JP2017042617A - Microcapsule and liquid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel microcapsule containing a formaldehyde reaction agent.SOLUTION: A microcapsule has a polycondensate as a film formation component, and contains a formaldehyde reaction agent that has reactivity with formaldehyde and does not have an amino group or a group in which an amino group forms salt.SELECTED DRAWING: None

Description

  The present invention relates to a novel microcapsule and a liquid composition.

  Some building interior materials and furniture are manufactured using formaldehyde-containing adhesives and binders, and some products contain formaldehyde. From such a product, formaldehyde is released, and thus the emitted formaldehyde stays indoors, causing a health hazard to humans and animals. Therefore, development of a remover that removes formaldehyde is underway.

  As such a removing agent, for example, one using a formaldehyde reactant capable of reacting with formaldehyde to convert formaldehyde into another compound is known. It is said that formaldehyde can be removed by treating the target product with such a remover. And as a formaldehyde reaction agent, a hydrazide compound (refer to patent documents 1) etc. are known.

Japanese Patent No. 2913093

  However, the conventional removal agent using a formaldehyde reactant as disclosed in Patent Document 1 is insufficient in terms of long-term sustainability that maintains the removal effect of formaldehyde for a long time. As a result, there is a problem that the amount of the formaldehyde reactant used becomes large.

  On the other hand, in order to maintain the effect for a long period of time without significantly increasing the amount of the active ingredient that exhibits the desired effect, the active ingredient is encapsulated in a microcapsule formed of a film-forming component. In some cases, a technique of microencapsulation may be employed. As the active ingredient is encapsulated inside the microcapsule, it will be gradually released to the outside of the microcapsule over time (indicating sustained release), so that the effect of the active ingredient will last for a long time Become. Such microcapsule technology has been actively studied especially in the fields of medicine, agricultural chemicals and the like. Formaldehyde reactant is also encapsulated in microcapsules and microencapsulated, so that the removal effect of formaldehyde is expected to be sustainable over a long period of time. However, a microcapsule containing a formaldehyde reactant has not been known so far.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the novel microcapsule which included the formaldehyde reagent.

  In order to solve the above-mentioned problems, the present invention provides a formaldehyde reactant that uses a polycondensate as a film-forming component, has reactivity with formaldehyde, and does not have an amino group and a group in which the amino group forms a salt. A microcapsule to be included is provided.

The microcapsule of the present invention preferably further contains a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less.
In the microcapsule of the present invention, the polycondensate is preferably obtained by using an isocyanate compound.
The present invention also provides a liquid composition containing the microcapsules.

  According to the present invention, a novel microcapsule encapsulating a formaldehyde reactant is provided.

<Microcapsule>
The microcapsule of the present invention comprises a polycondensate as a film-forming component, a reactivity with formaldehyde, and an amino group and a group in which the amino group forms a salt (hereinafter referred to as “amino group salt-forming group”). A formaldehyde reactant (hereinafter sometimes abbreviated as “formaldehyde reactant”) that does not have (which may be abbreviated) is included.
By using a polycondensate as a film-forming component, and a formaldehyde reagent having reactivity with formaldehyde and not having an amino group or an amino group salt-forming group, a microcapsule enclosing the formaldehyde reagent is obtained. It can be formed stably.

Examples of the amino group salt-forming group include a group in which the amino group is a monovalent cation moiety, and this cation moiety forms a salt with an anion.
Here, examples of the cation moiety include those in which a hydrogen ion (H ⁺ ) is coordinated to a nitrogen atom of an amino group (—NH ₂ ). In this case, the valence of the anion is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the anion is monovalent, the number of the anions forming the salt and the number of the cation parts are both 1. In addition, when the anion is n-valent (n is an integer of 2 or more), the number of the anions forming the salt is usually 1, and the number of the cation parts is n or less. Is n. In this case, the plurality of the cation moieties may all be the same, all may be different, or only a part may be the same.

