JP2005213379A - Thermally expandable microcapsule - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermally expandable microcapsule high in expansion ratio and heat resistance. <P>SOLUTION: The thermally expandable microcapsule is such that a volatile liquid and/or sublimable solid is included in a polymer shell consisting of a polymer made from (I) a cyano group-containing monomer, (II) a vinyl monomer having a functional group(F1) blocked by a blocking agent and/or a functional group(F1)-bearing crosslinking agent, and (III) a vinyl monomer having a functional group(F2) reactive with the functional group(F1) and/or a functional group(F2)-bearing crosslinking agent, and composed of the monomers I, II and/or III as the essential constituent units. In this microcapsule, it is preferable that the functional group F2 be a hydroxy, amino, carboxy or epoxy group when the functional group F1 is a blocked isocyanato group, be a hydroxy or amino group when the functional group F1 is a blocked carboxy group, or be an isocyanato or epoxy group when the functional group F1 is a blocked hydroxy, blocked amino or blocked carboxy group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a thermally expandable microcapsule.

Expandable inside the polymer shell containing acrylonitrile (1), a carboxy group-containing vinyl monomer (2) and a vinyl monomer (3) containing a group (epoxy group, amino group, hydroxyl group, etc.) that reacts with the carboxy group. Thermally expandable microcapsules designed to contain a solid or liquid and to form a crosslinked structure in a polymer shell when heated and expanded to improve the heat resistance of hollow resin particles are known (Patent Literature) 1).
International Publication W099 / 43758 Pamphlet

Conventional heat-expandable microcapsules do not expand sufficiently (expansion ratio of the expansion ratio) because a crosslinked structure is formed even before heat expansion {formation of polymer shell (polymerization), storage of heat-expandable microcapsules, etc.}. There is a problem of reduction. That is, an object of the present invention is to provide a thermally expandable microcapsule excellent in expansion magnification and heat resistance.

The thermally expandable microcapsule of the present invention is characterized by a cyano group-containing vinyl monomer (I),
A vinyl monomer (II) having a functional group (F1) blocked by a blocking agent (II) and / or a crosslinking agent (IV) having (F1);
A vinyl monomer (III) having a functional group (F2) that reacts with (F1) and / or a crosslinking agent (V) having (F2),
A volatile liquid and / or a sublimable solid (SL) is included in a polymer shell (PS) composed of a polymer (P) having (I) and (II) and / or (III) as essential structural units. This is the gist.

The thermally expandable microcapsule of the present invention has an extremely excellent expansion ratio. The hollow resin particles obtained by heating and expanding the thermally expandable microcapsules of the present invention have extremely excellent heat resistance.

As the cyano group-containing vinyl monomer (I), any vinyl polymer having a cyano group can be used without limitation. (Meth) acrylonitrile, chloro (meth) acrylonitrile, ethoxy (meth) acrylonitrile, fumaronitrile, maleoylnitrile, cyanostyrene And mixtures thereof. In addition, (meth) acrylonitrile means acrylonitrile and methacrylonitrile.
Among these, from the viewpoint of gas barrier properties, (meth) acrylonitrile, chloro (meth) acrylonitrile and ethoxy (meth) acrylonitrile are preferable, (meth) acrylonitrile is more preferable, and acrylonitrile is particularly preferable. The gas barrier property means that the volatile liquid and / or sublimable solid (SL) included in the polymer shell is difficult to leak out of the polymer shell.

The functional group (F1) blocked with the blocking agent reacts with the reactive functional group-containing compound {vinyl monomer (II) and cross-linking agent (IV)} by the reaction of the blocking agent with the reactive functional group. The reactivity of the functional functional group is suppressed by the dissociation of the blocking agent at a high temperature (including the case where the blocking agent dissociates simultaneously with the reaction of (F2) and (F1)). It means a functional group that recovers the reactivity of the functional group.
The high temperature is not limited as long as the blocking agent is dissociated, but is preferably 120 to 270 ° C., more preferably 150 to 250 ° C., particularly preferably 180 to 240 ° C. Preferably it is 200-230 degreeC.
Such a functional group (F1) includes a blocked isocyanate group, a blocked carboxy group, a blocked amino group, a blocked hydroxyl group, and the like.

The blocking agent is not particularly limited as long as it reacts with a reactive functional group-containing compound and the blocking agent dissociates at a high temperature, and includes the following compounds.
As the blocking agent for the isocyana group, lactam, phenol, oxime, alcohol, mercaptan, amide, imide, amine, and a mixture of two or more thereof can be used. As the blocking agent for the carboxy group, lactam, oxime, mercaptan, epoxide, isocyanate, vinyl compound and a mixture of two or more thereof can be used.
As the amino group blocking agent, ketones, carboxylic acids, isocyanates, and mixtures of two or more thereof can be used.
As a blocking agent for a hydroxyl group, ketone, carboxylic acid, isocyanate, a mixture of two or more of these, and the like can be used.

As a lactam, a C6-C15 lactam etc. are used, and (epsilon) -caprolactam, (delta) -valerolactam, (gamma) -butyrolactam, etc. are mentioned.
As the phenol, phenol having 6 to 15 carbon atoms and the like are used, and examples thereof include phenol, cresol, ethylphenol, butylphenol, nonylphenol and dinonylphenol.
As the oxime, an oxime having 3 to 15 carbon atoms is used, and examples thereof include methyl ethyl ketone oxime, acetophenone oxime (MEK oxime), and benzophenone oxime.
As alcohol, C1-C15 alcohol etc. are used, and methanol, ethanol, butanol, cyclohexanol, t-butanol, triethyl carbinol, tributyl carbinol, triphenyl carbinol, etc. are mentioned.
As the mercaptan, a mercaptan having 1 to 15 carbon atoms is used, and examples thereof include methyl mercaptan, ethyl mercaptan, butyl mercaptan, and dodecyl mercaptan.

As the amide, an amide having 1 to 15 carbon atoms is used, and examples thereof include acetamide, ethylamide, ethylacetamide, butylamide, acetanilide, and acetic acid amide.
As the imide, an imide having 3 to 12 carbon atoms is used, and examples thereof include malonic imide, phthalimide, succinimide, maleimide, and naphthalenedicarboxylic imide.
As the amine, an amine having 1 to 15 carbon atoms is used, and examples thereof include methylamine, ethylamine, butylamine, diethylamine, diphenylamine, aniline, and toluidine.
Examples of the vinyl compound include 2-methylpropene (isobutene) and 2-methylhexene (isoheptane).
As the ketone, a C3-C15 ketone or the like is used, and examples thereof include acetone, methyl isobutyl ketone, methyl ethyl ketone, benzophenone, dicyclohexyl ketone, methyl acetoacetate, ethyl acetoacetate, and acetylacetone.
As the carboxylic acid, a carboxylic acid having 1 to 15 carbon atoms is used, and examples thereof include methanoic acid, ethanoic acid, butanoic acid, lauric acid, benzoic acid, and toluic acid.

As isocyanate, C1-C15 isocyanate etc. are used, and ethyl isocyanate, butyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate, benzyl isocyanate, etc. are mentioned.
As the epoxide, an epoxide having 2 to 15 carbon atoms is used, and ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, 2-methyloctyl glycidyl ether, Examples thereof include phenyl glycidyl ether and cresyl glycidyl ether.
The blocking agent for the isocyanato group is preferably oxime, phenol and alcohol, more preferably oxime and alcohol, particularly preferably methyl ethyl ketone oxime, methanol and butanol.
The carboxyl group blocking agent is preferably an oxime or vinyl compound, more preferably a vinyl compound, and particularly preferably 2-methylpropene (isobutene).
As the amino group blocking agent, ketones and carboxylic acids are preferable, and ketones are more preferable.
As the hydroxyl blocking agent, ketones and carboxylic acids are preferable, and ketones are more preferable.

