JP2006199904A - Method for producing heat expansible microcapsule and method for producing hollow resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing heat expansible microcapsules and hollow resin particles with excellent heat resistance. <P>SOLUTION: The invention relates to the method for producing the heat expansible microcapsules comprising polymer (X) wherein the polymer (X) comprises at least one resins selected from a group comprising polyurethane resins, epoxy resins and polyamide resins. The method for producing expansible microcapsules comprising polymer (X) comprises a step preparing an O/W type emulsion (E) by dispersing a mixture (D) comprising a polymer precursor (a) and a solvent (C), in water, a step mixing the emulsion (E) with a polymer precursor (b) or a solution (F) of (b) and then carrying out an interfacial polymerization. The hollow resin particles are obtained by heating the heat expansible microcapsules. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing thermally expandable microcapsules and a method for producing hollow resin particles obtained by heating and expanding the thermally expandable microcapsules. More specifically, the present invention relates to a thermally expandable microcapsule having excellent heat resistance and a method for producing hollow resin particles.

  Thermally expandable microcapsules encapsulate a liquid that is gaseous at or below the softening temperature of the shell, and expand the shell by heating above the softening temperature of the shell. Therefore, the resin constituting the shell is a thermoplastic resin and needs to have high gas barrier properties and heat resistance higher than the heating expansion temperature. Resins that satisfy all of these conditions include vinyl chloride resin, vinyl alcohol resin, and acrylic resin mainly composed of acrylonitrile, but vinyl chloride resin has a large environmental impact, and vinyl alcohol resin is very water-soluble. It has a problem that it is difficult to handle. In view of this, a thermally expandable microcapsule having an acrylic resin whose main component is acrylonitrile as a shell has been studied (Patent Document 1).

Japanese Examined Patent Publication No. 42-26524

  As a conventional production method for obtaining hollow resin particles, (1) a method of encapsulating a low-boiling solvent such as pentane in a resin and then gasifying and expanding the low-boiling solvent (Patent Document 2) (2) A method in which an alkali-swelling substance is contained in the polymer particles, and an alkali liquid is infiltrated into the polymer particles to expand the alkali-swelling substance (Patent Document 3), (3) two types Examples include a method using the above resin and utilizing the difference in compatibility and curing shrinkage (Patent Document 4).

International Publication WO99 / 43758 Pamphlet Japanese Patent Laid-Open No. 11-349839 JP 05-125127 A

However, the resin composition of the hollow resin particles is limited to vinyl or the like, and there is a problem inferior in heat resistance.
The present invention has been made in view of the above circumstances in the prior art. That is, it aims at providing the thermal expansion microcapsule excellent in heat resistance, and the manufacturing method of a hollow resin particle.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention
An O / W emulsion (E) obtained by dispersing a mixture (D) containing a polymer precursor (a) and a solvent (C) in water, and a solution (F) of the polymer precursor (b) or (b) ), And a method for producing a thermally expandable microcapsule (Y) comprising a polymer (X) characterized by interfacial polymerization: a method for producing a hollow resin particle (Z) characterized by further heat treatment is there.

  In the production method of the present invention, the resin composition and particle size range can be applied in a very wide range as compared with the conventional production methods of thermally expandable microcapsules and hollow resin particles, and characteristics required for use at high temperatures ( Thermally expandable microcapsules and hollow particles according to heat resistance and the like can be produced.

  The thermally expandable microcapsule (Y) of the present invention is a resin particle that can be converted into a hollow resin particle (Z) by heat treatment, and has an expansion ratio of 10 times or more in volume.

The manufacturing method of the thermally expandable microcapsule (Y) of the present invention comprises the following steps.
1. Step 1 for producing an O / W emulsion (E) by dispersing a mixture (D) containing a polymer precursor (a) and a solvent (C) in water.
2. O / W emulsion (E) and polymer precursor (b) or solution (F) solution (F) are mixed and subjected to interfacial polymerization, whereby suspension of thermally expandable microcapsules (Y) comprising polymer (X) is suspended. Step 2 to make a suspension.
3. Step 3 of obtaining thermally expandable microcapsules (Y) by removing thermally expandable microcapsules (Y) from the suspension and drying.

The polymer (X) is formed by interfacial polymerization of a polymer precursor (a) and a polymer precursor (b). As the polymer (X), any resin that can form an aqueous dispersion can be used, and it may be a thermoplastic resin or a thermosetting resin.
For example, a polyurethane resin, an epoxy resin, a polyester resin, a polyamide resin, a polyimide resin, a phenol resin, a melamine resin, and the like can be given.
As the polymer (X), two or more of the above resins may be used in combination. Among these, a polyurethane resin, an epoxy resin, a polyamide resin, and a combination thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

The polymer precursor (a) and the polymer precursor (b) used in the present invention are not particularly limited as long as they can become the polymer (X) by interfacial polymerization. (A) is preferably hydrophobic, and (b) is preferably water-soluble.
For example, when the polymer (X) is a polyurethane resin, (a) is an isocyanate group-terminated prepolymer (G), and (b) is an active hydrogen group-containing compound (H).
For example, when (X) is an epoxy resin, (a) is polyepoxide (K), and (b) is an active hydrogen group-containing compound (H ′).
For example, when (X) is a polyamide resin, (a) includes dicarboxylic acid (H3), and (b) includes polyamine (H5).
Hereinafter, specific examples of the polymer precursor (a) and the polymer precursor (b) will be described below for each polymer (X).

When (X) is a polyurethane resin As the polyurethane resin, an isocyanate group-terminated prepolymer (G) [polymer precursor (a)] and an active hydrogen group-containing compound (H) {water, low molecular polyol [low molecular diol ( H1) trivalent or higher molecular polyol (H2), dicarboxylic acid (H3), trivalent or higher polycarboxylic acid (H4), polyamine (H5), polythiol (H6), high molecular polyol (H7), etc. } Polyaddition product with [polymer precursor (b)] and the like.

The isocyanate group-terminated prepolymer (G) is preferably formed by the reaction of the polyisocyanate (G1) and the active hydrogen group-containing compound (H). In this case, the equivalent ratio of (G1) to (H) is usually 0.1 to 0.8 equivalent, preferably 0.2 to 0.6 equivalent, with respect to 1 equivalent of (G1).
Moreover, the isocyanate group content of (G) is 0.5-10 weight% normally, Preferably it is 1.5-6 weight%.

As polyisocyanate (G1), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (except for carbon in NCO group) Formula polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.
Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / 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 wt. %) Of trifunctional or higher polyamines] phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate Such as theft and the like.
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 And aliphatic polyisocyanates.
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- and / or 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- and / 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 of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Among these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the low molecular diol (H1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecane. Diol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .; alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) ); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) Knoll S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; other, poly Examples include lactone diols (such as poly-ε-caprolactone diol) and polybutadiene diols. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
The trivalent or higher molecular weight polyol (H2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (trisphenol) PA, etc.); novolak resins (phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins. Acrylic polyols [Copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers]

Dicarboxylic acids (H3) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.) Branched alkylene dicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl) Succinic acid); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (H4) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). As the dicarboxylic acid (H3) or the trivalent or higher polycarboxylic acid (H4), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Examples of the polyamine (H5) include aliphatic polyamines (C2 to C18): aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2 -C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.}}; these alkyl (C1 -C4) or hydroxyalkyl (C2 ~ C4) Substituent [Dialkyl (C1 -C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methylimi Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]; aromatic ring Containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4 , 4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc., heterocyclic polyamines (C4 -C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2- Aromatic polyamines such as (amino-2-methylpropyl) piperazine (C6 to C20): unsubstituted aromatic polyamine [ , 2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 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 .; nucleus-substituted alkyl group [methyl, ethyl , N- and i-propyl, C1-C4 alkyl groups such as butyl), such as 2,4- and 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-diethyl-2,4-diaminobenzene, 1,3-dimethyl- 2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4- Diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diamy Naphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5 '-Tetraisopropylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-Diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenyl Tan, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraisopropyl- 4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone, etc. And mixtures of these isomers in various proportions; aromatic polyamines [methylene bis] having a nuclear substitution electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy, ethoxy; nitro group, etc.) -O-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, -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′-me Renbis (2-iodoaniline), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; secondary amino group [In the aromatic polyamine, a 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 (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) Polyamines such as low molecular weight polyamide polyamines obtained by condensation with polyamines (the above alkylene diamines, polyalkylene polyamines, etc.) Ether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol and the like).

  Examples of polythiol (H6) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

As the polymer polyol (H7), an OH equivalent [number average molecular weight per hydroxyl group] is 300 or more, preferably 300 to 10,000, more preferably 2 to 4 or more, preferably 2 to 3 valence polyol. Can be used.
(H7) includes polyester polyol (H71), polyether polyol (H72), and mixtures of two or more thereof.

Examples of (H71) include condensed polyester polyol (H711) (by polycondensation of polyol and polycarboxylic acids), polylactone polyol (H712) (one obtained by ring-opening polymerization of a lactone monomer using a polyol as an initiator). Polycarbonate polyol (H713) [by reaction of polyol and alkylene (2 to 4 carbon atoms) carbonate (such as ethylene carbonate), phosgenation or transesterification with diphenyl carbonate]; and mixtures of two or more of these It is done.

The polycarboxylic acids in (H711) include polycarboxylic acids and ester-forming derivatives thereof.
Specific examples include aliphatic polycarboxylic acids [polycarboxylic acids having 2 to 6 functional groups and 3 to 30 carbon atoms such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, hexa Hydrophthalic acid, etc.], aromatic polycarboxylic acids [polycarboxylic acids having 2 to 6 functional groups and 8 to 30 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, trimellit Acid, pyromellitic acid, etc.]; these ester-forming derivatives [acid anhydrides, lower alkyl (carbon number 1-4) esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc.): for example, maleic anhydride Acid, phthalic anhydride, dimethyl terephthalate, etc.]; and mixtures of two or more thereof.
Of these, aliphatic polycarboxylic acids are preferred.