  The anion in the amino group salt-forming group is the same as the anion moiety in the group (“—NH—” salt-forming group) described later, wherein the group represented by the formula “—NH—” forms a salt. Things.

[Formaldehyde reagent]
The formaldehyde reactant has reactivity with formaldehyde and does not have an amino group or an amino group salt-forming group. As used herein, “having reactivity with formaldehyde” means having the ability to react with formaldehyde to convert formaldehyde into another compound. That is, the formaldehyde reactant includes a group having reactivity with formaldehyde. By using the microcapsules of the present invention, formaldehyde is removed in the form of conversion to another compound by reaction with a formaldehyde reactant.

The formaldehyde reactant is preferably an organic compound, and as such a formaldehyde reactant, for example, a group represented by the formula “—NH—” (hereinafter abbreviated as ““ —NH— ”group”). And a group represented by the formula “—NH—” is selected from the group consisting of a group forming a salt (hereinafter sometimes abbreviated as ““ —NH— ”salt-forming group”) The compound which has 1 type, or 2 or more types is mentioned. In the formaldehyde reactant, the “—NH—” group indicates reactivity with formaldehyde, and the “—NH—” salt-forming group itself or “—NH—” group becomes this “—NH—” group. The group is presumed to be reactive with formaldehyde.
Formaldehyde reactants are those that do not have amino groups and amino group salt-forming groups, so when formaldehyde reactants have “—NH—” groups or “—NH—” salt-forming groups, the nitrogen in these groups The atom is not further covalently bonded to a hydrogen atom other than one hydrogen atom that is already covalently bonded.

  The total number of “—NH—” groups and “—NH—” salt-forming groups in one molecule of the formaldehyde reactant may be only one, two or more, and if two or more, these two The above groups may be the same as or different from each other. That is, these two or more groups may all be the same, may all be different, or may be partially the same. Usually, these two or more groups are all identical, i.e., are all "-NH-" groups, or all identical " -NH- "salt-forming groups are preferred.

Examples of the “—NH—” salt-forming group include a group in which the “—NH—” group is a monovalent cation moiety, and this cation moiety forms a salt with an anion.
Here, examples of the cation moiety include those in which a hydrogen ion (H ⁺ ) is coordinate-bonded to the nitrogen atom of the “—NH—” group. In this case, the valence of the anion is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the anion is monovalent, the number of the anions forming the salt and the number of the cation parts are both 1. When the anion is m-valent (m is an integer of 2 or more), the number of the anions forming the salt is usually 1, the number of the cation parts is m or less, m It is preferable that In this case, the plurality of the cation moieties may all be the same, all may be different, or only a part may be the same.

The anion in the “—NH—” salt-forming group is not particularly limited, and may be either an inorganic anion or an organic anion.
Preferred inorganic anions include, for example, nitrate ions, sulfate ions, hydrogen sulfate ions, carbonate ions, hydrogen carbonate ions, halide ions, and the like, and the halide ions include fluoride ions, chloride ions, bromides. Ions, iodide ions and the like.
Preferable examples of the organic anion include a carboxylic acid anion and a sulfonic acid anion.
The anion of the carboxylic acid may be an anion of a monocarboxylic acid (monovalent carboxylic acid) or an anion of a polyvalent carboxylic acid such as a dicarboxylic acid or a tricarboxylic acid.

The said anion which a formaldehyde reactant has may be only 1 type, 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
That is, when one molecule of formaldehyde reactant has two or more of the anions, these two or more anions may be all the same, all different, or only partly the same. Also good.
However, the formaldehyde reactant is electrically neutral as a whole molecule, that is, the total value of the valence of the cation moiety and the total value of the valence of the anion in one molecule of the formaldehyde reactant are the same. Preferably there is.

  The total number of “—NH—” groups and “—NH—” salt-forming groups in one molecule of formaldehyde reactant is preferably 1 to 4, and more preferably 1 to 3.