The blocking method is not particularly limited, and can be performed by a known method.
The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.2 to 1.8 molar equivalents, relative to 1 molar equivalent of the functional group to be blocked.
The reaction temperature for blocking is usually 10 to 150 ° C., but when vinyl monomer (II) is obtained, it is preferably carried out at a low temperature so that (II) is not polymerized, and preferably 10 to 30 ° C. Moreover, you may accelerate | stimulate reaction by adding a well-known catalyst.

The blocking method can be performed by a known method, for example, as shown below.
Reaction of isocyanato group-containing compound {vinyl monomer (II) and cross-linking agent (IV)} with oxime, alcohol or amine varies depending on the type of (II) or (IV) and the type of oxime, alcohol or amine, but usually Since the reactivity is extremely high, it is preferable that the blocking agent is slowly dropped into (II) or (IV) for reaction. The reaction temperature is preferably 0 to 150 ° C. {low temperature (0 to 30 ° C. when obtaining vinyl monomer (II))}. The reaction time is preferably about 1 to 20 hours after completion of the dropping. The dropping speed can be appropriately adjusted as long as the reaction does not run away due to an exothermic reaction. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.1 to 1.5 molar equivalents with respect to 1 molar equivalent of the isocyanate group.
The reaction between the isocyanato group-containing compounds {(II) and (IV)} and other blocking agents (lactams, phenols, etc.) is generally not highly reactive. May be.
Moreover, you may accelerate | stimulate reaction by adding a well-known catalyst. The reaction temperature is preferably 0 to 150 ° C. {when obtaining vinyl monomer (II), low temperature (0 to 30 ° C.)}. The reaction time is preferably about 1 to 20 hours. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.2 to 1.8 molar equivalents with respect to 1 molar equivalent of the carboxyl group.

  Since the reaction of the carboxy group-containing compound {vinyl monomer (II) and crosslinking agent (IV)} and the blocking agent is generally not highly reactive, both may be mixed and reacted at the same time. Moreover, you may accelerate | stimulate reaction by adding a well-known catalyst. In addition, since water produces | generates as a by-product, it is necessary to remove water out of the system. The reaction temperature is preferably 0 to 150 ° C. {when obtaining vinyl monomer (II), low temperature (0 to 30 ° C.)}. The reaction time is preferably about 1 to 20 hours. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.2 to 1.8 molar equivalents with respect to 1 molar equivalent of the carboxyl group.

  In the case of a blocking reaction between an amino group or a hydroxyl group-containing compound {vinyl monomer (II) and cross-linking agent (IV)} and a carboxylic acid or a ketone, the reactivity is low. Good. Moreover, you may accelerate | stimulate reaction by adding a well-known catalyst. In addition, when water produces | generates as a by-product, it is necessary to remove water out of the system. The reaction temperature is preferably 0 to 150 ° C. {when obtaining vinyl monomer (II), low temperature (0 to 30 ° C.)}. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.2 to 1.8 molar equivalents, relative to 1 molar equivalent of amino group or hydroxyl group.

The blocking reaction of an amino group or hydroxyl group-containing compound {vinyl monomer (II) and crosslinking agent (IV)} with an epoxide or isocyanate varies depending on the type of (II) or (IV) and the type of epoxide or isocyanate. Since the reactivity is extremely high, it is preferable that the blocking agent is slowly dropped into (II) or (IV) for reaction. The reaction temperature is preferably 0 to 150 ° C. {when obtaining vinyl monomer (II), low temperature (0 to 30 ° C.)}. The reaction time is preferably about 1 to 20 hours after completion of the dropping. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.1 to 1.5 molar equivalents with respect to 1 molar equivalent of amino group or hydroxyl group.
The blocking reaction of the functional group (F1) may be performed in a known solvent (dimethylformamide, toluene, tetrahydrofuran, etc.).

The functional group (F2) can be used without limitation as long as it is a functional group that reacts with the functional group (F1), and is a hydroxyl group, amino group, epoxy group, carboxy group, isocyanato group, mercapto group, carbamoyl group (H ₂ NCO— ) And imino groups (HN <) and the like. Note that (F2) may be blocked with a blocking agent as in (F1) (the same applies hereinafter).
When blocking about a hydroxyl group, an amino group, a carboxy group, and an isocyanato group, it can block by the blocking agent and blocking method similar to a functional group (F1).
In the case of blocking an epoxy group, as a blocking agent, lactam, phenol, oxime, alcohol, mercaptan, amide, imide, vinyl compound, amine and a mixture of two or more of these can be used. Of these, amines and carboxylic acids are preferred, amines are more preferred, and butylamine is particularly preferred.

  In the case of a blocking reaction other than the epoxy group-containing compound {vinyl monomer (III) and cross-linking agent (V)} and amine, the reactivity may be low, and both may be mixed and reacted at the same time. Moreover, you may accelerate | stimulate reaction by adding a well-known catalyst. The reaction temperature is preferably 0 to 150 ° C. {when obtaining vinyl monomer (II), low temperature (0 to 30 ° C.)}. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.2 to 1.8 molar equivalents with respect to 1 molar equivalent of the epoxy group. In addition, in the case of a blocking reaction between an epoxy group-containing compound and an amine, although depending on the type of (II) or (IV) and the type of amine, the reactivity is usually extremely high, so (II) or (IV) It is preferable that the blocking agent is slowly dropped and reacted. The reaction temperature is preferably 0 to 150 ° C. {when obtaining vinyl monomer (II), low temperature (0 to 30 ° C.)}. The reaction time is preferably about 1 to 20 hours after completion of the dropping. The addition amount of the blocking agent is preferably 1 to 2 molar equivalents, more preferably 1.1 to 1.5 molar equivalents per 1 molar equivalent of epoxy group.

Examples of the combination of the functional group (F1) and the functional group (F2) include the following combinations.
When the functional group (F1) is a blocked isocyanate group, the functional group (F2) is preferably a hydroxyl group, an amino group, a carboxy group and an epoxy group, more preferably a hydroxyl group, an amino group and a carboxy group, particularly preferably a hydroxyl group and an amino group. It is.
When the functional group (F1) is a blocked carboxy group, the functional group (F2) is preferably a hydroxyl group or an amino group, more preferably a hydroxyl group.
When the functional group (F1) is a blocked amino group, a blocked hydroxyl group and / or a blocked carboxy group, the functional group (F2) is preferably an isocyanato group or an epoxy group, more preferably an isocyanato group.

The vinyl monomer (II) only needs to have at least one functional group (F1) blocked with a blocking agent, and when it has two or more (F1), it may be the same type or different types. The number (number) of the functional groups (F1) contained in the vinyl monomer (II) is preferably 1 to 4, more preferably 1 to 3, particularly preferably 1 or 2, and most preferably from the viewpoint of expansibility. 1.
The vinyl monomer (II) includes (1) a blocked isocyanate group-containing vinyl monomer, (2) a blocked carboxy group-containing vinyl monomer, (3) a blocked amino group-containing vinyl monomer, and (4) a blocked hydroxyl group-containing vinyl monomer. (5) Vinyl monomers having different types of functional groups (F1) and mixtures of two or more thereof can be used.

(1) The blocked isocyanate group-containing vinyl monomer has a structure that can be produced by reacting a blocking agent with an isocyanate group-containing vinyl monomer.
As the isocyanato group-containing vinyl monomer, isocyanatoalkyl (meth) acrylate having 4 to 20 carbon atoms is used, and isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, isocyanatobutyl (meth) acrylate, and And isocyanatohexyl (meth) acrylate.
Among these, from the viewpoint of heat resistance, alkyl (meth) acrylate is preferable, and isocyanatohexyl (meth) acrylate is particularly preferable.