  Examples of the lactone monomer in (H712) include lactones having 3 to 17 carbon atoms (preferably 4 to 12), such as γ-butyrolactone, ε-caprolactone, γ-valerolactone, and mixtures of two or more thereof.

  (H72) includes a compound having AO added to a compound having two or more active hydrogen atoms.

  Examples of the compound having an active hydrogen atom include low-molecular polyols (for example, the above (H1)); divalent phenols (for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), monocyclic phenols (catechol, hydroquinone, etc.) )]; Amines [primary monoamines such as alkyl or alkenyl amines (1 to 20 carbon atoms), anilines, alkanolamines (2 to 4 carbon atoms of the hydroxyl alkyl group) (such as those mentioned in the terminators below), polyamines such as (A22), heterocyclic polyamines such as piperazine, aminoalkyl (2 to 4 carbon atoms) piperazine (such as aminoethylpiperazine)] and the like.

As AO, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- and 2,3-butylene oxide, styrene oxide, carbon number 5 -10 or more α-olefin oxides, epichlorohydrin, and combinations of two or more thereof (block and / or random addition).
Of these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and alkylene oxide adducts of novolac resins, and particularly preferred are alkylene oxide adducts of novolac resins.

When (X) is an epoxy resin As an epoxy resin, polyepoxide (K) [polymer precursor (a)] and active hydrogen group-containing compound (H ′), {for example, dicarboxylic acid (H3), trivalent or higher Polycarboxylic acid (H4), polyamine (H5), polythiol (H6), dicarboxylic acid (H3) or acid anhydride of trivalent or higher polycarboxylic acid (H4), etc.} [polymer precursor (b)] Examples include adducts and cured products.

  The polyepoxide (K) of the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. A thing preferable as polyepoxide (K) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (K) is usually 65 to 1000, preferably 90 to 500.

  Examples of the polyepoxide (K) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates 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, Of glycol ether of enolic or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether 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 condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. 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. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, 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 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 Can be mentioned. 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 type also 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.

  Examples of the dicarboxylic acid (H3), trivalent or higher polycarboxylic acid (H4), and acid anhydrides thereof include those described above.

When (X) is a polyamide resin As a polyamide resin, a polycondensate of the dicarboxylic acid (H3) [polymer precursor (a)] and the polyamine (H5) [polymer precursor (b)], or a dicarboxylic acid Examples thereof include polycondensates of a dihalide (L) [polymer precursor (a)] and the polyamine (H5) [polymer precursor (b)].

As dicarboxylic acid dihalide (L), aliphatic dicarboxylic acid dihalide,
Examples thereof include alicyclic dicarboxylic acid dihalides and aromatic dicarboxylic acid dihalides. Examples of aliphatic dicarboxylic acid dihalides include aliphatic dicarboxylic acid dichlorides (oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, glutaric acid dichloride, adipic acid dichloride, muconic acid dichloride, sebacic acid dichloride, nonane. Acid dichloride, undecanoic acid dichloride, and aliphatic dicarboxylic acid dichlorides (such as oxalic acid dibromide, malonic acid dibromide, succinic acid dibromide, and fumaric acid dibromide).
Examples of the alicyclic dicarboxylic acid dihalide include alicyclic dicarboxylic acid dichloride (1,2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,3 -Cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, etc.), alicyclic dicarboxylic acid dibromide (1,2-cyclopropanedicarboxylic acid dibromide, 1,3- And cyclobutane dicarboxylic acid dibromide).
Examples of aromatic dicarboxylic acid dihalides include aromatic dicarboxylic acid dichlorides (phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 1,5- (9-oxofluorene) dicarboxylic acid dichloride. 1,4-anthracene dicarboxylic acid dichloride, 1,4-anthraquinone dicarboxylic acid dichloride, 2,5-biphenyl dicarboxylic acid dichloride, 1,5-biphenylene dicarboxylic acid dichloride, 4,4′-biphenyl dicarbonyl chloride, 4,4 '-Methylene dibenzoic acid dichloride, 4,4'-isopropylidene dibenzoic acid dichloride, 4,4'-bibenzyldicarboxylic acid dichloride, 4,4'-stilbene dicarboxylic acid dichloride, 4,4' Transdicarboxylic acid dichloride, 4,4′-carbonyldibenzoic acid dichloride, 4,4′-oxydibenzoic acid dichloride, 4,4′-sulfonyldibenzoic acid dichloride, 4,4′-dithiodibenzoic acid dichloride, p -Phenylenediacetic acid dichloride, 3,3'-p-phenylenedipropionic acid dichloride, etc.), aromatic dicarboxylic acid dibromides (phthalic acid dibromide, isophthalic acid dibromide, terephthalic acid dibromide, etc.), etc. A mixture of seeds or more can be mentioned.
Of these, preferred are aromatic dicarboxylic acid dihalides, more preferred are aromatic dicarboxylic acid dichlorides, and most preferred are isophthalic acid dichloride and terephthalic acid dichloride.

When (X) is the following resin, examples of the polymer precursor (a) and the polymer precursor (b) include the following.
When (X) is a polyester resin, (a) a polycarboxylic acid, (b) a polyol;
When (X) is a polyimide resin, (a) polycarboxylic acid anhydride, (b) polyamine;
When (X) is a phenol resin, (a) phenol, (b) formaldehyde;
When (X) is a melamine resin, (a) melamine, (b) formaldehyde and the like can be mentioned.

  The glass transition temperature (Tg) of the polymer (X) is usually 0 ° C. to 300 ° C., preferably 20 ° C. to 250 ° C., more preferably from the viewpoint of the particle size uniformity and powder flowability of the hollow resin particles (Z). Is 50 ° C to 200 ° C. Tg in the present invention is a value obtained from differential scanning calorimetry (hereinafter referred to as DSC) measurement.

  From the viewpoint of reducing dissolution or swelling of the hollow resin particles (Z) in water or a solvent used for dispersion, the molecular weight of the polymer (X), the SP value (the calculation method of the SP value is Polymer Engineering). and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154), crystallinity, molecular weight between cross-linking points, and the like are preferably adjusted as appropriate.

  The number average molecular weight of the polymer (X) (measured by gel permeation chromatography (hereinafter referred to as GPC), hereinafter abbreviated as Mn) is usually 1,000 to 5,000,000, preferably 2,000 to 500,000, and the SP value is usually 7-18, preferably 8-14. The melting point (measured by DSC) of the polymer (X) is usually 50 ° C. or higher, preferably 80 ° C. or higher.

In the present invention, the solvent (C) is used for the purpose of thermally expanding to obtain hollow resin particles, and preferably has a boiling point of 0 to 150 ° C. without dissolving the polymer (X). More preferably, it is 25-120 degreeC, Most preferably, it is 35-105 degreeC.
The addition amount is preferably 2 to 35% by weight, more preferably 5 to 25% by weight, based on the weight of the polymer (X).
Specific examples of (C) include water; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane; aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; acetic acid Ester or ester ether solvents such as ethyl, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol , N-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol and other alcohol solvents; dimethylformamide, dimethylacetoa Amide solvents such as de; sulfoxide solvents such as dimethylsulfoxide, N- heterocycles and hydrocarbon solvents such as methylpyrrolidone, and a mixed solvent of two or more thereof. Of these, water and an aliphatic hydrocarbon solvent are preferable, and water, n-hexane, and n-heptane are more preferable.

  In the polymer (X) constituting the thermally expandable microcapsule (Y) of the present invention, other additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, oxidation agents) An inhibitor, an anti-blocking agent, a heat stabilizer, a flame retardant, and the like). As a method for adding other additives to the polymer (X), the polymer precursor (a) or the polymer precursor (b) and the additives may be mixed in advance when the dispersion is formed in water. More preferably, the mixture is dispersed in water after mixing. In the present invention, the additive does not necessarily have to be mixed when the particles are formed in water, and may be added after the particles are formed. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

Hereinafter, each process of the manufacturing method of a thermally expansible microcapsule (Y) is demonstrated.
Process 1
The O / W emulsion used in the present invention is obtained by dispersing a mixture (D) containing a polymer precursor (a) and a solvent (C) in water.

  Examples of the method for obtaining the O / W emulsion include a method in which the mixture (D) containing the polymer precursor (a) and the solvent (C) is dispersed in water in the presence of the following emulsifier or dispersant under the following dispersion conditions. . Known dispersers such as a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic type can be used. Of these, a more preferable method is a high-speed shearing method. When a high-speed shearing disperser is used, the number of rotations is preferably 1,000 to 30,000 rpm, more preferably 2,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 5 minutes. The dispersion temperature is preferably 20 to 40 ° C.

  In the above, as the emulsifier or dispersant used, a known surfactant (S), water-soluble polymer (T) and the like can be used. Moreover, a solvent (U) etc. can be used together as an auxiliary agent for emulsification or dispersion.

  As the surfactant (S), anionic surfactant (S-1), cationic surfactant (S-2), amphoteric surfactant (S-3), nonionic surfactant (S-4) and the like. Is mentioned. The surfactant (S) may be a combination of two or more surfactants.

  Examples of the anionic surfactant (S-1) include carboxylic acid or a salt thereof, a sulfate ester salt, a salt of carboxymethylated product, a sulfonate salt, and a phosphate ester salt.

  Examples of carboxylic acids or salts thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof. Specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. , Oleic acid, linoleic acid, ricinoleic acid and a mixture of higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like. Examples of the salt include salts of sodium, potassium, ammonium, alkanolamine and the like.

  Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms) and higher alkyl ether sulfate esters salts (1 to 10 moles of ethylene oxide of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated oils or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (sulfurized lower alcohol esters of unsaturated fatty acids) And sulphated olefins (sulphated and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt. Specific examples of higher alcohol sulfates include octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, alcohols synthesized using Ziegler catalysts (for example, ALFOL 1214: CONDEA's sulfate ester salt, alcohols synthesized by the oxo method (for example, Dovanol 23, 25, 45: Mitsubishi Yuka, Tridecanol: Kyowa Hakko, Oxocol 1213, 1215, 1415: Nissan Chemical, Diadol 115 -L, 115H, 135: manufactured by Mitsubishi Chemical); specific examples of higher alkyl ether sulfates include lauryl alcohol ethylene oxide 2-mol adduct sulfate, octyl alcohol ethylene Oxide 3-mole adduct sulfate ester; Specific examples of sulfated oils include sodium, potassium, ammonium, alkanolamine salts sulfated fatty acids of castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, sheep fat, etc. Specific examples of the ester include sodium, potassium, ammonium, and alkanolamine salts of sulfates such as butyl oleate and butyl ricinoleate; specific examples of the sulfated olefin include Typol (manufactured by Shell).

  Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms and a carboxymethylated salt of an ethylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms. It is done. Specific examples of salts of carboxymethylated products of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol Specific examples of salts of carboxymethylated sodium salt of carboxymethylated product of aliphatic alcohol ethylene oxide 1-10 mol adduct include octyl alcohol ethylene oxide 3 mol adduct carboxymethylated sodium salt, lauryl alcohol ethylene oxide 4 Mole adduct carboxymethylated sodium salt, dovanol 23 ethylene oxide 3 mol adduct carboxymethylated sodium salt, tridecanol ethylene oxide Such as 5 mole adduct carboxymethylated sodium salt.

  Examples of the sulfonate include (d1) alkylbenzene sulfonate, (d2) alkylnaphthalene sulfonate, (d3) sulfosuccinic acid diester type, (d4) α-olefin sulfonate, (d5) Igepon T type, (d6 ) Other sulfonates of aromatic ring-containing compounds. Specific examples of alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of alkyl naphthalene sulfonate; sodium dodecyl naphthalene sulfonate; specific examples of sulfosuccinic acid diester type include di-2 sulfosuccinic acid di-2 -Ethylhexyl ester sodium salt and the like. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether, styrenated phenol sulfonate, and the like.

  Examples of phosphoric acid ester salts include (e1) higher alcohol phosphoric acid ester salts and (e2) higher alcohol ethylene oxide adduct phosphoric acid ester salts.

  Specific examples of higher alcohol phosphoric acid ester salts include lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester sodium salt; specific examples of higher alcohol ethylene oxide adduct phosphoric acid ester salts include oleyl alcohol ethylene oxide 5 mol adduct phosphate monoester disodium salt.

  Examples of the cationic surfactant (S-2) include a quaternary ammonium salt type and an amine salt type.

  The quaternary ammonium salt type is obtained by a reaction between a tertiary amine and a quaternizing agent (an alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, dimethyl sulfate; ethylene oxide, etc.) For example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride, polyoxyethylene trimethyl ammonium chloride, stearamide ethyl diethyl Examples include methylammonium methosulfate.

  As amine salt type, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkylphosphoric acid, etc.) It is obtained by neutralizing with For example, the primary amine salt type includes inorganic or organic acid salts of higher aliphatic amines (higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine); Examples include fatty acid (stearic acid, oleic acid, etc.) salts and the like. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines. Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), ethylene oxides of aliphatic amines (2 moles). Above) Adducts, alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) -7-undecene, etc.) , Inorganic acid salts or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.); triethanolamine monostearate, stearamide ethyl diethyl methyl ethanol Examples include inorganic acid salts or organic acid salts of tertiary amines such as amines.

  Examples of the amphoteric surfactant (S-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Examples of the carboxylate type amphoteric surfactant include an amino acid type amphoteric surfactant and a betaine type amphoteric surfactant.

Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.
[R-NH- (CH2) n-COO] mM [wherein R is a monovalent hydrocarbon group; n is usually 1 or 2; m is 1 or 2; M is a hydrogen atom, alkali metal atom, alkaline earth Metal atom, ammonium cation, amine cation, alkanolamine cation and the like. Specific examples include, for example, alkylaminopropionic acid type amphoteric surfactants (such as sodium stearylaminopropionate and sodium laurylaminopropionate); alkylaminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate), and the like. It is done.

  Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule. For example, alkyldimethylbetaine (stearyl) represented by the following general formula: Dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, etc.), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyl dihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.) etc. are mentioned.

  Furthermore, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of other amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; pentadecylsulfotaurine and the like Examples include sulfobetaine-type amphoteric surfactants.

  Examples of the nonionic surfactant (S-4) include alkylene oxide addition type nonionic surfactants and polyvalent alcohol type nonionic surfactants.

  Alkylene oxide addition type nonionic surfactants include polyalkylene glycols obtained by adding alkylene oxide directly to higher alcohols, higher fatty acids or alkylamines, or by adding alkylene oxides to glycols. It is obtained by reacting a higher fatty acid with a higher fatty acid, adding an alkylene oxide to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or adding an alkylene oxide to a higher fatty acid amide.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Of these, preferred are ethylene oxide and random or block adducts of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is preferably 10 to 50 moles, and 50 to 100% by weight of the alkylene oxide is preferably ethylene oxide.

  Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol ethylene oxide addition product, lauryl alcohol ethylene oxide addition product, stearyl alcohol ethylene oxide addition product, oleyl alcohol ethylene oxide addition product). , Lauryl alcohol ethylene oxide propylene oxide block adduct, etc.); polyoxyalkylene higher fatty acid ester (eg, stearyl acid ethylene oxide adduct, lauric acid ethylene oxide adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (For example, polyethylene glycol lauric acid diester, polyethylene glycol oleic acid diester, polyethylene glycol Polyoxyalkylene alkylphenyl ether (eg, nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonylphenol ethylene oxide addition) Polyoxyalkylene alkylamino ether and (for example, laurylamine ethylene oxide adduct, stearylamine ethylene oxide adduct, etc.); polyoxyalkylene alkyl alkanolamide (for example, Hydroxyethyl lauric acid amide ethylene oxide adduct, hydroxypropyl oleic acid Ethylene oxide adducts of bromide, ethylene oxide adducts of dihydroxy ethyl lauric acid amide, etc.) and the like.

  Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts.

  Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned. Specific examples of the polyhydric alcohol fatty acid ester alkylene oxide adduct include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan mono Examples include laurate ethylene oxide adduct, sorbitan monostearate ethylene oxide adduct, sorbitan distearate ethylene oxide adduct, sorbitan dilaurate ethylene oxide propylene oxide random adduct, and the like. Specific examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like. Specific examples of polyhydric alcohol alkyl ether alkylene oxide adducts include sorbitan monostearyl ether ethylene oxide adduct, methylglycoside ethylene oxide propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, stearyl glycoside ethylene oxide propylene oxide random adduct Etc.

  Examples of the water-soluble polymer (T) include cellulosic compounds (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and saponified products thereof), gelatin, starch, dextrin, gum arabic, and chitin. , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

  The total amount of the surfactant (S) and the water-soluble polymer (T) used is generally 0 to 5% based on the weight of the polymer precursor (a) (hereinafter, unless otherwise specified,% represents% by weight). Preferably, it is 0.2 to 4%. The amount of emulsifier or dispersant used is preferably 0.01 to 5%, more preferably 0.1 to 3% based on the weight of water. If it is 0.01 to 5%, resin fine particles having a preferable average particle diameter are easily obtained. Moreover, the usage-amount of water with respect to the weight of W / O emulsion becomes like this. Preferably it is 50 to 1,000%, More preferably, it is 100 to 300%. If it is 50 to 1000%, the dispersed state tends to be good, and resin fine particles having a preferable average particle diameter are easily obtained. If necessary, the polymer precursor (a) may be heated to 40 to 60 ° C. in order to reduce the viscosity.

The solvent (U) is used for the purpose of imparting dispersion stability, and may be added to an aqueous medium as needed during emulsification dispersion. The solvent (U) needs to have a solubility in water of 1% by weight or more.
As specific examples, preferred are ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate; ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and t-butanol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, N -Heterocyclic compound type | system | group solvents, such as methylpyrrolidone, and these 2 or more types of mixed solvents are mentioned. Of these, ketone solvents are particularly preferable, and acetone and methyl ethyl ketone are more preferable.
Moreover, 0.1 to 10% is preferable with respect to the weight of a polymer precursor (a), and, as for the addition amount of a solvent (U), More preferably, it is 0.3 to 3%.

Process 2
O / W emulsion (E) and polymer precursor (b) or solution (F) solution (F) are mixed and subjected to interfacial polymerization, whereby suspension of thermally expandable microcapsules (Y) comprising polymer (X) is suspended. A turbid liquid is obtained.

The method of obtaining a polymer (X) by polymerizing a polymer precursor (a) and a polymer precursor (b) is to prepare an O / W emulsion, and then mix this with the polymer precursor (b) at the O / W interface. Polymerization, that is, a method of obtaining (X) by an interfacial polymerization method.
The solvent (N) used in the solution (F) of (b) is water; aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve Ester or ester ether solvents such as acetate; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol; dimethylformamide, dimethylacetamide An amide solvent such as dimethyl sulfoxide; a heterocyclic compound solvent such as N-methylpyrrolidone; and a mixed solvent of two or more of these. Of the above, it is preferable to use water and a mixture of water and the above.

  The O / W emulsion (E) and the polymer precursor (b) or the solution (F) (F) are mixed and subjected to interfacial polymerization.

  The polymerization can be carried out in an ordinary reaction tank, and the reaction temperature is preferably 60 ° C to 200 ° C, more preferably 100 ° C to 150 ° C, and particularly preferably 110 ° C to 130 ° C. The reaction time is preferably 3 to 25 hours, more preferably 7 to 15 hours.