  The positions of the “—NH—” group and the “—NH—” salt-forming group in the molecule of the formaldehyde reagent are not particularly limited. For example, when the formaldehyde reagent has a chain structure, the terminal of the molecule Any position other than the portion may be used.

  The formaldehyde reactant may be linear, branched or cyclic, and may have both a chain structure and a cyclic structure.

When the formaldehyde reactant has a cyclic structure, the ring may be monocyclic or polycyclic, may be either an aliphatic ring or an aromatic ring, and the aliphatic ring and aromatic ring are A condensed polycyclic ring may be used.
When the formaldehyde reactant has a cyclic structure, the “—NH—” group and the “—NH—” salt-forming group may form the ring skeleton of the cyclic structure, or without forming the ring skeleton, It may be bonded to a group forming a ring skeleton.

In the formaldehyde reactant, the nitrogen atom of the “—NH—” group and the “—NH—” salt-forming group is preferably bonded to the nitrogen atom or the carbon atom of the carbonyl group.
The total number of “—NH—” groups and “—NH—” salt-forming groups thus bonded to one carbonyl group may be only one or two.
The total number of “—NH—” groups and “—NH—” salt-forming groups thus bonded to one nitrogen atom may be only one or two, but one. Is preferred.

That is, as a preferable formaldehyde reactant, for example, a group represented by the formula “—C (═O) —NH—” (an amide bond; hereinafter, abbreviated as ““ —C (═O) —NH— ”group”). And a group represented by the formula “—NH—C (═O) —NH—” (hereinafter, abbreviated as ““ —NH—C (═O) —NH— ”group”). ), A group in which a group represented by the formula “—C (═O) —NH—” forms a salt (hereinafter abbreviated as ““ —C (═O) —NH— ”salt-forming group”). A group represented by the formula “—NH—C (═O) —NH—” forming a salt (hereinafter ““ —NH—C (═O) —NH— ”salt formation) Group ”), a group represented by the formula“ ═N—NH— ”(hereinafter sometimes abbreviated as“ “N—NH—” group ”), a formula“ —HN—N ”. (-)-NH- " Groups (hereinafter sometimes abbreviated as ““ —HN—N (—) — NH— ”group”), groups in which the group represented by the formula “═N—NH—” forms a salt ( Hereinafter, a group represented by “(= N—NH—” salt-forming group ”) and a group represented by the formula“ —HN—N (—) — NH— ”(hereinafter referred to as a salt). And those having one or more selected from the group consisting of “sometimes abbreviated as“ —HN—N (—) — NH— ”salt-forming group” ”. Here, for example, the “—HN—N (—) — NH—” group means one nitrogen atom, two “—NH—” group nitrogen atoms, and another group, Means a single bond.
In the “—NH—C (═O) —NH—” salt forming group and “—HN—N (—) — NH—” salt forming group, the number of “—NH—” salt forming groups may be one. It may be two or more.

  As a preferable formaldehyde reactant having a cyclic structure, for example, one or more selected from the group consisting of “—NH—” group and “—NH—” salt-forming group is a ring skeleton having a cyclic structure. , “—C (═O) —NH—” group, “—NH—C (═O) —NH—” group, “—C (═O) —NH—” salt Forming group, “—NH—C (═O) —NH—” salt forming group, “═N—NH—” group, “—HN—N (—) — NH—” group, “═N—NH—” A formaldehyde reagent in which one or more selected from the group consisting of a salt-forming group and a “—HN—N (—) — NH—” salt-forming group forms a ring skeleton having a cyclic structure is more preferable. .

  When the formaldehyde reactant has a cyclic structure, the number of ring members of the ring skeleton, that is, the number of atoms forming the ring skeleton (pieces) is preferably 5 to 7, more preferably Is 5 or 6, and when it is polycyclic, it is preferably 8-10.

