and sealed while stirring. The mixture was heated and the temperature in the system was raised to 56 ° C. to prepare a stearyl stearate solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, the stearyl stearate solution was introduced at a flow rate of 0.65 L / h from the dissolution tank (tank) T1 and the pump P1, and the liquid mixture line-blended with M1 was maintained at 8 MPa and 40 ° C. (T2). By opening from the nozzle into the dispersion liquid receiving tank T2 (0.1 MPa), stearyl stearate was precipitated and carbon dioxide was vaporized and removed to disperse particles (C-38) containing stearyl stearate. A dispersion (L-38) was obtained. The temperature (T3) of the dispersion (L-38) immediately after the volume expansion is -7 ° C., the median diameter of the particles (C-38) by LA-920 is 0.41 μm, and the amount of coarse particles is 0.0 % By volume. The median diameter of the particles (C-38) after standing at 10 ° C. for 24 hours was 0.41 μm, the change rate of the median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. It was. Moreover, T1 was 19 degreeC from the measurement by DSC.

<Example 39>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] Charge 168.0 parts of ethyl acetate, 24.0 parts of [Dispersant 1] obtained in Production Example 1, and 48.0 parts of paraffin wax (HNP-9, T0 (melting point): 76 ° C., manufactured by Nippon Seiwa). The mixture was sealed and heated with stirring, and the system temperature was raised to 76 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, the paraffin wax solution was introduced at a flow rate of 0.65 L / h from the dissolution tank (tank) T1 and the pump P1, and the liquid mixture line-blended with M1 was maintained at 8 MPa at 70 ° C. (T2). To the dispersion receiving tank T2 (0.1 MPa) to precipitate the paraffin wax, vaporize and remove the carbon dioxide, and the dispersion liquid in which the particles (C-39) containing the paraffin wax are dispersed ( L-39) was obtained. The temperature (T3) of the dispersion (L-37) immediately after volume expansion is 13 ° C., the median diameter of the particles (C-39) by LA-920 is 0.46 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-39) after standing at 10 ° C. for 24 hours was 0.46 μm, the change in median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 40>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 168.0 parts of water, 24.0 parts of [Dispersant 1] obtained in Production Example 1, and 48.0 parts of paraffin wax (HNP-9, T0 (melting point): 76 ° C., Nippon Seiwa) were charged and sealed. Then, the mixture was heated with stirring, and the temperature in the system was raised to 76 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, the paraffin wax solution was introduced at a flow rate of 0.65 L / h from the dissolution tank (tank) T1 and the pump P1, and the liquid mixture line-blended with M1 was maintained at 8 MPa at 70 ° C. (T2). To the dispersion receiving tank T2 (0.1 MPa) to precipitate the paraffin wax, vaporize and remove the carbon dioxide, and the dispersion liquid in which the particles (C-40) containing the paraffin wax are dispersed ( L-40) was obtained. The temperature (T3) of the dispersion (L-40) immediately after volume expansion is 13 ° C., the median diameter of particles (C-40) by LA-920 is 0.45 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-40) after standing at 10 ° C. for 24 hours was 0.46 μm, the median diameter change was 2.2%, and the increase in coarse particles was 0.0 vol%. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 41>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 168.0 parts of acetone, 24.0 parts of [Dispersant 1] obtained in Production Example 1, and 48.0 parts of paraffin wax (HNP-9, T0 (melting point): 76 ° C., Nippon Seiwa) were charged and sealed. Then, the mixture was heated with stirring, and the temperature in the system was raised to 76 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.70 L / h, and the valve V1 was adjusted to 10 MPa. Next, a paraffin wax solution is introduced at a flow rate of 0.83 L / h from a dissolution tank (tank) T1 and a pump P1, and the mixture liquid line-blended with M1 is maintained at 10 MPa at 70 ° C. (T2). To the dispersion receiving tank T2 (0.1 MPa) to precipitate the paraffin wax, vaporize and remove the carbon dioxide, and disperse the dispersion liquid (C-41) containing the paraffin wax (C-41). L-41) was obtained. The temperature (T3) of the dispersion (L-41) immediately after volume expansion is 13 ° C., the median diameter of the particles (C-41) by LA-920 is 0.39 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-41) after standing at 10 ° C. for 24 hours was 0.39 μm, the change in median diameter was 0.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 42>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 168.0 parts of acetone, 24.0 parts of [Dispersant 1] obtained in Production Example 1, and 48.0 parts of paraffin wax (HNP-9, T0 (melting point): 76 ° C., Nippon Seiwa) were charged and sealed. Then, the mixture was heated with stirring, and the temperature in the system was raised to 76 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, a paraffin wax solution was introduced from the tank T1 and the pump P1 at a flow rate of 0.65 L / h, and the liquid mixture line-blended with M1 was received from the nozzle while maintaining 8 MPa and 60 ° C. (T2). Dispersion liquid (L-42) in which particles (C-42) containing paraffin wax are dispersed by depositing paraffin wax, vaporizing and removing carbon dioxide by opening in tank T2 (0.1 MPa) Got. The temperature (T3) of the dispersion (L-42) immediately after the volume expansion is 1 ° C., the median diameter of the particles (C-42) by LA-920 is 0.38 μm, and the amount of coarse particles is 0.0 volume. %Met. The median diameter of the particles (C-42) after standing at 10 ° C. for 24 hours was 0.39 μm, the median diameter change was 2.6%, and the increase in coarse particles was 0.0 vol%. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Example 43>
In an experimental apparatus using the line blending method shown in FIG. 1 [as a line blending apparatus, a static mixer M1 (manufactured by Noritake Company Limited; inner diameter 3.4 mm, element number 27) was used] 168.0 parts of acetone, 24.0 parts of [Dispersant 1] obtained in Production Example 1, and 48.0 parts of paraffin wax (HNP-9, T0 (melting point): 76 ° C., Nippon Seiwa) were charged and sealed. Then, the mixture was heated with stirring, and the temperature in the system was raised to 76 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, the paraffin wax solution was introduced at a flow rate of 0.65 L / h from the dissolution tank (tank) T1 and the pump P1, and the liquid mixture line-blended with M1 was maintained at 8 MPa at 70 ° C. (T2). To the dispersion receiving tank T2 (0.1 MPa) to precipitate the paraffin wax, vaporize and remove the carbon dioxide, and disperse the dispersion liquid containing particles (C-43) containing the paraffin wax (C-43). L-43) was obtained. The temperature (T3) of the dispersion (L-43) immediately after volume expansion is 13 ° C., the median diameter of the particles (C-43) by LA-920 is 0.51 μm, and the amount of coarse particles is 0.0 volume. %Met. Further, the median diameter of the particles (C-43) after standing at 10 ° C. for 24 hours was 0.52 μm, the change in median diameter was 2.0%, and the increase in coarse particles was 0.0% by volume. Moreover, T1 was 29 degreeC from the measurement by DSC.

<Comparative Example 1>
The same procedure as in Example 1 was carried out except that T2 was set to 70 ° C. and T3 was set to 25 ° C. to obtain a dispersion liquid (RL-1) in which comparative particles (RC-1) were dispersed. The median diameter of the particles (RC-1) by LA-920 was 8.90 μm, and the amount of coarse particles was 3.2% by volume. The median diameter of the particles (RC-1) after standing at 10 ° C. for 24 hours was 10.20 μm, and the amount of coarse particles was 3.4% by volume. The change rate of the median diameter was 14.6%, and the increase amount of coarse particles was 0.2% by volume.