Process 3
The thermally expandable microcapsule (Y) is taken out from the suspension of (Y) and dried to obtain the thermally expandable microcapsule (Y).
The method for taking out the heat-expandable microcapsule (Y) from the suspension is not particularly limited. For example, the suspension is filtered or separated using a known equipment such as a filter press, a spatula filter, a centrifuge. It is preferable to do this.
The obtained fine particles can be dried using a known facility such as a circulating dryer, a spray dryer or a fluidized bed dryer.

The hollow resin particles (Z) can be obtained by further heat-treating the heat-expandable microcapsules (Y) obtained by the above method.
By heating (Y), the solvent (C) contained in (Y) expands and hollow resin particles (Z) are obtained. The heating condition (Y) is preferably 60 to 250 ° C., more preferably 120 to 200 ° C. as the temperature. The heating time is preferably 0.1 to 3 hours, more preferably 0.3 to 1 hour.
(Y) can be heated using a known facility such as a circulating dryer, a planetary mixer, a spray dryer, or a fluidized bed dryer.

    The method for producing hollow resin particles of the present invention can be applied in a wide resin composition and particle diameter range, and can be widely used as an organic material such as a light diffusing agent and a lightweight / heat insulating filler.

As a manufacturing method of the thermally expandable microcapsule and hollow resin particle of the present invention, it is preferable to obtain by the following method from the viewpoint of safety. That is, when the solvent (C) is water and the mixture (D) is a polymer precursor (a1) in which water is dispersed, W / obtained by further dispersing the (D) in water. A thermally expandable microcapsule (Y1) composed of the polymer (X1) can be obtained by mixing and interfacial polymerization of the O / W emulsion (E1) and the polymer precursor (b1).
The hollow resin particles (Z1) can be obtained by further heating (Y1).

More specifically, the process includes the following steps.
1. Step 1 in which water is dispersed in the polymer precursor (a1) to produce a W / O emulsion.
2. Step 2 for producing a W / O / W emulsion by dispersing the W / O emulsion in water.
3. Step 3 of mixing and polymerizing the W / O / W emulsion and the polymer precursor (b) to form a suspension of resin particles (Y1) made of the polymer (X1).
4). Step 4 of taking the resin particles (Y1) from the suspension and heating to obtain hollow resin particles (Z1).
Hereinafter, each step will be described.

Process 1
The W / O emulsion that is the internal phase of the W / O / W emulsion used in the present invention is a polymer precursor (a1) in which water is dispersed, and the weight of water is (a1) from the viewpoint of the specific gravity of the hollow resin particles. It is preferably 10 to 150%, more preferably 30 to 120%, and particularly preferably 50 to 100% with respect to the weight.

  The method for obtaining the W / O emulsion serving as the internal phase is not particularly limited, and examples thereof include a method of dispersing water in the polymer precursor (a1) in the presence of the following dispersant.

  As the water dispersion method in the above method, a known disperser such as a high-speed shearing method, a friction method, a high-pressure jet method, or an ultrasonic method can be preferably used. Of these, a more preferable method is a high-speed shearing method. When a high-speed shearing disperser is used, the number of rotations is preferably 1,000 to 30,000 rpm, more preferably 2,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 5 minutes.

  Examples of the dispersant used in the preparation of the W / O emulsion include sorbitan fatty acid esters such as surfactants sorbitan monolaurate, sorbitan monooleate, sorbitan monoisostearate, sorbitan tristearate, glycerol monostearate, Examples include glycerin fatty acid esters such as glycerol monooleate, polyoxyethylene hydrogenated castor oil such as POE (5), POE (7.5), POE (10) hydrogenated castor oil, and polyether-based silicone surfactants. . Of these, sorbitan fatty acid esters are preferred.

  The amount of the dispersant is preferably 0.1 to 5% by weight based on the total amount of the W / O emulsion.

  A solvent can be used for the polymer precursor (a) as needed for the purpose of reducing the viscosity.

The solvent is used for the purpose of dissolving the resin and needs to be able to uniformly dissolve the polymer precursor (a1). The addition amount is usually 0 to 20% by weight, preferably 0.5 to 5% by weight, based on the weight of water.
Specific examples of the solvent include aromatic hydrocarbon solvents such as dodecylbenzene and naphthalene; ester or ester ether solvents such as methoxybutyl acetate, ethoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate; 2-octanol, Alcohol solvents such as furfuryl alcohol; amide solvents such as dimethylformamide and acetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and a mixture of two or more of these solvents Can be mentioned. Of these, amide solvents are preferred, and dimethylformamide is more preferred.

Process 2
The W / O / W emulsion of the present invention can be obtained by further dispersing the W / O emulsion in water.
A solvent (M) may be added to the water used in this step, and the addition amount is usually 0 to 15% by weight, preferably 0.5 to 10% by weight, based on the weight of water.

The solvent (M) is used for the purpose of imparting dispersion stability, and may be added to an aqueous medium as needed during emulsification dispersion. The solvent (M) needs to have a solubility in water of 1% by weight or more.
As specific examples, preferred are ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate; ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and t-butanol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, N -Heterocyclic compound type | system | group solvents, such as methylpyrrolidone, and these 2 or more types of mixed solvents are mentioned. Of these, ketone solvents are particularly preferable, and acetone and methyl ethyl ketone are more preferable.

  Examples of the method for obtaining the W / O / W emulsion of the present invention include a method in which the W / O emulsion is dispersed in water in the presence of the following emulsifier or dispersant.

  In the above, as the emulsifier or dispersant to be used, the surfactant (S), the water-soluble polymer (T) and the like can be used. Moreover, you may add the said solvent (U) as an auxiliary | assistant of emulsification or dispersion | distribution, and the addition amount is 0-15 weight% normally with respect to the weight of water, Preferably it is 0.5-10 weight%.

Process 3
The suspension of the thermally expandable microcapsule comprising the polymer (X1) of the present invention is obtained by polymerizing the polymer precursor (a1) and the polymer precursor (b1) in the W / O / W emulsion obtained above. It can be obtained as (X1).

  As a method of polymerizing (a1) and a polymer precursor (b1) to obtain a polymer (X1), for example, after preparing a W / O / W emulsion, this is mixed with the polymer precursor (b1) to obtain an O / W interface. And (X1) is obtained by an interfacial polymerization method.

  As the dispersion method in Step 1 and Step 2, known dispersers such as a high-speed shearing method, a friction method, a high-pressure jet method, and an ultrasonic method can be preferably used. Of these, a more preferable method is a high-speed shearing method. When a high-speed shearing disperser is used, the number of rotations is preferably 1,000 to 30,000 rpm, more preferably 2,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 5 minutes. If the rotation speed and dispersion time are within these ranges, resin fine particles having a preferable average particle diameter can be easily obtained.

Process 4
By taking out the heat-expandable microcapsules from the suspension and heating, the water contained in the heat-expandable microcapsules expands to obtain hollow resin particles (Z1).
The method for taking out the heat-expandable microcapsules from the suspension is not particularly limited. For example, the heat-expandable microcapsules (Y) can be taken out by the same method. In order to heat the obtained heat-expandable microcapsule, for example, the same method as the method of heat-treating the heat-expandable microcapsule (Y) can be performed.

  Moreover, as a manufacturing method of the thermally expansible microcapsule (Y) of this invention, the manufacturing method of the following polyamide thermally expansible microcapsules is preferable from a heat resistant viewpoint.

   As the first method for producing a polyamide thermally expandable microcapsule, the dicarboxylic acid dihalides (a2) and (a2) are dissolved, the following polyamide (X2) is not dissolved, and the boiling point is 0 ° C. or higher and 150 ° C. or lower. Dissolve diamine (b2) or (b2) and (b2) in suspension (E2) obtained by adding solvent (C2) that does not dissolve (a2) to solution (D2) consisting of solvent (C1) This is a method of obtaining a polyamide thermally expandable microcapsule (Y2) made of polyamide (X2) by mixing and reacting a solution (F2) made of solvent (J2).

As dicarboxylic acid dihalide (a2), the same thing as what was described as said dicarboxylic acid dihalide (L) is mentioned.
Of these, preferred are aromatic dicarboxylic acid dihalides, more preferred are aromatic dicarboxylic acid dichlorides, and most preferred are isophthalic acid dichloride and terephthalic acid dichloride.

The solvent (C1) dissolves the dicarboxylic acid dihalide (a2) and has a boiling point of 0 ° C. or higher and 150 ° C. or lower.
The boiling point of the solvent (C1) is 0 ° C. or higher, preferably 15 ° C. or higher, more preferably 25 ° C. or higher, 150 ° C. or lower, preferably 120 ° C. or lower, more preferably 100 ° C. or lower. If it is less than 0 ° C., it becomes difficult to encapsulate it in the microcapsule, and if it exceeds 150 ° C., the expansibility decreases.

It is necessary that the solvent (C1) does not dissolve the polyamide resin (X2) that forms the shell of the thermally expandable microcapsule (Y2).
The solvent (C1) does not dissolve the polymer (X2), and therefore phase-separates with the polyamide resin (X2) to form the center (core) in the thermally expanded microcapsule. Conversely, the polyamide resin (X2) forms a shell in the thermally expanded microcapsule.
In order to cause phase separation from the polyamide resin (X2), the absolute value of the difference obtained by subtracting the SP value of the solvent (C1) from the solubility parameter (hereinafter referred to as SP value) of the polyamide resin (X2) of the present invention is preferably 1.5 or more, more preferably 2 or more.

The SP value is calculated by the Fedors method.
The SP value can be expressed by the following equation.
SP value (δ) = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm ³ ).
ΔH and V are the sum of the heat of molar evaporation (ΔH) of the atomic group described in “POLYMER ENGINEERING AND FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153)” The total molar volume (V) can be used.
Those having a close numerical value are easy to mix with each other (high compatibility), and those having a close numerical value are indices that indicate that they are difficult to mix.