  Particularly preferred formaldehyde reactants include, for example, optionally substituted hydantoin and its salt, optionally substituted 2-imidazolidinone and its salt, and optionally substituted. Preferred 5-pyrazolone and salts thereof, optionally having 3-pyrazolone and salts thereof, optionally having 1,2,4-triazol-3-one and salts and substituents thereof Phthalimide and its salt, optionally substituted glycoluril and its salt, optionally substituted pyrazole and its salt, optionally substituted 1,2,3-triazole and a salt thereof, 1,2,4-triazole optionally having a substituent and a salt thereof, and 1,2,3-benzotriazole optionally having a substituent and The salt etc. It is below.

Hydantoin, 2-imidazolidinone, 5-pyrazolone, 3-pyrazolone, 1,2,4-triazol-3-one, phthalimide, glycoluril, pyrazole, 1,2,3-triazole, 1,2,4-triazole And the structure of 1,2,3-benzotriazole is shown below.
Hydantoin, 2-imidazolidinone, 5-pyrazolone, 3-pyrazolone, 1,2,4-triazol-3-one, pyrazole, 1,2,3-triazole and 1,2,4-triazole are all cyclic It is a compound with 5 members. Both phthalimide and 1,2,3-benzotriazole are compounds having 9 ring members. Glycoluril is a compound having 8 ring members.
The compounds shown here are only examples of formaldehyde reagents.

Here, as a salt of hydantoin, for example, one in which one or both of two “—NH—” groups in hydantoin become “—NH—” salt-forming groups can be mentioned.
As the salt of 2-imidazolidinone, for example, one or both of the two “—NH—” groups in 2-imidazolidinone are “—NH—” salt-forming groups. Is mentioned.
Examples of the salt of 5-pyrazolone include, for example, those in which the “—NH—” group in 5-pyrazolone is converted to a “—NH—” salt-forming group, and the nitrogen atom not bonded to a hydrogen atom is a salt. And those in which the “—NH—” group becomes a “—NH—” salt-forming group and the nitrogen atom that is not bonded to a hydrogen atom forms a salt.
Examples of the salt of 3-pyrazolone include those in which one or both of two “—NH—” groups in 3-pyrazolone are converted to “—NH—” salt-forming groups.
In addition, as a salt of 1,2,4-triazol-3-one, for example, one or both of two “—NH—” groups in 1,2,4-triazol-3-one are What became a "-NH-" salt formation group is mentioned.
Moreover, as a salt of phthalimide, for example, one in which one “—NH—” group in phthalimide becomes a “—NH—” salt-forming group can be mentioned.
Examples of the glycoluril salt include those in which at least one of the four “—NH—” groups in the glycoluril is a “—NH—” salt-forming group.

Examples of the pyrazole salt include those in which the “—NH—” group in the pyrazole becomes a “—NH—” salt-forming group, or the nitrogen atom that is not bonded to a hydrogen atom forms a salt. And a group in which a “—NH—” group becomes a “—NH—” salt-forming group and a nitrogen atom not bonded to a hydrogen atom forms a salt.
Examples of the salt of 1,2,3-triazole include, for example, those in which the “—NH—” group in 1,2,3-triazole is converted to a “—NH—” salt-forming group, and bonded to a hydrogen atom. The one in which one or both of the two non-nitrogen atoms form a salt, and the one in which the “—NH—” group becomes a “—NH—” salt-forming group and is not bonded to a hydrogen atom In which one or both of the two nitrogen atoms form a salt.
Examples of 1,2,4-triazole salts include, for example, those in which the “—NH—” group in 1,2,4-triazole is converted to a “—NH—” salt-forming group, and bonded to a hydrogen atom. The one in which one or both of the two non-nitrogen atoms form a salt, and the one in which the “—NH—” group becomes a “—NH—” salt-forming group and is not bonded to a hydrogen atom In which one or both of the two nitrogen atoms form a salt.
Examples of the salt of 1,2,3-benzotriazole include, for example, those in which the “—NH—” group in 1,2,3-benzotriazole becomes a “—NH—” salt-forming group, Either one or both of the two non-bonded nitrogen atoms form a salt, and the “—NH—” group becomes a “—NH—” salt-forming group and is bonded to a hydrogen atom. One in which either one or both of the two nitrogen atoms which are not present forms a salt.