<Comparative example 2>
The same procedure as in Example 1 was conducted except that T2 was set to 70 ° C. and the pre-expansion pressure was set to 10 MPa to obtain a dispersion liquid (RL-2) in which comparative particles (RC-2) were dispersed. The median diameter of the particles (RC-2) by LA-920 was 0.51 μm, and the amount of coarse particles was 0.0% by volume. The median diameter of the particles (RC-2) after standing at 10 ° C. for 24 hours was 3.62 μm, and the amount of coarse particles was 1.5% by volume. The change rate of the median diameter was 609.8%, and the increase amount of coarse particles was 1.5% by volume.

<Comparative Example 3>
The same procedure as in Example 1 was performed except that the pre-expansion pressure was 1 MPa and T3 was 19 ° C., to obtain a dispersion liquid (RL-3) in which comparative particles (RC-3) were dispersed. The median particle size of RC-920 particles (RC-3) was 5.40 μm, and the amount of coarse particles was 3.2% by volume. The median diameter of the particles (RC-3) after standing at 10 ° C. for 24 hours was 7.30 μm, and the amount of coarse particles was 4.5 vol%. The rate of change in median diameter was 35.2%, and the increase in coarse particles was 1.3% by volume.

<Comparative example 4>
The same procedure as in Example 1 was performed except that the pressure after expansion was 3 MPa and T3 was 25 ° C., to obtain a dispersion liquid (RL-4) in which comparative particles (RC-4) were dispersed. The median diameter of particles (RC-4) by LA-920 was 5.70 μm, and the amount of coarse particles was 2.1% by volume. The median diameter of the particles (RC-4) after standing at 10 ° C. for 24 hours was 8.48 μm, and the amount of coarse particles was 5.5% by volume. The change rate of the median diameter was 48.8%, and the increase amount of coarse particles was 3.4% by volume.

<Comparative Example 5>
The same procedure as in Example 26 was carried out except that T2 was 90 ° C. and T3 was 33 ° C., to obtain a dispersion liquid (RL-5) in which comparative particles (RC-5) were dispersed. The median particle size of RC-920 particles (RC-5) was 7.60 μm, and the amount of coarse particles was 3.2% by volume. The median diameter of the particles (RC-5) after standing at 10 ° C. for 24 hours was 11.30 μm, and the amount of coarse particles was 3.5% by volume. The change rate of the median diameter was 48.7%, and the increase amount of coarse particles was 0.3% by volume.

<Comparative Example 6>
The same procedure as in Example 26 was carried out except that T2 was 90 ° C. and the pre-expansion pressure was 10 MPa, to obtain a dispersion liquid (RL-6) in which comparative particles (RC-6) were dispersed. The median particle size of RC-920 particles (RC-6) was 0.45 μm, and the amount of coarse particles was 0.2% by volume. The median diameter of the particles (RC-6) after standing at 10 ° C. for 24 hours was 1.62 μm, and the amount of coarse particles was 4.3% by volume. The rate of change in median diameter was 260.0%, and the increase in coarse particles was 4.1% by volume.

<Comparative Example 7>
The same procedure as in Example 26 was performed except that the pre-expansion pressure was 1 MPa and the post-expansion temperature (T3) was 25 ° C., to obtain a dispersion liquid (RL-7) in which comparative particles (RC-7) were dispersed. The median diameter of particles (RC-7) by LA-920 was 5.61 μm, and the amount of coarse particles was 4.1% by volume. The median diameter of the particles (RC-7) after standing at 10 ° C. for 24 hours was 7.61 μm, and the amount of coarse particles was 5.1% by volume. The rate of change in median diameter was 35.7%, and the increase in coarse particles was 1.0% by volume.

<Comparative Example 8>
The same procedure as in Example 26 was performed except that the pre-expansion pressure was 8 MPa and the post-expansion pressure was 5 MPa, to obtain a dispersion liquid (RL-8) in which comparative particles (RC-8) were dispersed. The median diameter of the particles by RC-920 (RC-8) was 4.32 μm, and the amount of coarse particles was 3.5% by volume. The median diameter of the particles (RC-8) after standing at 10 ° C. for 24 hours was 4.53 μm, and the amount of coarse particles was 4.1% by volume. The rate of change in median diameter was 4.9%, and the increase in coarse particles was 0.6% by volume.