  Specific examples of the solvent (C1) include hydrocarbon (C11), halogenated hydrocarbon (C12), alcohol (C13), ether (C14), and ketone (C15) solvents. Examples of the hydrocarbon type (C11) include an aliphatic hydrocarbon type (C111), an aromatic hydrocarbon type (C112), and an alicyclic hydrocarbon type (C113). Examples of the aliphatic hydrocarbon (C111) include pentane and its isomer, hexane, its isomer, heptane and its isomer, and the like. Examples of the aromatic hydrocarbon type (C112) include benzene, toluene, xylene and the like. Examples of the alicyclic hydrocarbon (C113) include cyclohexane, cyclopentane, and methylcyclohexane. Examples of the halogenated hydrocarbon (C12) include ethyl chloride and methyl bromide. Examples of the alcohol (C13) include methanol, ethanol, butanol and the like. Examples of the ether type (C14) include diethyl ether and tetrahydrofuran. Examples of the ketone (C15) include acetone, methyl ethyl ketone, and a mixture of two or more thereof. Of these, hydrocarbon type (C11) is preferable from the viewpoint of expansion ratio, more preferably aliphatic hydrocarbon type (C111), and alicyclic hydrocarbon type (C113), and particularly preferably low temperature foaming property. From the point of view, pentane, and its isomer, hexane, and its isomer, cyclohexane.

  The content of the solvent (C1) in the solution (D1) is preferably 1 to 50% by weight, more preferably 5 to 20% by weight from the viewpoint of the expansion ratio with respect to the weight of the dicarboxylic acid dihalide (a2). .

The solution (D1) may contain a solvent (C3) as necessary in addition to the dicarboxylic acid dihalide (a2) and the solvent (C1). As the solvent (C3), it is preferable that the boiling point exceeds 150 ° C., the dicarboxylic acid dihalide (a2) is dissolved, and the mixed solvent (C1) and (C3) does not dissolve the polyamide (X2).
Specific examples include aromatic hydrocarbon solvents such as dodecylbenzene and naphthalene; ester or ester ether solvents such as methoxybutyl acetate, ethoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; 2-octanol, furfuryl alcohol, etc. Alcohol solvents; amide solvents such as dimethylformamide and acetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these. Of these, amide solvents are preferred, and dimethylformamide is more preferred.

  The content of the solvent (C3) is preferably 0 to 100% by weight, more preferably 20 to 50% by weight, from the viewpoint of the expansion ratio with respect to the weight of the solvent (C1).

  The concentration of the dicarboxylic acid dihalide (a2) in the solution (D2) is preferably 0.005 mol / liter or more, more preferably 0.01 mol / liter or more from the viewpoint of productivity, and from the viewpoint of sharpness of the particle size distribution. 1 mol / liter or less, more preferably 0.5 mol / liter or less.

  The solution (D2) and the solvent (C2) are added to obtain a suspension (E2). The solvent (C2) is not particularly limited as long as it does not dissolve the dicarboxylic acid dihalide (a2). Specific examples include water; alcohols having 1 to 12 carbon atoms, for example, monohydric alcohols having 1 to 12 carbon atoms such as methanol, ethanol, and propanol, ethylene glycol, 1,2-propanediol, and 1,3-propane. Examples include diols, dihydric alcohols having 2 to 7 carbon atoms such as 1,5-pentanediol, 3- to 6-valent alcohols having 3 to 8 carbon atoms such as 1,2,3-propanetriol, and mixtures thereof. . Of the above, it is preferable to use water and a mixture of water and the above.

  Selected from the group consisting of the dicarboxylic acid dihalide (a2), solvent (C1), solution (D2), solvent (C2), suspension (E2), diamine (b2), solvent (J2) and solution (F2). At least one of the above-mentioned basic salts is preferably dissolved or dispersed for the purpose of reaction removal of hydrochloric acid by-produced by amidation. By removing hydrochloric acid by reaction, the molecular weight can be increased, so that the expansion performance is improved and the specific gravity can be further reduced. In particular, it is preferable that the basic salt is dissolved or dispersed in (C2). The amount of the basic salt used is preferably 50 to 300% by weight, more preferably 100 to 250% by weight, based on the weight of the dicarboxylic acid dihalide (a2).

  Examples of basic salts include carbonates, phosphates, acetates and the like. Examples of the carbonate include calcium carbonate, sodium carbonate, magnesium carbonate, barium carbonate, and aluminum carbonate. Examples of the phosphate include sodium phosphate, sodium phosphite, sodium hypophosphite, sodium pyrophosphate and the like. Examples of acetate include sodium acetate and potassium acetate. Of these, carbonates are preferable from the viewpoint of economy, and calcium carbonate is particularly preferable.

  The content of the solution (D2) in the suspension (E2) is preferably 10 to 60% by weight, and more preferably 20 to 50% by weight from the viewpoint of productivity.

  The mixing of the solution (D2) and the solvent (C2) is preferably performed by adding the solution (D2) to the suspension while stirring the solvent (C2). Stirring can be carried out by a known stirring method (stirring device). In the present invention, stirring by mechanical shearing or ultrasonic waves is particularly preferable.

  The apparatus for giving mechanical shear is not particularly limited as long as it is generally marketed as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (special machine) Batch type emulsifiers such as Ebara Milder (manufactured by Aihara Seisakusho Co., Ltd.), TK Philmix, TK Pipeline Homomixer (made by Tokushu Kika Kogyo Co., Ltd.), colloid mill (made by Shinko Pantech), Continuous emulsifiers such as slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Captron (manufactured by Eurotech), fine flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), microfluidizer (manufactured by Mizuho Industrial Co., Ltd.), High pressure emulsifiers such as Nanomizer (made by Nanomizer), APV Gaurin (made by Gaurin), membrane emulsifier (made by Chilling Industries Co., Ltd.), etc. Membrane emulsification machine, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size. Further, the rotation speed is preferably 1000 to 25000 rpm, and more preferably 2000 to 10,000 rpm.

  For stirring by ultrasonic waves, a known ultrasonic device (for example, an ultrasonic cleaner) and operating conditions can be used as they are. What is necessary is just to set the frequency of an ultrasonic wave suitably according to a desired volume average particle diameter etc., Preferably it is 28-1000 kHz, More preferably, it is 28-100 kHz, Especially preferably, it is 28-45 kHz.

  The temperature during mixing of the solution (D2) and the solvent (C2) is preferably 0 to 60 ° C., more preferably 0 to 40 ° C. from the viewpoint of dispersion stability.

  In the following description, the solution (F2) is described as being composed of the diamine (b2) or the diamine (b2) dissolved in the solvent (J2).

Examples of the diamine (b2) include aromatic diamines, aliphatic diamines, and alicyclic diamines, and mixtures of two or more of these.
As aromatic diamines, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 1 , 4′-bis (4-aminophenoxy) benzene, 1,3′-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis (2- Chloroaniline), 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminodi Phenyl sulfide, 2,6′-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4 '-Diaminobenzophenone, 4,4'-diaminobibenzyl, R (+)-2,2'-diamino-1,1'-binaphthalene, S (+)-2,2'-diamino-1,1'- 1, n-bis (4- (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, etc. Aminophenoxy) alkane (n is 3 to 10), 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminopheny) ) Fluorene, 4,4'-diaminobenzanilide, and the like.
Aliphatic diamines include 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, and 1,10-diaminododecane. 1,11-diaminoundecane and the like.
Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4,4′-diaminodicyclohexylmethane, and the like. Of these, aromatic diamines are preferable, and 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, and 3,3′-diaminodiphenyl sulfone are more preferable.
Preferable are aromatic diamines, and 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 4,4′-bis (4-aminophenoxy) biphenyl are more preferable.

  The solvent (J2) is not particularly limited as long as it dissolves the diamine (b2). Specific examples include water; aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; methanol, Alcohol solvents such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide And heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these. Of the above, it is preferable to use water and a mixture of water and the above.

  The concentration of the diamine (b2) in the solution (F2) may be appropriately set according to the type of the diamine compound used, the concentration of the dicarboxylic acid dihalide (a2) in the solution (D2), etc. Is 10% by weight or more, more preferably 20% by weight or more, preferably 100% by weight or less, more preferably 80% by weight or less from the viewpoint of dispersion stability.

  The suspension (E2) and the solution (F2) are preferably mixed by adding the solution (F2) while stirring the suspension (E2). The stirring time is preferably about 30 seconds to 30 minutes.

  The temperature at the time of mixing the suspension (E2) and the solution (F2) is preferably 0 to 80 ° C., more preferably 25 to 45 ° C. from the viewpoint of dispersion stability.

After mixing and reacting the above (E2) and (F2), it is preferable to further raise the reaction temperature and perform the aging step. The reaction temperature in the aging step is preferably 60 ° C to 200 ° C, more preferably 100 ° C to 150 ° C, and particularly preferably 110 ° C to 130 ° C. The reaction time of the aging step is preferably 3 to 25 hours, more preferably 7 to 15 hours. It can be presumed that the polyamide has been made high in molecular weight by performing the aging step, which is preferable in that the expansion performance is improved and the specific gravity can be further reduced.
In addition, since the obtained polyamide has no solvent to dissolve, it is difficult to measure the molecular weight.

The dispersion obtained above is filtered or separated using a known equipment such as a filter press, a spatula filter, a centrifuge, etc., and the resulting fine particles are dried, so that the thermal expansibility comprising polyamide (X2) is obtained. Microcapsules (Y2) are obtained.
The obtained fine particles can be dried using a known facility such as a circulating dryer, a spray dryer or a fluidized bed dryer.

  The volume average particle diameter of the thermally expanded microcapsules obtained by the above production method is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 100 μm or less, more preferably 80 μm, from the viewpoint of foamability. It is as follows.

  The volume average particle diameter may be measured by a light scattering method. For example, it can be carried out with a laser scattering particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) using toluene as a solvent.