(2) The blocked carboxy group-containing vinyl monomer has a structure that can be produced by reacting a blocking agent with a carboxy group-containing vinyl monomer.
As the carboxy group-containing vinyl monomer, a vinyl carboxylic acid having 3 to 20 carbon atoms or the like is used. (Meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester (alkyl having 1 to 20 carbon atoms: maleic acid) Monoethyl ester, maleic acid monobutyl ester, maleic acid monohexyl ester, etc. (the same applies to alkyl), fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol mono Ethers (2-20 carbon atoms of glycol: ethylene glycol, propylene glycol, hexene glycol, etc.), citraconic acid, citraconic acid monoalkyl ester and cinnamic acid, etc., and alkali metal (sodium and potassium) salts, alkaline earth Metal (calcium and magnesium) salts, amines (C3-20: trimethylamine, triethylamine, butyl dimethylamine and triethanolamine) salts and ammonium salts.
Among these, (meth) acrylic acid is preferable from the viewpoint of heat resistance, and acrylic acid is particularly preferable.

(3) The blocked amino group-containing vinyl monomer has a structure that can be produced by reacting a blocking agent with an amino group-containing vinyl monomer.
As the amino group-containing vinyl monomer, an amino group-containing vinyl monomer having 4 to 50 carbon atoms can be used, and aminoalkyl (meth) acrylate (alkyl having 3 to 20 carbon atoms: aminoethyl (meth) acrylate, aminoisopropyl (meta ) Acrylate, aminobutyl (meth) acrylate, aminohexyl (meth) acrylate, etc. (the same applies to alkyl)), aminoalkylacrylamide (alkyl 3 to 20 carbon atoms), (meth) allylamine, crotylamine, aminostyrene, N -Allylphenylenediamine and 16- (meth) acryloylhexadecylamine, and alkali metal (sodium and potassium, etc.), alkaline earth metal (calcium and magnesium, etc.), amine (carbon number 3 to 20) salts thereof, and A And ammonium salts.
Of these, aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides are preferable from the viewpoint of heat resistance and the like, more preferably aminoalkyl (meth) acrylate, particularly preferably aminoethyl (meth) acrylate, aminoisopropyl ( And (meth) acrylate and aminobutyl (meth) acrylate.

(4) The blocked hydroxyl group-containing vinyl monomer has a structure that can be produced by reacting a blocking agent with a hydroxyl group-containing vinyl monomer.
As the hydroxyl group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer having 2 to 20 carbon atoms is used, and hydroxyalkyl (meth) acrylate (alkyl 3 to 20 carbon atoms: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate) And hydroxybutyl (meth) acrylate and the like (the same applies to alkyl below)), hydroxyacrylamide (alkyl 3 to 20 carbon atoms), hydroxystyrene, N-methylol (meth) acrylamide, (meth) allyl alcohol, crotyl alcohol, Others include isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether. , Polyethylene glycol (weight average molecular weight 100-10000) (meth) acrylate, polyethylene / polypropylene glycol (weight average molecular weight 200-10000, oxyethylene content 10-90% by weight) (meth) acrylate and polypropylene glycol (weight average molecular weight) 100-10000) (meth) acrylate and the like can also be used.
Of these, from the viewpoint of heat resistance, hydroxyalkyl (meth) acrylate and hydroxyalkyl (meth) acrylamide are preferable, hydroxyalkyl (meth) acrylate is more preferable, and hydroxyethyl methacrylate (HEMA) is particularly preferable.

(5) Vinyl monomers having different types of functional groups (F1) include those having a structure that can be produced by reacting a blocking agent with a hydroxyl group-containing vinyl monomer.
Examples of vinyl monomers having different types of functional groups (F1) include phthalic acid monoisocyanatopropyl ester and maleic acid monohydroxyethyl ester.

The cross-linking agent (IV) only needs to have at least two functional groups (F1) blocked with a blocking agent, and (F1) may be the same or different. The number (pieces) of the functional group (F1) contained in the crosslinking agent (IV) is preferably 2 to 8, more preferably 2 to 4, particularly preferably 2 or 3, and most preferably from the viewpoint of improving heat resistance. Is 2.
As the crosslinking agent (IV), (1) blocked polyisocyanate, (2) blocked polycarboxylic acid, (3) blocked polyamine, (4) blocked polyol, (5) different types of functional groups (F1) A blocked product having the above and a mixture of two or more of these can be used.
In addition, what is considered to be produced by reacting with a blocking agent is also included in the crosslinking agent (IV).

(1) The blocked polyisocyanate has a structure that can be produced by reacting a blocking agent with a polyisocyanate.
As the polyisocyanate, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate and modified products thereof can be used.

  As the aromatic polyisocyanate, aromatic polyisocyanate having 6 to 36 carbon atoms is used, and 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), Crude TDI, 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3 '-Dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 1,3- or 1,4-diisocyanatophenylsulfonyl isocyanate and 4,4', 4 "-tri Examples include phenylmethane triisocyanate.

  Examples of the aliphatic polyisocyanate include aliphatic polyisocyanates having 2 to 36 carbon atoms, such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatome. Tilcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2-isocyanatoethyl -2,6-diisocyanatohexanoate etc. are mentioned.

  As the alicyclic polyisocyanate, alicyclic polyisocyanate having 4 to 20 carbon atoms is used, and isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methyl Examples include cyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

As modified products, urethane modified products, carbodiimide modified products, allophanate modified products, urea modified products, burette modified products, uretdione modified products, uretoimine modified products, isocyanurate modified products and oxazolidone modified products of the above polyisocyanates are used. And modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI, biuret modified HDI, isocyanurate modified HDI, isocyanurate modified IPDI, and the like.
Of these, aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates having 1 to 6 carbon atoms are preferred from the viewpoint of heat resistance and the like, more preferably aromatic polyisocyanates and alicyclic polyisocyanates, particularly IPDI, MDI and TDI are preferred.

(2) The blocked polycarboxylic acid has a structure that can be produced by reacting a blocking agent with a polycarboxylic acid.
As the polycarboxylic acid, aromatic (aliphatic) polycarboxylic acid, aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, carboxy group-containing oligomer and the like can be used.

  As the aromatic (aliphatic) polycarboxylic acid, an aromatic (aliphatic) polycarboxylic acid having 7 to 36 carbon atoms is used, and phthalic acid, isophthalic acid, terephthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid is used. Acid, 2,2'-, 3,3'-, 2,7-, or 4,4'-biphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane Dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5- or 2,6-anthracene dicarboxylic acid, 1,2,4- Trimellitic acid, 1,2,5- or 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tri Rubonic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenyl ether-3,3 ′, 4-tricarboxylic acid, pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, benzophenone- 2,2 ′, 3,3′-tetracarboxylic acid, diphenylsulfone-2,2 ′, 3,3′-tetracarboxylic acid, diphenyl ether-2,2 ′, 3,3′-tetracarboxylic acid and the like can be mentioned. .

  As the aliphatic polycarboxylic acid, an aliphatic polycarboxylic acid having 1 to 36 carbon atoms is used, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid. , Undecanedioic acid, dodecanedioic acid, octenylsuccinic acid, and α, β, γ-tricarboxypropane.

As the alicyclic polycarboxylic acid, an alicyclic polycarboxylic acid having 1 to 36 carbon atoms or the like is used, and 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, Examples include 4-cyclohexanedicarboxylic acid, 1,3-dicarboxymethylcyclohexane, isophorone dicarboxylic acid, dicyclohexyl-4,4′-dicarboxylic acid, and camphoric acid.
As the carboxy group-containing oligomer, a polycarboxylic acid oligomer having a weight average molecular weight of 1,000 to 10,000 is used, and examples thereof include poly (meth) acrylic acid.
Among these, from the viewpoint of heat resistance, aromatic polycarboxylic acids and aliphatic polycarboxylic acids having 1 to 6 carbon atoms are preferable, aromatic polycarboxylic acids are more preferable, and phthalic acid is particularly preferable.