  In the present specification, “having a substituent” means one or more hydrogen atoms (excluding the hydrogen atom in the “—NH—” group and the “—NH—” salt-forming group) of the original compound. ) Is substituted with a group other than a hydrogen atom (substituent).

In the present specification, hydantoin having a substituent is sometimes referred to as “hydantoin derivative”, and hydantoin and hydantoin derivatives are sometimes collectively referred to as “hydantoin compounds”. And the salt of the hydantoin which has a substituent, ie, the salt of a hydantoin derivative, is what a hydantoin derivative formed a salt like the case of a hydantoin. The term “hydantoin optionally having a substituent and a salt thereof” refers in other words to a hydantoin compound and a salt thereof.
In the present specification, the “derivative” means one in which one or more hydrogen atoms of the original compound are substituted with a group other than a hydrogen atom.

The same applies to compounds other than hydantoin.
That is, in this specification, 2-imidazolidinone having a substituent is referred to as a “2-imidazolidinone derivative”, and includes both 2-imidazolidinone and 2-imidazolidinone derivatives, and includes “2-imidazolidinone”. It may be referred to as “non-compound”. And, a salt of 2-imidazolidinone having a substituent, that is, a salt of 2-imidazolidinone derivative, formed a salt in the same manner as in the case of 2-imidazolidinone derivative of 2-imidazolidinone. Is. The “2-imidazolidinone optionally having a substituent and a salt thereof” refers in other words to a 2-imidazolidinone compound and a salt thereof.

  In the present specification, 5-pyrazolone having a substituent may be referred to as “5-pyrazolone derivative”, and 5-pyrazolone and 5-pyrazolone derivatives may be collectively referred to as “5-pyrazolone compounds”. And the salt of 5-pyrazolone which has a substituent, ie, the salt of a 5-pyrazolone derivative, is a salt in which a 5-pyrazolone derivative forms a salt as in the case of 5-pyrazolone. The term “5-pyrazolone optionally having a substituent and a salt thereof” refers in other words to a 5-pyrazolone compound and a salt thereof.

  In the present specification, 3-pyrazolone having a substituent may be referred to as “3-pyrazolone derivative”, and 3-pyrazolone and 3-pyrazolone derivatives may be collectively referred to as “3-pyrazolone compounds”. And the salt of 3-pyrazolone having a substituent, that is, the salt of a 3-pyrazolone derivative is a salt of the 3-pyrazolone derivative as in the case of 3-pyrazolone. The “3-pyrazolone optionally having a substituent and a salt thereof” in other words refers to a 3-pyrazolone compound and a salt thereof.

  In the present specification, 1,2,4-triazol-3-one having a substituent is referred to as a “1,2,4-triazol-3-one derivative” and referred to as 1,2,4-triazol-3-one. And 1,2,4-triazol-3-one derivatives may be collectively referred to as “1,2,4-triazol-3-one compounds”. A salt of 1,2,4-triazol-3-one having a substituent, that is, a salt of a 1,2,4-triazol-3-one derivative is 1,2,4-triazol-3-one. The derivative forms a salt as in the case of 1,2,4-triazol-3-one. The phrase “1,2,4-triazol-3-one optionally having a substituent and a salt thereof” means, in other words, a 1,2,4-triazol-3-one compound and a salt thereof. is there.

  In the present specification, a phthalimide having a substituent is referred to as a “phthalimide derivative”, and phthalimide and a phthalimide derivative are sometimes collectively referred to as a “phthalimide compound”. And the salt of the phthalimide which has a substituent, ie, the salt of a phthalimide derivative, forms a salt similarly to the case of a phthalimide derivative. The “phthalimide optionally having a substituent and a salt thereof” refers in other words to a phthalimide compound and a salt thereof.