  The particle shape of the thermally expandable microcapsule (Y2) of the present invention may be indefinite or spherical, but preferably contains 50% or more of spherical particles from the viewpoint of fluidity at room temperature. . Here, the term “spherical” refers to particles having a major axis / minor axis ratio in the range of 1.0 to 1.5.

   As a second method for producing a polyamide thermally expandable microcapsule, a solvent which dissolves dicarboxylic acid dihalides (a2) and (a2) and does not dissolve the following polyamide (X3) has a boiling point of 0 ° C. or higher and 150 ° C. or lower. The solution (D3) comprising (C1) is mixed with a solution (F3) comprising a solvent (J3) in which diamines (b2) and (b2) are dissolved and (a2) is not dissolved, thereby reacting with polyamide (X3 Is a method for obtaining a thermally expandable microcapsule (Y3).

  The solution (D3) can be obtained in exactly the same manner as the solution (D2).

  The solution (F3) is obtained by dissolving the diamine (b2) in the solvent (J3). As the diamine (b2) and the solvent (J3), those exemplified above can be used.

  The solvent (J3) is not particularly limited as long as it dissolves diamine (b2) and does not dissolve (a2). Specific examples include water; ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide And solvents based on heterocyclic compounds such as N-methylpyrrolidone, and mixed solvents of two or more of these. Of the above, it is preferable to use water.

  At least one selected from the group consisting of the dicarboxylic acid dihalide (a2), solvent (C1), solution (D3), diamine (b2), solvent (J3) and solution (F3) was by-produced by amidation. It is preferable that a basic salt is dissolved or dispersed for the purpose of reaction removal of hydrochloric acid. By removing hydrochloric acid by reaction, the molecular weight can be increased, so that the expansion performance is improved and the specific gravity can be further reduced. In particular, it is preferable that the basic salt is dissolved or dispersed in (C4). The amount of the basic salt used is preferably 50 to 300% by weight, more preferably 100 to 250% by weight, based on the weight of the dicarboxylic acid dihalide (a2).

  Examples of the basic salt include those exemplified above, and carbonates are preferable from the viewpoint of economy, and calcium carbonate is more preferable.

  The concentration of the diamine (b2) in the solution (F3) may be appropriately set according to the kind of the diamine compound used, the concentration of the dicarboxylic acid dihalide (a2) in the solution (D3), etc. Is 5% by weight or more, more preferably 10% by weight or more, preferably 50% by weight or less, more preferably 30% by weight or less from the viewpoint of dispersion stability.

  The mixing of the solution (D3) and the solution (F3) is preferably carried out by adding the solution (F3) while stirring the solution (D3). Stirring can be carried out by a known stirring method (stirring device). In the present invention, stirring by mechanical shearing or ultrasonic waves is particularly preferable.

  The mechanical shearing or ultrasonic stirring method can be performed using the apparatus and conditions described above.

From the viewpoint of dispersion stability, the temperature during mixing of the solution (D3) and the solution (F3) is preferably 0 to 80 ° C, more preferably 25 to 65 ° C, and particularly preferably 40 ° C to 60 ° C.
The mixing time is preferably 10 seconds to 5 minutes from the viewpoint of dispersion stability, and more preferably 35 seconds to 3 minutes.

After mixing (D3) and (F3) and reacting, it is preferable to further raise the reaction temperature and perform the aging step. The reaction temperature in the aging step is preferably from 60 ° C to 200 ° C, more preferably from 100 ° C to 150 ° C, particularly preferably from 110 ° C to 130 ° C. The reaction time of the aging step is preferably 3 to 25 hours, more preferably 7 to 15 hours. It can be presumed that the polyamide has been made high in molecular weight by performing the aging step, which is preferable in that the expansion performance is improved and the specific gravity can be further reduced.
In addition, since the obtained polyamide has no solvent to dissolve, it is difficult to measure the molecular weight.

  The obtained thermally expandable macrocapsule (Y3) dispersion is subjected to the separation and drying described above to obtain a polyamide (X3) thermally expandable microcapsule (Y3). As for the volume average particle diameter, the coefficient of variation of the volume average particle diameter, and the particle shape of the thermally expandable microcapsule (Y3), the same ones as described above are preferable.

  The hollow resin particles (Z2) and (Z3) can be obtained by heat-treating the heat-expandable microcapsules (Y2) and (Y3) obtained above using, for example, an air circulation dryer. The heating conditions for (Y2) and (Y3) are the same as those for heating (Y) to obtain (Z).

True specific gravity of the hollow resin particles of the present invention (Z) is preferably from the viewpoint of friable and at 0.01 g / cm ³ or more, more preferably 0.05 g / cm ³ or more, particularly preferably 0.1 g / cm ³ or more. Further, from the viewpoint of a hollow function such as heat insulation, it is preferably 0.8 g / cm ³ or less, more preferably 0.4 g / cm ³ or less, and particularly preferably 0.3 g / cm ³ or less. The true specific gravity can be measured by, for example, the Le Chatelier specific gravity bottle method (JISR5201).

  The volume average particle size of the hollow resin particles (Z) of the present invention is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more from the viewpoint of application to a coating film. Further, it is preferably 150 μm or less, more preferably 70 μm or less, and particularly preferably 10 μm or less.

  The particle shape of the hollow resin particles (Z) of the present invention may be indefinite or spherical, but preferably contains 50% or more of spherical particles from the viewpoint of powder flowability at room temperature. . Here, the term “spherical” refers to particles having a major axis / minor axis ratio in the range of 1.0 to 1.5.

    The hollow resin particles (Z) of the present invention have better heat resistance of the polymer (X) that forms a shell than conventional ones.

Examples of the heat resistance index of the hollow resin particles (Z) include 5% thermal weight loss temperature (° C.) defined by the following formula. The 5% thermal weight loss temperature (° C.) is preferably 250 to 600, more preferably 270 to 550, and particularly preferably 300 to 500. Within this range, the mechanical strength of the hollow resin particles at a high temperature is further improved.
The 5% thermal weight loss temperature means that when 10 ± 3 mg of a sample is heated to 400 ° C. at a temperature increase rate of 5 ± 0.5 ° C./min under a nitrogen stream (gas flow rate: 10 ml / min). Based on the weight (w) of the sample before the test when reaching 150 ° C., the temperature when the weight decreases by 5% by weight {temperature when the weight of the sample becomes (w) × 0.95} means.
The 5% thermogravimetric temperature reduction temperature is measured in accordance with JIS K 7120-1987 “Method for Measuring Thermogravimetry of Plastics”. Here, the amount of the sample, the type of inflowing gas, the gas flow rate, and the heating rate are as described above. In addition, as a pretreatment of the sample, about 30 mg of the hollow resin particles were heated to 180 ° C. for 1 hour in a temperature control chamber with a humidity of 70% and a temperature of 25 ° C. using a smooth air dryer, and then the temperature control chamber. And cooled to 25 ° C.

Examples Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. In the following, parts and% indicate parts by weight and% by weight, respectively.

Glass transition temperature (hereinafter abbreviated as Tg), volume average particle diameter, storage elastic modulus, molecular weight between crosslinks and true specific gravity were measured by the following methods.
<Tg> The Tg of the polymer (X) is measured using a differential scanning calorimeter UV-DSC220C (manufactured by Seiko Co., Ltd.) after heat treatment at 180 ° C. for 10 hours and completely evaporating the solvent. It was.
<Volume Average Particle Size> The volume average particle size was measured with a laser scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) using toluene as a solvent.
<True specific gravity> The true specific gravity was measured using the Le Chatelier specific gravity bottle method (JISR5201).
<5% thermal weight loss temperature> The 5% thermal weight loss temperature was measured in accordance with JIS K7120-1987 "Method for measuring thermogravimetricity of plastics". In addition, as a pretreatment of the sample, about 30 mg of the hollow resin particles were heated to 180 ° C. for 1 hour in a temperature control chamber with a humidity of 70% and a temperature of 25 ° C. using a smooth air dryer, and then the temperature control chamber. And cooled to 25 ° C.

Example 1 <Production of polyamide thermally expandable microcapsule “Y-1”>
A solution obtained by adding 100 parts of terephthalic acid chloride and 5 parts of sorbitan tristearate was mixed with 20 parts of pentane, and the mixture was stirred using a homomixer at 4000 rpm × 1 minute to disperse the water. And 10 parts of emulsifier (Calibon B (Sanyo Chemicals: sodium acrylate-acrylic acid ester copolymer)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. To this dispersion, 80 parts of hexamethylenediamine is added, and the temperature is raised to 80 ° C. and reacted for 10 hours. After completion of the reaction, the obtained polyamide thermally expandable microcapsules (Y-1) were taken out of the water by filtration with a filter paper and dried for 1 hour in a circulating air dryer at 40 ° C. (Volume average particle size 2.7 μm)

Example 2 <Production of Epoxy Thermally Expandable Microcapsule “Y-2”>
20 parts of hexane was mixed with a solution obtained by adding 47 parts of sorbitan tristearate and 232 parts of bisphenol A diglycidyl ether (Epicoat 828, Yuka Shell Co., Ltd.) and dissolved, and using a homomixer at 4000 rpm × 1 minute. Stir to disperse water and make this oil phase. 10 parts of emulsifier (Caribbon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. This was heated to raise the system temperature to 70 ° C., and then a solution prepared by dissolving 20 parts of ethylenediamine in 446 parts of water was added dropwise over 2 hours while maintaining 70 ° C. After dropping, the reaction and aging were carried out at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain an aqueous epoxy resin dispersion. After completion of the reaction, the obtained epoxy thermally expandable microcapsule (Y-2) was taken out of the water by filtration with a filter paper and dried for 1 hour in a circulating air dryer at 40 ° C. (Volume average particle size 1.5 μm)