<Comparative Example 9>
Example 19 was carried out in the same manner except that T2 was set to 70 ° C. and T3 was set to 25 ° C., to obtain a dispersion liquid (RL-9) in which comparative particles (RC-9) were dispersed. The median particle size of RC-920 particles (RC-9) was 9.50 μm, and the amount of coarse particles was 2.9% by volume. The median diameter of the particles (RC-9) after standing at 10 ° C. for 24 hours was 11.50 μm, and the amount of coarse particles was 4.3% by volume. The rate of change in median diameter was 21.1%, and the increase in coarse particles was 1.4% by volume.

<Comparative Example 10>
A dispersion (RL-10) in which comparative particles (RC-10) were dispersed was obtained in the same manner as in Example 19 except that T2 was set at 70 ° C., T3 was set at 4 ° C., and the pressure before expansion was 10 MPa. The median particle size of RC-920 particles (RC-10) was 0.41 μm, and the amount of coarse particles was 0.0% by volume. The median diameter of the particles (RC-10) after standing at 10 ° C. for 24 hours was 3.21 μm, and the amount of coarse particles was 1.5% by volume. The change rate of the median diameter was 682.9%, and the increase amount of coarse particles was 1.5% by volume.

<Comparative Example 11>
The same procedure as in Example 19 was carried out except that T3 was 25 ° C. and the pre-expansion pressure was 1 MPa to obtain a dispersion liquid (RL-11) in which comparative particles (RC-11) were dispersed. The median diameter of the particles by RC-920 (RC-11) was 4.30 μm, and the amount of coarse particles was 1.7% by volume. The median diameter of the particles (RC-11) after standing at 10 ° C. for 24 hours was 5.37 μm, and the amount of coarse particles was 4.5 vol%. The change rate of the median diameter was 24.9%, and the increase amount of coarse particles was 2.8% by volume.

<Comparative Example 12>
The same procedure as in Example 19 was carried out except that T3 was 25 ° C. and the post-expansion pressure was 3 MPa to obtain a dispersion liquid (RL-12) in which comparative particles (RC-12) were dispersed. The median diameter of the particles by RC-920 (RC-12) was 6.10 μm, and the amount of coarse particles was 3.8% by volume. The median diameter of the particles (RC-12) after standing at 10 ° C. for 24 hours was 8.45 μm, and the amount of coarse particles was 5.1% by volume. The rate of change in median diameter was 38.5%, and the increase in coarse particles was 1.3% by volume.

<Comparative Example 13>
The same procedure as in Example 37 was conducted except that T2 was 80 ° C. and T3 was 33 ° C., to obtain a dispersion liquid (RL-13) in which comparative particles (RC-13) were dispersed. The median diameter of the particles by RC-920 (RC-13) was 5.60 μm, and the amount of coarse particles was 3.5% by volume. The median diameter of the particles (RC-13) after standing at 10 ° C. for 24 hours was 10.54 μm, and the amount of coarse particles was 4.1% by volume. The rate of change in median diameter was 88.2%, and the increase in coarse particles was 0.6% by volume.

<Comparative example 14>
The same procedure as in Example 37 was carried out except that T2 was 80 ° C. and the pre-expansion pressure was 10 MPa, to obtain a dispersion liquid (RL-14) in which comparative particles (RC-14) were dispersed. The median particle size of RC-920 particles (RC-14) was 0.41 μm, and the amount of coarse particles was 0.1% by volume. The median diameter of the particles (RC-14) after standing at 10 ° C. for 24 hours was 3.24 μm, and the amount of coarse particles was 3.5% by volume. The rate of change in median diameter was 690.2%, and the increase in coarse particles was 3.4% by volume. T1 was 20 degreeC from the measurement by DSC.