(3) The blocked polyamine has a structure that can be produced by reacting a blocking agent with a polyamine.
As the polyamine, aliphatic polyamines, alicyclic polyamines, heterocyclic ring-containing aliphatic polyamines, aromatic polyamines, and the like can be used.

  As the aliphatic polyamine, an aliphatic polyamine having 2 to 36 carbon atoms is used, and ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine. , Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like.

  As the alicyclic polyamine, an alicyclic polyamine having 4 to 36 carbon atoms or the like is used, and 1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4′-methylene dicyclohexane diamine (hydrogenated methylene diamine). Aniline) and 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.

As the heterocyclic polyamine, a heterocyclic polyamine having 4 to 36 carbon atoms is used, and piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methyl) is used. Propyl) piperazine and imidazoline.
As the araliphatic polyamine, an araliphatic polyamine having 8 to 12 carbon atoms is used, and examples thereof include xylylenediamine, tetrachloro-p-xylylenediamine, and diaminomethylnaphthalene.

As the aromatic polyamine, an aromatic polyamine having 4 to 36 carbon atoms is used, and 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine, methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylene Examples thereof include diamines and mixtures thereof. In addition, an aromatic polyamine having a secondary amino group (a part or all of —NH ₂ of the aromatic polyamine is —NH—R ′ (R ′ is an alkyl group having 1 to 20 carbon atoms: methyl, ethyl, isobutyl, etc.) ) Substituted with {4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.]) and the like.
Among these, from the viewpoint of heat resistance, aromatic polyamines and aliphatic polyamines having 1 to 6 carbon atoms are preferable, aliphatic polyamines having 1 to 6 carbon atoms are more preferable, and ethylenediamine and hexamethylenediamine are particularly preferable. .

(4) The blocked polyol has a structure that can be produced by reacting a blocking agent with a polyol.
As the polyol, polyhydric alcohols, polyhydric phenols, and these alkylene oxide adducts can be used.

  As the polyhydric alcohol, polyhydric alcohol having 2 to 20 carbon atoms or the like is used. Ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl Pentanediol, diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane, glycerin, tri Examples include methylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose and sucrose.

Examples of the polyhydric phenol include pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F and bisphenol S.
As these alkylene oxide adducts, polyhydric alcohol or polyhydric alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, and / or styrene oxide) adducts and the like can be used. The alkylene oxide may be a mixture of two or more, and in this case, any of block, random and a mixture thereof may be used. The addition number (pieces) of alkylene oxide is preferably 1 to 20, more preferably 2 to 10, and particularly preferably 3 to 5 per hydroxyl group.

  Among these, from the viewpoint of heat resistance, polyhydric alcohols having 1 to 6 carbon atoms and polyhydric phenols are preferable, more preferably polyhydric alcohols having 1 to 6 carbon atoms, particularly preferably ethylene glycol, propylene glycol (PPG). ), 1,3-butylene glycol and 1,4-butanediol.

(5) Blocked products having different types of functional groups (F1) include those having a structure that can be produced by reacting a blocking agent with a hydroxycarboxylic acid or an amino acid.
As the hydroxycarboxylic acid, a hydroxycarboxylic acid having 2 to 20 carbon atoms is used, and hydroxyacetic acid, hydroxypropanecarboxylic acid, salicylic acid, mandelic acid, hydroxybenzoic acid, tropic acid, tartronic acid, malic acid, tartaric acid and citric acid Etc.
As the amino acid, an aminocarboxylic acid having 2 to 20 carbon atoms is used, and examples thereof include glycine, phenylalanine, tyrosine, aspartic acid, glutamic acid, serine, histidine, and tryptophan.

The vinyl monomer (III) only needs to have at least one functional group (F2) that reacts with the blocked functional group (F1). When two or more (F2) are present, (F2) is the same type. But it can be a different type. The number (pieces) of the functional group (F2) contained in the vinyl monomer (III) is preferably 2 to 8, more preferably 2 to 4, particularly preferably 2 or 3, most preferably from the viewpoint of improving heat resistance. Is 2.
The vinyl monomer (III) having a functional group (F2) that reacts with the blocked functional group (F1) includes (1) a hydroxyl group-containing vinyl monomer, (2) an amino group-containing vinyl monomer, and (3) an epoxy group-containing vinyl monomer. Monomers, (4) carboxy group-containing vinyl monomers, (5) isocyanato group-containing vinyl monomers, and mixtures of two or more of these can be used.
(1) Hydroxyl group-containing vinyl monomer, (2) Amino group-containing vinyl monomer, (4) Carboxy group-containing vinyl monomer, (5) Isocyanato group-containing vinyl monomer, and preferred ranges thereof are the same as above.

(3) As the epoxy group-containing vinyl monomer, an epoxy group-containing vinyl monomer having 5 to 20 carbon atoms is used, and examples thereof include vinyl glycidyl ether, propenyl glycidyl ether, and glycidyl (meth) acrylate.
Among these, glycidyl methacrylate (GMA) is preferable from the viewpoint of heat resistance.

The cross-linking agent (V) has only to have at least two functional groups (F2) that react with the blocked functional group (F1), and (F2) may be the same or different. The number (number) of functional groups (F2) contained in the crosslinking agent (V) is preferably 2 to 8, more preferably 2 to 4, particularly preferably 2 or 3, and most preferably from the viewpoint of improving heat resistance. Is 2.
Examples of the crosslinking agent (V) having a functional group (F2) that reacts with the blocked functional group (F1) include (1) polyol, (2) polyamine, (3) polyepoxide, (4) polycarboxylic acid, (5 ) Polyisocyanates and mixtures of two or more thereof can be used.
(1) Polyol, (2) Polyamine, (4) Polycarboxylic acid, (5) Polyisocyanate and preferred ranges thereof are the same as above.

(3) As polyepoxides, aliphatic polyepoxides, alicyclic polyepoxides, aromatic polyepoxides and other polyepoxides can be used.
Examples of the aliphatic polyepoxide include polyol polyglycidyl ether and aliphatic polycarboxylic acid polyglycidyl ester.
Polyglycidyl ether having 6 to 36 carbon atoms is used as the polyol polyglycidyl ether, and ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetra Examples thereof include glycidyl ether, sorbitol polyglycidyl ether, and catechol diglycidyl ether. In addition, polyethylene glycol (weight average molecular weight 200-10000) diglycidyl ether, polyethylene / polypropylene glycol (weight average molecular weight 300-10000, oxyethylene content 10-90% by weight) diglycidyl ether and polypropylene glycol (weight average) (Molecular weight 100-10000) diglycidyl ether and the like can also be used.
Examples of the aliphatic polycarboxylic acid polyglycidyl ester include polyglycidyl esters having 6 to 36 carbon atoms, such as diglycidyl adipate, diglycidyl oxalate ester, diglycidyl malonate, diglycidyl succinate, and α, β , Γ-tricarboxypropane triglycidyl ester and the like.

  As the alicyclic polyepoxide, an alicyclic polyepoxide having 6 to 36 carbon atoms is used, and vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol. Bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, Examples include bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, 1,3-cyclobutanedicarboxylic acid diglycidyl ester, 1,3-cyclopentanedicarboxylic acid diglycidyl ester, and the like.