Example 3 <Production of polyurethane heat-expandable microcapsule “Y-3”>
After adding 650 parts of polypropylene glycol (number average molecular weight 2,000, acid value 0.2) and 142 parts of IPDI, the reaction was carried out at 120 ° C. for 5 hours (isocyanate group content 3.2%), and then to room temperature. Cooled to obtain a polymer precursor. 200 parts of water was mixed with a solution obtained by adding 400 parts of the obtained polymer precursor and 47 parts of sorbitan tristearate, and the mixture was stirred using a homomixer at 4000 rpm × 1 minute to disperse the water. Is the oil phase. 10 parts of emulsifier (Caribbon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. A solution prepared by dissolving 50 parts of ethylenediamine and 5 parts of diethylenetriamine in 446 parts of water was added dropwise thereto over 2 hours. After dripping, it reacted at 70 ° C. for 5 hours to obtain an aqueous polyurethane resin dispersion. After completion of the reaction, the obtained polyurethane thermally expandable microcapsules (Y-3) were taken out of the water by filtration with filter paper and dried for 1 hour in a circulating air dryer at 40 ° C. (Volume average particle size 1.9 μm)

Example 4 <Manufacture of polyamide hollow resin particle “Z-4”>
100 parts of water was mixed with a solution obtained by adding 100 parts of terephthalic acid chloride and 5 parts of sorbitan tristearate, and the mixture was stirred using a homomixer at 4000 rpm × 1 minute to disperse the water. And 10 parts of emulsifier (Caribbon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. To this dispersion, 80 parts of hexamethylenediamine is added and reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried for 10 hours in an air circulation dryer at 80 ° C. The spherical body was crushed by a sonic classifier and sieved to obtain 180 parts of polyamide hollow resin particles (Z-4) (volume average particle diameter 3.6 μm, polymer Tg: 119.6 ° C., true specific gravity: 0.31, 5% thermal weight loss temperature: 319.2 ° C.).

Example 5 <Manufacture of epoxy hollow resin particle “Z-5”>
100 parts of water was mixed in a solution obtained by adding 47 parts of sorbitan tristearate and 232 parts of bisphenol A diglycidyl ether (Epicoat 828, Yuka Shell Co., Ltd.) and dissolved, and using a homomixer at 4000 rpm × 1 minute. Stir to disperse water and make this oil phase. 10 parts of emulsifier (Caribbon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. This was heated to raise the temperature in the system to 70 ° C., and then a solution prepared by dissolving 20 parts of ethylenediamine in 446 parts of water was added dropwise over 2 hours while maintaining 70 ° C. After dropping, the reaction and aging were carried out at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain an aqueous epoxy resin dispersion. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried for 10 hours in an air circulation dryer at 80 ° C. The spherical body was crushed by a sonic classifier and sieved to obtain 240 parts of an epoxy hollow resin particle (Z-2) (volume average particle size 1.9 μm, polymer Tg: 135.9 ° C., true specific gravity: 0.34, 5%, thermal weight loss temperature: 312.2 ° C.).

Example 6; <Production of polyamide thermally expandable microcapsule “Y-6”>
20 parts of pentane (solvent (C1-6): boiling point 36 ° C.), 40 parts of isophthalic acid chloride and 60 parts of MEK are added and dissolved to prepare a solution (D1-6). A solution (F1-6) is prepared by dissolving 30 parts of 4,4′-diaminodiphenylmethane in 100 parts of ion-exchanged water. A solution (C2-6) is prepared by dissolving 5 parts of polyvinyl alcohol in 100 parts of ion-exchanged water. The solution (D1-6) and the solution (C2-6) are mixed and dispersed using a homomixer under the condition of 4000 rpm × 1 minute. The volume average particle diameter of the oil droplets was 20 μm. A solution (F1-6) is added to this dispersion at 60 ° C. and allowed to react for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain 80 parts of polyamide (X-6) thermally expandable microcapsules (Y-6) (volume average particle diameter 24.5 μm).

Example 7 <Manufacture of polyamide thermally expandable microcapsule “Y-7”>
Pentane 20 parts (solvent (C1-7): boiling point 36 ° C.), isophthalic acid chloride 40 parts, and MEK 60 parts are added and dissolved to prepare a solution (D1-7). In 100 parts of ion exchange water, 30 parts of 4,4′-diaminodiphenylmethane and 5 parts of polyvinyl alcohol are dissolved to prepare a solution (F1-7). The solution (D1-7) and the solution (F1-7) are mixed and dispersed using a homomixer under the condition of 4000 rpm × 1 minute. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain 80 parts of polyamide (X-7) thermally expandable microcapsules (Y-7) (volume average particle diameter 28.2 μm).

Example 8; <Production of polyamide thermally expandable microcapsule “Y-8”>
20 parts of n-hexane (solvent (C1-8): boiling point 69 ° C.), 40 parts of terephthalic acid dichloride and 60 parts of MEK are added and dissolved to prepare a solution (D1-8). A solution (F1-8) is prepared by dissolving 30 parts of 4,4'-diaminodiphenyl ether in 100 parts of ion-exchanged water. A solution (C2-8) is prepared by dissolving 5 parts of polyvinyl alcohol in 100 parts of ion-exchanged water. The solution (D1-8) and the solution (C2-8) are mixed and dispersed under the condition of 40 kHz using ultrasonic waves. The volume average particle diameter of the oil droplets was 20 μm. The solution (F1-8) is added to this dispersion under stirring at 60 ° C. over 1 minute, and the temperature is raised to 80 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was pulverized with a sonic classifier and sieved to obtain 80 parts of polyamide (D-3) thermally expandable microcapsules (Y-8) (volume average particle diameter 25.4 μm).

Example 9 <Production of polyamide thermal expansion microcapsule “Y-9”>
20 parts of n-hexane (solvent (C1-9): boiling point 69 ° C.), 40 parts of terephthalic acid dichloride and 60 parts of MEK are added and dissolved to prepare a solution (D1-9). A solution (F1-8) is prepared by dissolving 30 parts of 4,4′-diaminodiphenyl ether and 5 parts of polyvinyl alcohol in 100 parts of ion-exchanged water. The solution (D1-9) and the solution (F1-9) are mixed at 60 ° C. and dispersed using ultrasonic waves for 1 minute under the condition of 40 kHz. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain 80 parts of polyamide (X-9) thermally expandable microcapsules (Y-9) (volume average particle diameter 25.1 μm).

Example 10 <Production of polyamide thermally expandable microcapsule “Y-10”>
Pentane 20 parts (solvent (C1-10): boiling point 36 ° C.), isophthalic acid chloride 40 parts, and MEK 60 parts are added and dissolved to prepare a solution (D1-10). A solution (F1-10) is prepared by dissolving 30 parts of 4,4′-diaminodiphenylmethane in 100 parts of ion-exchanged water. A solution (C2-10) is prepared by dissolving 5 parts of polyvinyl alcohol in 100 parts of ion-exchanged water and further dispersing 5 parts of heavy calcium carbonate (Escalon 2000: Sankyo Flour Mills Co., Ltd.). The solution (D1-10) and the solution (C2-10) are mixed and dispersed using a homomixer under the condition of 4000 rpm × 1 minute. The volume average particle diameter of the oil droplets was 20 μm. A solution (F1-10) is added to this dispersion at 60 ° C., and the mixture is further reacted at 140 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain 82 parts of a polyamide (X-10) thermally expandable microcapsule (Y-10) (volume average particle diameter 25.1 μm).

Example 11 <Production of polyamide thermally expandable microcapsule “Y-11”>
Pentane 20 parts (solvent (C1-11): boiling point 36 ° C.), isophthalic acid chloride 40 parts, and MEK 60 parts are added and dissolved to prepare a solution (D2-11). A solution (F2-) in which 30 parts of 4,4′-diaminodiphenylmethane and 5 parts of polyvinyl alcohol are dissolved in 100 parts of ion-exchanged water, and 5 parts of heavy calcium carbonate (Escalon 2000: manufactured by Sankyo Flour Milling Co., Ltd.) are further dispersed. 11) is created. The solution (D2-11) and the solution (F2-11) are mixed at 80 ° C. and dispersed using a homomixer under the condition of 4000 rpm × 1 minute. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 140 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain 83 parts of a polyamide (X-11) thermally expandable microcapsule (Y-11) (volume average particle diameter 25.5 μm).

Examples 12 to 20; <Production of hollow resin particles (Z-1 to 3 and Z-6 to 11)>
100 g of the heat-expandable microcapsules (Y-1 to 3 and Y-6 to 11) obtained above are spread on a release paper to an area of about 100 cm ³ and heat-treated in a circulating dryer at 180 ° C. for 15 minutes. Thus, hollow resin fine particles (Z-1 to 3 and Z-6 to 11) were obtained.
Properties of (Z-1) (volume average particle diameter 3.7 μm, polymer Tg: 123.6 ° C., true specific gravity: 0.07, 5% thermal weight loss temperature: 314.2 ° C.)
Properties of (Z-2) (volume average particle diameter 2.1 μm, polymer Tg: 135.9 ° C., true specific gravity: 0.09, 5% thermal weight loss temperature: 309.2 ° C.)
Properties of (Z-3) (Volume Average Particle Size 3.2 μm, Polymer Tg: 105.9 ° C., True Specific Gravity: 0.31, 5% Thermal Weight Loss Temperature: 309.5 ° C.)
Properties of (Z-6) (volume average particle diameter: 59.4 μm, true specific gravity: 0.17, 5% thermal weight loss temperature: 324.2 ° C.),
Properties of (Z-7) (volume average particle diameter: 53.4 μm, true specific gravity: 0.15, 5% thermal weight loss temperature: 319.5 ° C.),
Properties of (Z-8) (volume average particle diameter: 59.4 μm, true specific gravity: 0.17, 5% thermal weight loss temperature: 308.6 ° C.),
Properties of (Z-9) (volume average particle diameter: 61.3 μm, true specific gravity: 0.11, 5% thermal weight loss temperature: 312.4 ° C.),
Properties of (Z-10) (volume average particle diameter: 66.9 μm, true specific gravity: 0.09, 5% thermal weight loss temperature: 309.9 ° C.),
Properties of (Z-11) (volume average particle diameter: 69.4 μm, true specific gravity: 0.07, 5% thermal weight loss temperature: 303.2 ° C.)