  In the present specification, glycoluril having a substituent is referred to as “glycoluril derivative”, and glycoluril and glycoluril derivatives are sometimes collectively referred to as “glycoluril-based compounds”. A glycoluril salt having a substituent, that is, a salt of a glycoluril derivative is a salt formed by the glycoluril derivative in the same manner as in the case of glycoluril. The term “glycoluril optionally having a substituent and a salt thereof” refers to a glycoluril-based compound and a salt thereof in other words.

  In the present specification, a pyrazole having a substituent is referred to as a “pyrazole derivative”, and pyrazole and a pyrazole derivative may be collectively referred to as a “pyrazole compound”. And the salt of the pyrazole which has a substituent, ie, the salt of a pyrazole derivative, forms a salt like the case where the pyrazole derivative is pyrazole. The “pyrazole optionally having a substituent and a salt thereof” is, in other words, a pyrazole compound and a salt thereof.

  In the present specification, 1,2,3-triazole having a substituent is referred to as “1,2,3-triazole derivative” and includes 1,2,3-triazole and 1,2,3-triazole derivatives. Sometimes referred to as “1,2,3-triazole compounds”. And a salt of 1,2,3-triazole having a substituent, that is, a salt of a 1,2,3-triazole derivative is a case where the 1,2,3-triazole derivative is 1,2,3-triazole. In the same manner as above, a salt is formed. The phrase “1,2,3-triazole optionally having a substituent and a salt thereof” refers to a 1,2,3-triazole compound and a salt thereof in other words.

  In the present specification, 1,2,4-triazole having a substituent is referred to as “1,2,4-triazole derivative” and includes 1,2,4-triazole and 1,2,4-triazole derivatives. Sometimes referred to as “1,2,4-triazole compounds”. And, a salt of 1,2,4-triazole having a substituent, that is, a salt of a 1,2,4-triazole derivative is a case where the 1,2,4-triazole derivative is 1,2,4-triazole. In the same manner as above, a salt is formed. The phrase “1,2,4-triazole optionally having a substituent and a salt thereof” means, in other words, a 1,2,4-triazole compound and a salt thereof.

  In the present specification, 1,2,3-benzotriazole having a substituent is referred to as a “1,2,3-benzotriazole derivative” and is referred to as 1,2,3-benzotriazole and 1,2,3-benzotriazole. Derivatives are sometimes collectively referred to as “1,2,3-benzotriazole compounds”. A 1,2,3-benzotriazole salt having a substituent, that is, a salt of a 1,2,3-benzotriazole derivative, means that a 1,2,3-benzotriazole derivative is 1,2,3- As in the case of benzotriazole, a salt is formed. The phrase “1,2,3-benzotriazole and a salt thereof optionally having a substituent” refers to a 1,2,3-benzotriazole-based compound and a salt thereof in other words.

  The substituent is not particularly limited, and preferred examples include an alkyl group, an alkenyl group, an aryl group, an aralkyl group (arylalkyl group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, and the like. .

The alkyl group in the substituent may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.
The alkyl group preferably has 1 to 10 carbon atoms.

  The linear or branched alkyl group preferably has 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methyl Pentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl Group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl , Isooctyl group, 2-ethylhexyl group, nonyl group, decyl group.

  The cyclic alkyl group preferably has 3 to 10 carbon atoms. Examples of the alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. , A cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, a tricyclodecyl group, and the like. Furthermore, one or more hydrogen atoms of these cyclic alkyl groups are linear, branched Examples thereof include those substituted with a chain or cyclic alkyl group. Here, examples of the linear, branched, and cyclic alkyl groups for substituting a hydrogen atom include the same alkyl groups listed as substituents of the above-mentioned formaldehyde reactant.