As the aromatic polyepoxide, polyhydric phenol polyglycidyl ether, polyglycidyl aromatic polyamine, aromatic polycarboxylic acid polyglycidyl ester and the like can be used.
As polyhydric phenol polyglycidyl ether, C6-C36 polyhydric phenol polyglycidyl ester etc. are used, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, Bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetrachlorobisphenol A diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, Dihydroxybiphenyl diglycidyl ether and octachloro-4,4'-dihydroxy Biphenyl diglycidyl ether etc. are mentioned.
As the glycidyl aromatic polyamine, a polyglycidyl aromatic polyamine having 12 to 25 carbon atoms or the like is used. N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine, N, N ′ -Diglycidyl-1,4-naphthalenediamine, N, N'-diglycidyl-2,4-pyridinediamine and the like.
As the aromatic polycarboxylic acid polyglycidyl ester, aromatic polycarboxylic acid polyglycidyl ester having 14 to 22 carbon atoms and the like are used. Diglycidyl phthalate, diglycidyl naphthalene dicarboxylic acid ester, 4,4′-diphenyl ether dicarboxylic acid diester Examples thereof include glycidyl ester, 4,4′-diphenylmethanedicarboxylic acid diglycidyl ester, and 1,2,4-trimellitic acid triglycidyl ester.

Other epoxides include diglycidyl ether and trisglycidyl melamine.
Of these, aromatic polyepoxides and aliphatic polyepoxides having 2 to 10 carbon atoms are preferred from the viewpoint of heat resistance, etc., more preferably aliphatic polyepoxides having 2 to 10 carbon atoms, particularly preferably tylene glycol diglycidyl ether, propylene. Glycol diglycidyl ether and tetramethylene glycol diglycidyl ether.

The polymer (P) comprises a cyano group-containing vinyl monomer (I) and a vinyl monomer (II) and / or vinyl monomer (III) as essential constituent units. ) As a structural unit.
As the vinyl monomer (VI), a crosslinkable vinyl monomer (C) and other vinyl monomers (D) can be used.

As the crosslinkable vinyl monomer (C), a vinyl monomer having at least two vinyl groups can be used, and a diene (C1) having 4 to 10 carbon atoms, a bis (meth) acrylamide (C2) having 8 to 12 carbon atoms, Poly (meth) acrylate (C3) of polyol (2 to 10 carbon atoms), polyallylamine (C4) having 6 to 9 carbon atoms, polyallyl ether (C5) having 6 to 17 carbon atoms and diallyl having 9 to 14 carbon atoms Esters (C6) and the like are included.
Examples of the diene (C1) include butadiene, pentadiene, hexadiene, cyclopentadiene, ethylidene norbornene, divinylbenzene, divinyltoluene, divinylxylene, and diallylcarbinol.
Examples of bis (meth) acrylamide (C2) include N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide and N, N′-propylenebis (meth) acrylamide.

Poly (meth) acrylate (C3) of polyol is polyol di (meth) acrylate {ethylene glycol di (meth) acrylate, poly (degree of polymerization 2 to 5) ethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate and glycerin di (meth) acrylate, etc.} and polyol tri or tetra (meth) acrylate {glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, diglycerin tetra (meth) acrylate, etc.} and the like. .
Examples of polyallylamine (C4) include diallylamine and triallylamine.
Examples of the polyvinyl ether (C5) include divinyl ether, diallyl ether {diallyl ether, diaryloxymethane, diaryloxyethane, pentaerythritol diallyl ether, etc.}, and tri- or tetra-allyl ether {tetraallyloxyethane, pentaerythritol Triallyl ether and pentaerythritol tetraallyl ether} and the like.
Examples of diallyl esters (C6) include diallyl phthalate, diallyl malonate, diallyl succinate, and diallyl adipate.

  Among these crosslinkable vinyl monomers (C), from the viewpoint of heat resistance, vinyl monomers having two vinyl groups {diene, bis (meth) acrylamide, polyol di (meth) acrylate, diallylamine, divinyl ether, diallyl Ethers and diallyl esters} are preferred, more preferred are dienes, bis (meth) acrylamides, divinyl ethers and di (meth) allyl ethers, and particularly preferred are dienes and di (meth) allyl ethers.

  Other vinyl monomers (D) include aromatic vinyl hydrocarbons having 8 to 12 carbon atoms (D1), aliphatic vinyl hydrocarbons having 2 to 18 carbon atoms (D2), and alicyclic vinyls having 5 to 15 carbon atoms. Hydrocarbon (D3), C4-C22 (meth) acrylate (D4), C3-C22 (meth) acrylamide (D5), C3-C5 carboxylic acid and acid anhydride (D6), Examples thereof include a vinyl sulfonic acid having 2 to 10 carbon atoms (D7), a vinyl ether having 3 to 10 carbon atoms (D8), a vinyl ketone having 4 to 11 carbon atoms (D9), and the like.

Examples of the aromatic vinyl hydrocarbon having 8 to 12 carbon atoms (D1) include styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, and benzyl. Examples include styrene, crotylbenzene, hydroxystyrene, vinyl naphthalene, vinyl pyridine, chlorostyrene, and dichlorostyrene.
Examples of the aliphatic vinyl hydrocarbon (D2) having 2 to 18 carbon atoms include ethylene, propylene, butene, isobutylene, pentene, heptene, octene, dodecene and octadecene.
Examples of the alicyclic vinyl hydrocarbon (D3) having 5 to 15 carbon atoms include vinylcyclohexane, cyclohexene, pinene, limonene, and indene.

  Examples of the (meth) acrylate (D4) having 4 to 22 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) Octadecyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, triethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid In addition to dihydroxymethylaminoethyl, morpholinoethyl (meth) acrylate and the like, maleic acid ester having 6 to 12 carbon atoms {dimethyl maleate, monomethyl maleate, diethyl maleate, dihexyl maleate, monohexyl maleate, maleate Acid monobe Zyl and dimethylaminoethyl maleate, etc.} and polyoxyalkylene (oxyethylene and / or oxypropylene: random and / or block) mono (meth) acrylate having a weight average molecular weight of 100 to 2,000 {terminal hydroxyl group has 1 to 4 carbon atoms Or an alkyl group (such as methyl, ethyl and butyl) or a saturated fatty acid having 2 to 3 carbon atoms (such as acetic acid and propionic acid) may be used.

  Examples of the (meth) acrylamide (D5) having 3 to 22 carbon atoms include (meth) acrylamide, N-alkyl (meth) acrylamide {N-methyl (meth) acrylamide, N-butyl (meth) acrylamide and N-benzyl (meth) ) Acrylamide etc.}, N, N-dialkyl (meth) acrylamide {N, N-dimethyl (meth) acrylamide and N, N-dipropyl (meth) acrylamide etc.}, N-hydroxyalkyl (meth) acrylamide {N-hydroxymethyl (Meth) acrylamide and N-hydroxyethyl (meth) acrylamide etc.}, N, N-dihydroxyalkyl (meth) acrylamide {N, N-dihydroxyethyl (meth) acrylamide etc.} and aminoalkyl (meth) acrylamide {dimethylaminoethyl (Me ) Besides acrylamide and of diethylaminoethyl (meth) acrylamide and the like}, N- vinyl lactams (N- vinylpyrrolidone), and the like can be used.

Examples of the carboxylic acid having 3 to 5 carbon atoms and the acid anhydride (D6) include (meth) acrylic acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride and citraconic anhydride.
Examples of the vinyl ester (D7) having 3 to 10 carbon atoms include vinyl formate, vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate, vinyl benzoate, isoprenyl acetate and allyl acetate.

  Examples of the vinyl sulfonic acid (D7) having 2 to 10 carbon atoms include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, (meth) acryloxypropyl sulfonic acid, and (meth) acryloxyethane sulfone. Acids, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid and propylallylsulfosuccinic acid, and alkali metal (such as sodium and potassium) salts, alkaline earth metal (such as calcium and magnesium) salts, amine salts or An ammonium salt etc. are mentioned.

  Examples of the vinyl ether having 3 to 10 carbon atoms (D8) include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, vinyl 2-butoxyethyl. Examples include ether, 2-butoxy-2′-vinyloxydiethyl ether, and vinyl 2-ethylmercaptoethyl ether.