Comparative Example 1 <Production of polyamide thermal expansion microcapsule “Y′-1”>
100 parts of pentane, 100 parts of isophthalic acid chloride, 80 parts of hexamethylenediamine, 15 parts of diethylenetriamine and 120 parts of MEK are added and dissolved to obtain an oil phase. 10 parts of emulsifier (Caribbon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filter paper filtration and dried with a circulating dryer at 40 ° C. The spherical body was pulverized with a sonic classifier and sieved to obtain 280 parts of thermally expandable microcapsules (Y′-1) (volume average particle diameter 24.7 μm).

Comparative Example 2; <Production of polyamide thermal expansion microcapsule “Y′-2”>
100 parts of pentane, 100 parts of terephthalic acid chloride, 100 parts of metaxylenediamine and 120 parts of MEK are added and dissolved to obtain an oil phase. 10 parts of an emulsifier (Calibon B (manufactured by Sanyo Chemical Industries)) is dissolved in 800 parts of ion-exchanged water to obtain an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained resin was taken out of the water by filter paper filtration and dried by a circulating air dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain thermally expandable microcapsules (Y′-2) (volume average particle diameter 26.1 μm).

Comparative Example 3 <Production of polyurethane heat-expandable microcapsule “Y′-3”>
1,000 parts of toluene is added to 650 parts of polyethylene terephthalate (number average molecular weight 2,000, acid value 0.2), 142 parts of IPDI is added, and the mixture is reacted at 120 ° C. for 5 hours under toluene reflux. (Isocyanate group content: 3.2%), cooled to room temperature, added 25 parts of hexamethylenediamine and 20 parts of diethylenetriamine, and reacted at 60 ° C. for 5 hours. Distilling off, a polyurethane resin having hydroxyl groups at both ends and having urethane and urea bonds was obtained. 400 parts of the obtained resin, 12 parts of yellow iron oxide, 62 parts of n-hexane and 380 parts of ethyl acetate were mixed and dispersed while being dropped into 2000 parts of a 0.5% aqueous polyvinyl alcohol solution prepared in advance. The obtained resin was taken out of the water by filter paper filtration and dried by a circulating air dryer at 40 ° C. The spherical body was pulverized with a sonic classifier and sieved to obtain thermally expandable microcapsules (Y′-3) (volume average particle diameter 28.5 μm).

Comparative Example 4 <Production of polyester thermal expansion microcapsule “Y′-4”>
To 450 parts of bisphenol A ethylene oxide (EO) 2 mol adduct (BPE-20T manufactured by Sanyo Kasei Kogyo Co., Ltd.), 242 parts of terephthalic acid and 28 parts of trimellitic anhydride are added, and 3 parts of dibutyltin oxide is added as a catalyst. The reaction was carried out at 230 ° C. for 10 hours (acid value 0.5, number average molecular weight 5000). This was taken out into a vat at 150 ° C. and cooled to room temperature to obtain a polyester resin. 400 parts of the obtained resin, 62 parts of n-hexane (solvent (B-4): boiling point 69 ° C.), and 380 parts of ethyl acetate are mixed to form an oil phase. 20 parts of emulsifier (Calibon B (manufactured by Sanyo Chemical Industries)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. While the aqueous phase was stirred at 8,000 rpm with a TK homomixer, the oil phase was added and stirred for 3 minutes. Next, this mixed liquid was transferred to a reaction vessel equipped with a stir bar and a thermometer, and the temperature was raised to distill off ethyl acetate. The resulting resin dispersion was removed from the water by filtration with a filter paper, and a circulating dryer at 40 ° C. Dried. The spherical body was pulverized with a sonic classifier and sieved to obtain thermally expandable microcapsules (Y′-4) (volume average particle diameter 23.5 μm).

Comparative Example 5; <Production of Epoxy Resin Thermally Expandable Microcapsule “Y′-5”>
In a reaction vessel equipped with a stir bar and a thermometer, 47 parts of a styrenated phenol polyethylene oxide adduct (Eleminol HB-12, Sanyo Chemical Industries) and bisphenol A diglycidyl ether (Epicoat 828, Yuka Shell) 232 Then, 38 parts of 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and 23 parts of n-hexane were added and dissolved uniformly. Water was added dropwise to the reaction vessel with stirring. When 38 parts of water was added, the system emulsified milky white. Further, 224 parts of water was added dropwise to obtain an emulsion. This was heated to raise the system temperature to 70 ° C., and then reacted and aged at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain an aqueous epoxy resin dispersion. Subsequently, the obtained resin dispersion was taken out of the water by filter paper filtration and dried by a circulating air dryer at 40 ° C. The spherical body was crushed with a sonic classifier and sieved to obtain thermally expandable microcapsules (Y′-5) (volume average particle diameter 18.5 μm).

Comparative Examples 6 to 10; <Production of Hollow Resin Particles (Z′-1 to Z′-5)>
100 g of the heat-expandable microcapsules (Y′-1 to Y′-5) obtained above were spread on a release paper to an area of about 100 cm ³ 1 and heated for 0.4 hours with a circulating dryer at 180 ° C. As a result, hollow resin fine particles (Z′-1 to Z′-5) were obtained.
Properties of (Z′-1) (volume average particle diameter: 64.5 μm, true specific gravity: 0.05, 5% thermal weight loss temperature: 299.2 ° C.),
Properties of (Z′-2) (volume average particle diameter: 77.2 μm, true specific gravity: 0.04, 5% thermal weight loss temperature: 295.6 ° C.),
Properties of (Z′-3) (volume average particle diameter: 62.5 μm, true specific gravity: 0.07, 5% thermal weight loss temperature: 259.5 ° C.),
Properties of (Z′-4) (volume average particle diameter: 58.5 μm, true specific gravity: 0.15, 5% thermal weight loss temperature: 243.2 ° C.),
Properties of (Z′-5) (volume average particle diameter: 51.5 μm, true specific gravity: 0.13, 5% thermal weight loss temperature: 297.1.2 ° C.)

The thermally expandable microcapsules and hollow resin particles obtained by the production method of the present invention can be widely used as an organic material such as a light diffusing agent or a light weight / heat insulating filler. It is particularly useful in fields where high heat resistance is required, for example, for lightening materials for engineering plastics used in automobiles, heat insulating materials for fixing rolls of printers, and the like.

Claims (14)

  An O / W emulsion (E) obtained by dispersing a mixture (D) containing a polymer precursor (a) and a solvent (C) in water, and a solution (F) of the polymer precursor (b) or (b) ) And interfacial polymerization, and a method for producing a thermally expandable microcapsule (Y) comprising polymer (X).   The production method according to claim 1, wherein the polymer (X) is at least one selected from the group consisting of a polyurethane resin, an epoxy resin, and a polyamide resin.   The process according to claim 1 or 2, wherein the solvent (C) does not dissolve the polymer (X) and has a boiling point of 0 ° C or higher and 150 ° C or lower.   A polymer characterized by mixing and interfacially polymerizing a W / O / W emulsion (E1) obtained by further dispersing a water-dispersed polymer precursor (a1) in water and the polymer precursor (b1). The manufacturing method according to claim 1, comprising (X1).   A solution (D2) comprising a solvent (C1) in which the dicarboxylic acid dihalides (a2) and (a2) are dissolved and the following polyamide (X2) is not dissolved and the boiling point is 0 ° C. or higher and 150 ° C. or lower is added to (A2) The suspension (E2) obtained by adding the solvent (C2) that does not dissolve the diamine is mixed with the diamine (b2) or the solution (F2) composed of the solvent (J2) that dissolves (b2) and (b2). The production method according to any one of claims 1 to 3, comprising a polyamide (X2) which is reacted.   Selected from the group consisting of the dicarboxylic acid dihalide (a2), solvent (C1), solution (D2), solvent (C2), suspension (E2), diamine (b2), solvent (J2) and solution (F2). The production method according to claim 5, wherein at least one kind contains a basic salt.   The suspension (E2) and the diamine (b2) or the solution (F2) are mixed at a temperature of 0 to 80 ° C and further mixed at a temperature of 60 to 200 ° C. The manufacturing method as described.   A solution (D3) comprising a solvent (C1) in which the dicarboxylic acid dihalides (a2) and (a2) are dissolved and the following polyamide (X3) is not dissolved and the boiling point is 0 ° C. or higher and 150 ° C. or lower is added to the diamine (b2 And (b2) and a solution (F3) comprising a solvent (J3) that does not dissolve (a2) is mixed and reacted to form a polyamide (X3). Manufacturing method.   Claim that at least one selected from the group consisting of the dicarboxylic acid dihalide (a2), the solvent (C1), the solution (D3), the diamine (b2), the solvent (J3) and the solution (F3) contains a basic salt. Item 9. The manufacturing method according to Item 8.   The solution (D3) and the diamine (b2) or the solution (F3) are mixed at a temperature of 0 to 80 ° C, and further mixed at a temperature of 60 to 200 ° C. Production method.   A method for producing hollow resin particles (Z), wherein the heat-expandable microcapsules (Y) obtained by the production method according to claim 1 are further heat-treated.   The hollow resin particles obtained by the production method according to claim 11, wherein the volume average particle diameter is from 0.5 μm to 150 μm.   The hollow resin particles obtained by the production method according to claim 11, wherein the true specific gravity is 0.01 or more and 0.8 or less. The hollow resin particles obtained by the production method according to claim 11, wherein the 5% thermal weight loss temperature is 250 ° C. or more and 600 ° C. or less.