<Comparative Example 15>
The same procedure as in Example 37 was performed except that the pre-expansion pressure was 1 MPa and T2 was 40 ° C., to obtain a dispersion liquid (RL-15) in which comparative particles (RC-15) were dispersed. The median particle size of RC-920 particles (RC-15) was 4.65 μm, and the amount of coarse particles was 4.5% by volume. The median diameter of the particles (RC-15) after standing at 10 ° C. for 24 hours was 5.65 μm, and the amount of coarse particles was 4.7% by volume. The change rate of the median diameter was 21.5%, and the increase amount of coarse particles was 0.2% by volume.

<Comparative Example 16>
The same procedure as in Example 37 was performed except that the pressure after expansion was 5 MPa and T2 was 40 ° C., to obtain a dispersion liquid (RL-16) in which comparative particles (RC-16) were dispersed. The median particle size of RC-920 particles (RC-16) was 3.32 μm, and the amount of coarse particles was 3.8% by volume. The median diameter of the particles (RC-16) after standing at 10 ° C. for 24 hours was 5.57 μm, and the amount of coarse particles was 4.8% by volume. The rate of change in median diameter was 67.8%, and the increase in coarse particles was 1.0% by volume.

Tables 1 to 6 show the evaluation results of the dispersions in Examples 1 to 43 and Comparative Examples 1 to 16.

As shown above, it can be seen that the dispersion liquid of the example is a dispersion liquid in which particles containing a dispersoid are finely and stably dispersed in a solvent as compared with the dispersion liquid of the comparative example.

The dispersion of fine particles can be rapidly obtained by the method for producing a dispersion of the present invention. The dispersion produced by the production method of the present invention is suitable for various uses such as paints, inks, cosmetics, foods, pharmaceuticals and the like.

T1: Dissolution tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T2: Dispersion tank B1: Carbon dioxide cylinder P1: Solution pump P2: Carbon dioxide pump M1: Static mixer V1: Valve

Claims

The particle (C) containing the dispersoid (A) includes the step of expanding the volume of the mixture (X) containing the dispersoid (A), the solvent (S), and the compressible fluid (F). A method for producing a dispersed dispersion (L), wherein the dispersoid (A) is dissolved in the solvent (S) and / or the compressive fluid (F) at a temperature below the melting point or softening point of the dispersoid (A). In this state, the mixture (X) is volume-expanded below the melting point or softening point of the dispersoid (A), and the median diameter of the particles (C) is 3.0 μm or less. ) Manufacturing method.
The method for producing a dispersion (L) according to claim 1, wherein the dispersoid (A) has a melting point and satisfies the following condition 1.
Condition 1
T3 <T1 <T2 <T0
T0: Melting point of dispersoid (A) T1: Exothermic peak temperature derived from dispersoid (A) when DSC temperature drop measurement of dispersion (L) T2: Temperature of mixture (X) immediately before volume expansion T3: Mixture Temperature of dispersion liquid (L) immediately after volume expansion of (X)
The manufacturing method of the dispersion liquid (L) of Claim 2 which satisfy | fills the following conditions 2. FIG.
Condition 2
T3 + 10 <T1
T1: Exothermic peak temperature derived from the dispersoid (A) when the dispersion (L) was subjected to DSC temperature drop measurement. T3: Temperature of the dispersion (L) immediately after volumetric expansion of the mixture (X)
In the mixture (X), the dispersoid (A) is subjected to liquid-liquid two-phase separation from at least one liquid selected from the group consisting of a solvent (S) and a compressive fluid (F). The manufacturing method of the dispersion liquid (L) in any one of.
The method for producing a dispersion (L) according to claim 1, wherein the dispersoid (A) is an amorphous material.
The method for producing a dispersion (L) according to any one of claims 1 to 5, wherein the compressive fluid (F) is liquid carbon dioxide, subcritical carbon dioxide or supercritical carbon dioxide.
A dispersion produced by the production method according to any one of claims 1 to 6.