  Examples of the vinyl ketone having 4 to 11 carbon atoms (D9) include vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, and vinyl 2-ethylhexyl ketone.

  Of these, (meth) acrylate and (meth) acrylamide are preferable from the viewpoint of heat resistance and the like, more preferably (meth) acrylate, particularly preferably methyl (meth) acrylate, ethyl (meth) acrylate and (meth) acrylate. ) Butyl acrylate.

Content of each structural unit of a polymer (P) is as follows based on the total number of moles of the vinyl monomer made into a structural unit.
The content (mol%) of the cyano group-containing vinyl monomer (I) unit is preferably from 50 to 99.5, more preferably from 60 to 96, particularly preferably from 70 to 93. Within this range, the gas barrier properties can be sufficiently exerted and the expansion ratio becomes good.
When the vinyl monomer (II) is used as a structural unit, the content (mol%) of the (II) unit is preferably 0.05 to 15 based on the total number of moles of the vinyl monomer as the structural unit, more preferably It is 0.07-10, Most preferably, it is 0.1-5. Within this range, the expansibility and heat resistance are further improved.
When the vinyl monomer (III) is a structural unit, the content (% by weight) of the (III) unit is preferably 0.05 to 15 based on the total number of moles of the vinyl monomer as the structural unit, more preferably It is 0.07-10, Most preferably, it is 0.1-5. Within this range, the expansibility and heat resistance are further improved.
When both vinyl monomer (II) and vinyl monomer (III) are used as structural units, the number ratio (II / III) is preferably 1/2 to 1 / 0.5, more preferably 1 / 1.5. ˜1 / 0.7, particularly preferably 1 / 1.2 to 1 / 0.8. Within this range, the expansibility is further improved.
When other vinyl monomer (VI) is used as the structural unit, the content (mol%) of the (VI) unit is preferably 1 to 49.5 based on the total number of moles of the vinyl monomer as the structural unit, Preferably it is 2-30, Most preferably, it is 5-20.
When the crosslinkable vinyl monomer (C) is included as a structural unit, the content (mol%) is preferably 0.01 to 10 based on the total number of moles of the vinyl monomer as the structural unit, more preferably 0.8. 05 to 5, particularly preferably 0.09 to 1. Within this range, the expansibility and heat resistance are further improved.

The weight average molecular weight (Mw) of the polymer (P) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 20,000 to 300,000. Mw is measured by gel permeation chromatography using polystyrene as a standard substance.
Moreover, 110-250 are preferable, as for the softening temperature (degreeC) of a polymer (P), More preferably, it is 120-220, Most preferably, it is 130-200. The softening temperature is measured according to the 5.1 powder method of JIS K5601-2-2: 1999 (the measurement sample was heat-treated at 50 ° C. and 0.1 to 3 torr for 90 minutes).

(1) When the polymer (P) is composed of a cyano group-containing vinyl monomer (I), a vinyl monomer (II) and, if necessary, another vinyl monomer (VI) as a constituent unit, the crosslinking agent (V) is a polymer (P) And / or an essential component of volatile liquids and / or sublimable solids (SL).
(2) When the polymer (P) is composed of a cyano group-containing vinyl monomer (I), a vinyl monomer (III) and, if necessary, another vinyl monomer (VI) as a constituent unit, the crosslinking agent (IV) is a polymer (P) And / or an essential component of volatile liquids and / or sublimable solids (SL).
(3) When the polymer (P) comprises a cyano group-containing vinyl monomer (I), a vinyl monomer (II), a vinyl monomer (III) and, if necessary, other vinyl monomers (VI) as a constituent unit, a crosslinking agent (IV) And the crosslinking agent (V) may not be contained as a constituent in the polymer (P) and / or volatile liquid and / or sublimable solid (SL), and (IV) and / or (v) may constitute It may be included as a component.

In the case of (1), the content (mol%) of the crosslinking agent (V) is preferably 0.05 to 15 and more preferably 0.07 to 10 based on the total number of moles of the polymer (P) structural unit. Especially preferably, it is 0.1-5. Within this range, the expansibility and heat resistance are further improved.
In the case of (2), the content (mol%) of the crosslinking agent (IV) is preferably 0.05 to 15 and more preferably 0.07 to 10 based on the total number of moles of the polymer (P) structural unit. Especially preferably, it is 0.1-5. Within this range, the expansibility and heat resistance are further improved.
In the case of (3), the content (mol%) of (IV) in the case of containing the crosslinking agent (IV) as a constituent component is based on the total number of moles of the polymer (P) constituent unit, 15 is preferable, more preferably 0.07 to 10, and particularly preferably 0.1 to 5. Within this range, the expansibility and heat resistance are further improved.
In the case of (3), the content (mol%) of (V) in the case of containing the crosslinking agent (V) as a constituent component is 0.05 to based on the total number of moles of the polymer (P) constituent unit. 15 is preferable, more preferably 0.07 to 10, and particularly preferably 0.1 to 5. Within this range, the expansibility and heat resistance are further improved.

As a constituent component of the polymer shell (PS), in addition to the polymer (P), a thermoplastic resin (acrylic resin, epoxy resin, urethane resin, amide resin, imide resin, etc.), inorganic filler (silica, titanium oxide, talc and calcium carbonate) Etc.), organic fillers (polystyrene filler, polymethyl methacrylate filler, etc.), colorants (dyes, pigments, etc.) and the like.
When the thermoplastic resin is a constituent component, the content (% by weight) is preferably 0.1 to 20, more preferably 0.3 to 10, based on the total weight of the constituent units of the polymer (P). Especially preferably, it is 0.5-5.
When the inorganic filler is used as a constituent component, the content (% by weight) is preferably 0.1 to 20, more preferably 0.3 to 10, particularly preferably based on the total weight of the constituent units of the polymer (P). Preferably it is 0.5-5.
When the organic filler is a constituent component, the content (% by weight) is preferably 0.1 to 20, more preferably 0.3 to 10, especially based on the total weight of the constituent units of the polymer (P). Preferably it is 0.5-5.
When the colorant is a constituent component, the content (% by weight) is preferably from 0.1 to 20, more preferably from 0.3 to 10, based on the total weight of the constituent units of the polymer (P). Preferably it is 0.5-5.

The volatile liquid and / or sublimable solid (SL) is not particularly limited as long as it does not dissolve the constituent components of the polymer shell (PS), and known ones can be used, including hydrocarbons, halogenated hydrocarbons, Alcohols, ethers, ketones and sublimable compounds are included.
Examples of the hydrocarbon include hydrocarbons having 3 to 15 carbon atoms, such as propane, butane, pentane, n-hexane, isohexane, heptane, benzene, toluene, xylene, cyclohexane, cyclopentane, and methylcyclohexane.
Examples of the halogenated hydrocarbon include halides having 1 to 4 carbon atoms such as ethyl chloride, methyl chloride, methyl bromide, chloroform, dichlorobutane, and trichloroethane.
As alcohol, C1-C20 alcohol etc. are used, and methanol, ethanol, butanol, cyclohexanol, t-butanol, etc. are mentioned.
As ether, C2-C15 ether etc. are used, and dimethyl ether, diethyl ether, dibutyl ether, diethylene glycol, dioxane, tetrahydrofuran, etc. are mentioned.
As a ketone, a C3-C13 ketone etc. are used, and acetone, methyl isobutyl ketone, methyl ethyl ketone, benzophenone, dicyclohexyl ketone, etc. are mentioned.
Examples of the sublimable compound include hexachloroethane, iodine and camphor.
In addition to these, compounds that decompose at a high temperature (for example, 180 to 190 ° C.) to generate gas (for example, azodicarbonamide (NH ₂ CON = NCONH ₂ , decomposed to cyanuric acid and ammonia at 180 ° C.)) and Shu Acid (decomposed into formic acid, carbon monoxide and carbon dioxide at 180 to 190 ° C.), etc.} can also be used.