  The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

Examples of the alkenyl group in the substituent include a group in which one single bond (C—C) between carbon atoms of the alkyl group is substituted with a double bond (C═C). Examples include ethenyl group (vinyl group), 2-propenyl group (allyl group), cyclohexenyl group and the like.
The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

The aryl group in the substituent may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group), and the like. One or more hydrogen atoms of these aryl groups are further substituted with these aryl groups and the above-mentioned formaldehyde reagents. The thing substituted by the mentioned alkyl group is also mentioned. The aryl group having these substituents preferably has 6 to 15 carbon atoms including the substituents.
The aryl group preferably has 6 to 10 carbon atoms.

Examples of the aralkyl group in the substituent include a monovalent group in which one hydrogen atom of the alkyl group is substituted with the aryl group, such as a benzyl group (phenylmethyl group) and a phenethyl group (phenylethyl group). Is mentioned.
The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 11 carbon atoms.

Examples of the alkoxy group in the substituent include monovalent groups in which the alkyl group is bonded to an oxygen atom, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a cyclopropoxy group.
The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5.

Examples of the alkenyloxy group in the substituent include monovalent groups formed by bonding the alkenyl group to an oxygen atom, such as ethenyloxy group (vinyloxy group), 2-propenyloxy group (allyloxy group), and cyclohexenyloxy group. Is mentioned.
The alkenyloxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

Examples of the aryloxy group in the substituent include monovalent groups formed by bonding the aryl group to an oxygen atom, such as a phenyloxy group and a 1-naphthyloxy group.
The aryloxy group preferably has 6 to 10 carbon atoms.

Examples of the aralkyloxy group in the substituent include monovalent groups in which the aralkyl group is bonded to an oxygen atom, such as a benzyloxy group (phenylmethyloxy group) and a phenethyloxy group (phenylethyloxy group). It is done.
The aralkyloxy group preferably has 7 to 20 carbon atoms, and more preferably 7 to 11 carbon atoms.

Only one substituent may be included in one molecule of formaldehyde reactant, or two or more substituents. When there are two or more substituents, these substituents may be the same as or different from each other. That is, two or more substituents may all be the same, may all be different, or may be the same in only part.
Usually, the number of the substituents contained in one molecule of the formaldehyde reagent is preferably 1 to 4, and more preferably 1 to 3.

The position of the substituent in the molecule of the formaldehyde reagent is not particularly limited. For example, when the formaldehyde reagent has a chain structure, it may be the terminal part of the molecule or other than the terminal part. It may be a site.
When the formaldehyde reactant has two or more of the above substituents, the bonding positions of these substituents may all be the same, all may be different, or only a part may be the same.

Among the above-mentioned particularly preferred formaldehyde reagents, those having the above substituents include 5,5-dimethylhydantoin which is a hydantoin derivative; 3-methyl-5-pyrazolone which is a 5-pyrazolone derivative; 3, which is a pyrazole derivative; 5-dimethylpyrazole; 3-n-butyl-1,2,4-triazole, which is a 1,2,4-triazole derivative, 3,5-dimethyl-1,2,4-triazole, 3,5-di-n -Butyl-1,2,4-triazole, 3,5-diphenyl-1,2,4-triazole; 4-methyl-1H-benzotriazole, which is a 1,2,3-benzotriazole derivative, 5-methyl-1H -A benzotriazole etc. are mentioned.
5,5-dimethylhydantoin, 3-methyl-5-pyrazolone, 3,5-dimethylpyrazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3,5-Di-n-butyl-1,2,4-triazole and 3,5-diphenyl-1,2,4-triazole are both compounds having 5 ring members. 4-Methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole are both compounds having 9 ring members.
In addition, the compound shown here is only an example of the formaldehyde reagent which has the said substituent.

  The formaldehyde reactant is preferably solid at room temperature. And when using the formaldehyde reagent which is solid at normal temperature, it is preferable to use together the solvent mentioned later. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example.

  Particularly preferred formaldehyde reactants include, for example, hydantoin, 5,5-dimethylhydantoin, 2-imidazolidinone, 5-pyrazolone, 3-methyl-5-pyrazolone, 3-pyrazolone, 3,5-dimethylpyrazole, Phthalimide, glycoluril, 1,2,3-triazole, 1,2,4-triazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3 , 5-Di-n-butyl-1,2,4-triazole, 3,5-diphenyl-1,2,4-triazole, 1,2,4-triazol-3-one, 1,2,3-benzo Examples include triazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole.