Of these, hydrocarbons and halogenated hydrocarbons are preferable from the viewpoint of expansibility, etc., more preferably hydrocarbons, and particularly preferably pentane, n-hexane, cyclohexane and isohexane.
The content (% by weight) of the volatile liquid and / or sublimable solid (SL) is preferably 1 to 50, more preferably 5 to 20, particularly preferably 10 to 10% based on the weight of the polymer shell (PS). 15.

The heat-expandable microcapsules of the present invention can be produced by known methods, such as vinyl monomers (I and II, III and / or VI), volatile liquids or sublimable solids (SL) and optionally polymerized. An initiator is mixed, and the mixture is suspension-polymerized in an aqueous medium containing a surfactant and / or a dispersion stabilizer (Japanese Patent Publication No. 42-26524).
In addition, thermoplastic resin (acrylic resin, epoxy resin, urethane resin, amide resin, imide resin, etc.), inorganic filler (silica, titanium oxide, talc, calcium carbonate, etc.), organic filler (polystyrene filler, polymethyl methacrylate filler, etc.) Colorants (dyes and pigments) and the like can be added at any stage of suspension polymerization.
The polymerization temperature (° C.) is preferably 50 to 120, more preferably 55 to 90, and particularly preferably 60 to 80. The polymerization may be performed under atmospheric pressure, but is preferably performed under pressure (atmospheric pressure +0.1 to 1 MPa) so as not to make the volatile liquid or the like (SL) gaseous.
The suspension polymerization is preferably performed in a sealed state using a pressure vessel. Moreover, after suspending with a disperser etc., it may transfer to a pressure-resistant container and suspension polymerization may be carried out, and you may make it suspend in a pressure-resistant container.
After completion of the polymerization, solid-liquid separation and / or washing may be performed by a known method (such as centrifugation or filtration). On the other hand, the product can be produced in a state dispersed in water or in a solvent or the like without performing solid-liquid separation.
In the case of solid-liquid separation and / or washing, it may be dried and / or pulverized below the softening temperature of the polymer shell (PS). Drying and pulverization can be performed by a known method, and an air dryer, a smooth air dryer, a nauter mixer, or the like can be used. Further, drying and pulverization can be simultaneously performed by a pulverization dryer or the like.

Although it does not specifically limit as a polymerization initiator, The oil-soluble initiator soluble in a cyano group containing vinyl monomer is preferable, and a well-known peroxide initiator, an azo initiator, etc. can be used. Of these, azo initiators are preferred, more preferably 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis-4-methoxy-2. , 4-dimethylvaleronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile, particularly preferably 2,2′-azobisisobutyronitrile.
When a polymerization initiator is used, the amount used (% by weight) is preferably 0.01 to 5, more preferably 0.05 to 2, particularly preferably 0, based on the total weight of the vinyl monomer as a constituent unit. .1-1.

Examples of the surfactant include anionic surfactants (sodium lauryl sulfate, (poly) oxyethylene (degree of polymerization 1 to 100) sodium lauryl sulfate and (poly) oxyethylene (degree of polymerization 1 to 100) lauryl sulfate triethanolamine, etc. ), Cationic surfactants (stearyltrimethylammonium chloride, diethylaminoethylamide stearate lactate, dilaurylamine hydrochloride and oleylamine lactate, etc.), nonionic surfactants (diethanolamine adipic acid condensate, lauryldimethylamine oxide, Glyceryl monostearate, sorbitan monolaurate and diethylaminoethylamide lactate stearate) and amphoteric surfactants (coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryl hydroxysulfobe Included in and β- laurylamino sodium propionate, etc.), in addition to these surfactants, it is possible to use a polymer type dispersant (polyvinyl alcohol, starch and carboxymethyl cellulose).
Of these, cationic, nonionic and amphoteric surfactants and their combined use with polymeric dispersants are preferred, and more preferred are nonionic active agents and nonionic active agents with polymeric dispersants. Particularly preferred is a combined use of a nonionic active agent and a polymeric dispersant.
When a surfactant is used, the amount used (% by weight) is 0.01 to 10 based on the total weight of the vinyl monomer as a constituent unit and the volatile liquid and / or sublimable solid (SL). More preferably, it is 0.05-5, Most preferably, it is 0.1-2.
When using a polymeric dispersant, the amount used is preferably 0.01 to 5, based on the total weight of the vinyl monomer as a constituent unit and the volatile liquid and / or sublimable solid (SL), More preferably, it is 0.02-3, Most preferably, it is 0.03-1.

As the dispersion stabilizer, silica (such as colloidal silica), calcium carbonate, calcium phosphate, aluminum hydroxide, barium carbonate, magnesium hydroxide, or the like is used, and two or more kinds can be used in combination.
Of these, colloidal silica is preferable from the viewpoint of dispersion stability.
When a dispersion stabilizer is used, the amount used (% by weight) is 0.01 to 20 based on the total weight of the vinyl monomer as the constituent unit and the volatile liquid and / or sublimable solid (SL). More preferably, it is 0.1-10, Most preferably, it is 0.5-5.

  In addition, you may use various additives as needed, for example, antioxidants (hindert phenol, phosphorus, lactone, etc.), ultraviolet absorbers (benzotriazole, etc.), antibacterial agents (phenyl ether, etc.) and An antistatic agent (polyamide copolymer or the like) can be added.

The volume average particle size (μm) of the thermally expanded microcapsule is preferably 0.1 to 150, more preferably 0.5 to 100, and particularly preferably 1 to 50.
In addition, when used for lightening materials, such as resin, 10-150 micrometers is preferable, More preferably, it is 20-100 micrometers. Moreover, when using for the coating materials for motor vehicles etc., 0.5-100 micrometers is preferable, More preferably, it is 1-20 micrometers. The volume average particle size is measured by a laser diffraction type particle size distribution measuring apparatus having a measurement principle {light scattering method (25 ° C.)} described in JIS Z8825-1: 2001 {for example, LA-920 manufactured by Horiba, Shimadzu Manufactured by SALD-1100, etc.).
The volume average particle diameter can be controlled by a known method. The type and amount of the surfactant (decreases as the amount increases), the type and amount of the dispersion stabilizer (decreases as the amount increases), the dispersion condition (conditions It can be arbitrarily controlled by, for example, decreasing when tightened).
The shape of the thermally expandable microcapsule may be a needle shape or a flat shape, but is preferably spherical from the viewpoint of expandability. The thickness of the shell varies depending on the volume average particle diameter and the like, but is usually about 0.5 to 75 μm, and can be adjusted by the amount of (SL) (decreasing as the amount is increased).

When the heat-expandable microcapsules of the present invention are heated, the heat-expandable microcapsules can be expanded with a remarkably excellent expansion ratio to form hollow resin particles.
As a heating method, a known method can be applied, and an air dryer, a normal air dryer, a nauter mixer, or the like can be used.
The heating temperature (° C) is preferably {polymer softening temperature (NT) -20 to (NT) +70} ° C (90 to 320 ° C), more preferably 100 to 290, particularly preferably 140 to 200. Most preferably, it is 150-180.
The heating time is preferably 1 minute to 6 hours, more preferably 5 minutes to 3 hours, and particularly preferably 10 minutes to 1 hour.
Heating may be performed in an atmosphere of air, inert gas (such as nitrogen and argon) or vacuum, and resin (urethane resin, acrylic resin, epoxy resin, silicone resin, polyester resin, polyamide resin, polyimide resin, and polyolefin resin) Etc.), in a solvent (DMF, toluene, silicone oil, etc.), etc.
The hollow resin particles can be adjusted in particle size or sharpened in particle size distribution by classification.

The specific gravity (g / cm ³ ) of the hollow resin particles is preferably 0.5 to 0.008, more preferably 0.3 to 0.01, and particularly preferably 0.2 to 0.02.
Here, the specific gravity of the hollow resin particles means the specific gravity (apparent density) of the whole particle including the hollow portion.
The specific gravity is described in 2. of JIS Z8807-1976 “Method for Measuring Solid Specific Gravity”. It is measured according to a measurement method using a specific gravity bottle (liquid; distilled water or methanol).

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Parts or% means parts by weight or% by weight unless otherwise specified.
<Synthesis Example 1>
[Synthesis of 2-methacryloyloxyethyl isocyanate blocked with MEK oxime]
A reaction vessel purged with nitrogen was charged with 64 parts of 2-methacryloyloxyethyl isocyanate, and reacted while dropping 36 parts of MEK oxime slowly so that the reaction temperature became 20-30 ° C. After completion of the dropping, the reaction was carried out at 30 ° C. for 3 hours to obtain MEK oxime block 2-methacryloyloxyethyl isocyanate (vinyl monomer II-1).

<Synthesis Example 2>
[Synthesis of 2-methacryloyloxyethyl isocyanate blocked with butanol]
Butanol block 2-methacryloyloxyethyl isocyanate (vinyl monomer II-2) was obtained in the same manner as in Synthesis Example 1 except that 36 parts of MEK oxime was changed to 70 parts of butanol.

<Synthesis Example 3>
[Synthesis of methacrylic acid blocked with MEK oxime]
A reaction vessel purged with nitrogen was charged with 64 parts of methacrylic acid, and reacted while dropping 77 parts of MEK oxime slowly so that the reaction temperature became 20-30 ° C. MEK oxime block 2 methacrylic acid (vinyl monomer II-3) was obtained by making it react at 30 degreeC after completion | finish of dripping for 10 hours.

<Synthesis Example 4>
[Synthesis of IPDI blocked with MEK oxime]
In a reaction vessel purged with nitrogen, 64 parts of IPDI were charged and reacted while dropping 50 parts by weight of MEK oxime slowly so that the reaction temperature would be 100-110 ° C. MEK oxime block IPDI (crosslinking agent IV-1) was obtained by making it react for 3 hours after completion | finish of dripping.

<Synthesis Example 5>
[Synthesis of terephthalic acid blocked with 2-methylpropene]
80 parts of terephthalic acid was charged in a nitrogen-substituted reaction vessel and reacted while slowly dropping 55 parts by weight of 2-methylpropene so that the reaction temperature became 100 to 110 ° C. 2-methylpropene block terephthalic acid (crosslinking agent IV-2) was obtained by making it react for 3 hours after completion | finish of dripping.

<Example 1>
After uniformly mixing 340 parts of deionized water, 17 parts of a 20% colloidal silica aqueous solution and 10 parts of a 10% adipic acid-diethanolamine condensate aqueous solution and 110 parts of sodium chloride, the MEK oxime block 2-methacryloyloxyethyl isocyanate ( Vinyl monomer II-1) 3.3 mmol part (0.8 part), acrylonitrile 1526 mmol part (80.9 parts), hydroxyethyl methacrylate 3.1 mmol part (0.4 part), ethylene glycol dimethacrylate A solution consisting of 0 mmol part (0.4 part), methyl methacrylate 200 mmol part (20.0 parts), pentane 25 parts and azobisisobutyronitrile 0.5 part was added, and a homomixer (special machine (stock) ) Made by ROBOMICS, 4000rpm) for 1 minute Te, to obtain a suspension. This suspension was transferred to a pressure resistant reactor and polymerized at a gauge pressure of 0.3 MPa and 60 ° C. for 20 hours. Next, the polymerization solution was filtered and then dried at 40 ° C. for 3 hours to obtain thermally expandable microcapsules (1). The volume-average particle diameter and expandability (expansion ratio, expandability ratio) of this thermally expandable microcapsule (1) and the heat resistance of the hollow resin particles were evaluated by the following methods and are shown in Table 1.

<Volume average particle diameter (TH1)>
Measurement sample 0.1g was disperse | distributed to 100 ml of methyl alcohol, and it measured using the laser scattering type particle size distribution measuring device LA-920 (25 degreeC, Horiba Ltd. make).

<Expandability 1>
In a smooth air dryer, 1 g of the measurement sample was heated to 180 ° C. for 15 minutes.
After cooling to 25 ° C., the volume average particle diameter (TH2) was measured in the same manner as described above, and the expansion ratio (BT1) was calculated from the following formula. In addition, it can be said that it is excellent in expansibility, so that a numerical value is large.

<Expansion 2>
Using the measurement sample left at 60 ° C. for 30 days, the expansion ratio (BT2) was calculated in the same manner as the expandability 1, and the expandability ratio (BT2 / BT1) was calculated from the following equation. It was. In addition, it can be said that it is excellent in the expansibility 2, so that a numerical value is small.

<Heat resistance>
About the measurement sample heated by evaluation of the expansibility 1, using a thermogravimetric measuring apparatus TGA-50 (manufactured by Shimadzu Corporation, under nitrogen flow, 10 ° C./min heating rate), the weight reduction rate was 5%. The resulting temperature was measured and made heat resistant. In addition, it can be said that it is excellent in heat resistance, so that a numerical value is high.

<Examples 2 to 11>
A thermally expandable microcapsule was obtained in the same manner as in Example 1 except that the structural unit and the amount used (mole part) shown in Table 1 were used. In addition, Table 1 shows the volume average particle diameter, expandability (expansion ratio, expandability ratio) and heat resistance evaluated in the same manner as in Example 1.

<Comparative Examples 1-2>
A thermally expandable microcapsule was obtained in the same manner as in Example 1 except that the structural unit and the amount used (mole part) shown in Table 1 were used. In addition, Table 1 shows the volume average particle diameter, expandability (expansion ratio, expandability ratio) and heat resistance evaluated in the same manner as in Example 1.

The thermally expandable microcapsule of the present invention can be used in a field where expandability is also required under a wide range of temperature conditions (100 to 200 ° C. or ultrahigh temperature of 200 ° C. or higher depending on the application). For example, it is suitable for automobile paints and expansive inks.
Further, the hollow resin particles obtained by heating and expanding the thermally expandable microcapsules of the present invention can be used in fields where weight reduction and high heat resistance are required. For example, it is suitable for various resin materials and rubber material weight reduction materials, heat fixing materials for fixing rolls of printers, and the like.

Claims (5)

A cyano group-containing vinyl monomer (I);
A vinyl monomer (II) having a functional group (F1) blocked by a blocking agent (II) and / or a crosslinking agent (IV) having (F1);
A vinyl monomer (III) having a functional group (F2) that reacts with (F1) and / or a crosslinking agent (V) having (F2),
A volatile liquid and / or a sublimable solid (SL) is included in a polymer shell (PS) composed of a polymer (P) having (I) and (II) and / or (III) as essential structural units. A thermally expandable microcapsule characterized by comprising: The thermally expandable microcapsule according to claim 1, wherein (F1) is a blocked isocyanate group, and (F2) is a hydroxyl group, an amino group, a carboxy group and / or an epoxy group. The thermally expandable microcapsule according to claim 1, wherein (F1) is a blocked carboxy group and (F2) is a hydroxyl group and / or an amino group. The thermally expandable microcapsule according to claim 1, wherein (F1) is a blocked hydroxyl group, a blocked amino group and / or a blocked carboxy group, and (F2) is an isocyanato group and / or an epoxy group. The thermally expandable microcapsule according to any one of claims 1 to 4 is expanded by heating to a temperature of {polymer (P) softening temperature (NT) -20} to {(NT) + 70 ° C}. Hollow resin particles.