  The formaldehyde reactant contained in the microcapsule of the present invention may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The amount (content) of the formaldehyde reactant contained in the microcapsule of the present invention is not particularly limited and can be appropriately adjusted according to the purpose.
The amount (content) of the formaldehyde reactant contained in the microcapsule of the present invention can be adjusted, for example, according to the microcapsule production conditions described later.

[Film forming component]
The microcapsule of the present invention uses a polycondensate as a film-forming component. In the present invention, the “film-forming component” is a component that forms an outer shell film that encloses an active formaldehyde reagent.
The polycondensate is an oligomer or polymer and is not particularly limited as long as it is an organic compound having film-forming ability, but an interfacial polycondensate obtained by an interfacial polycondensation method is preferred. By using the interfacial polycondensate, better quality microcapsules can be obtained.

Preferred examples of the polycondensate include polyurea, polyurethane, and polyamide.
Here, “polyurea” means an oligomer or polymer having a bond (urea bond) represented by the formula “—NH—C (═O) —NH—”. It can be obtained by polycondensation reaction of an isocyanate compound having an isocyanate group and an amine compound having two or more amino groups.
“Polyurethane” means an oligomer or polymer having a bond (urethane bond) represented by the formula “—NH—C (═O) —O—”. For example, as a raw material compound, two or more It can be obtained by polycondensation reaction of an isocyanate compound having an isocyanate group and a hydroxy compound having two or more hydroxyl groups (—OH).
In addition, “polyamide” means an oligomer or polymer having a bond (amide bond) represented by the formula “—NH—C (═O) —”. For example, as a raw material compound, two or more carboxy groups A carboxylic acid having (—C (═O) —OH), or a carboxylic acid chloride in which one or more carboxy groups are substituted with a chlorocarbonyl group (—C (═O) —Cl); It can be obtained by polycondensation reaction with an amine compound having two or more amino groups.

  The isocyanate compound for producing polyurea and polyurethane preferably has no amino group or hydroxyl group, and more preferably has neither an amino group nor a hydroxyl group.

  The number of isocyanate groups in the molecule of the isocyanate compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, The number is more preferably 4, and particularly preferably 2 or 3.

  Examples of the isocyanate compound include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, xylylene-1,3-diisocyanate, xylene-1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate, and diphenylmethane. Organic polyvalent isocyanate compounds such as -2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate; Derivatives of polyisocyanate compounds (provided that the isocyanate group is not substituted); trimethylol pro of the organic polyisocyanate compounds Emissions adducts; derivative of the organic polyvalent isocyanate compound (provided that the isocyanate groups is not intended to be replaced) include trimethylolpropane adduct of. In the present specification, the trimethylolpropane adduct may be referred to as a trimethylolpropane adduct.

  The said isocyanate compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  The amine compound for producing polyurea preferably has no isocyanate group or hydroxyl group, and more preferably has neither an isocyanate group nor a hydroxyl group.

  The number of amino groups in the molecule of the amine compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, The number is more preferably 4, and particularly preferably 2 or 3.

  Examples of the amine compound include organic polyvalent amine compounds such as melamine, urea, and 1,3-bis (aminomethyl) cyclohexane.

  The said amine compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  The hydroxy compound for producing polyurea preferably has no isocyanate group or amino group, and more preferably has neither an isocyanate group nor an amino group.

  The number of hydroxyl groups in one molecule of the hydroxy compound is not particularly limited as long as it is 2 or more, but is preferably 2-6, more preferably 2-5, The number is more preferably 4, and particularly preferably 2 or 3.

  Examples of the hydroxy compound include organic polyvalent hydroxy compounds. Examples of the organic polyvalent hydroxy compound include alkylene glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol.

  The said hydroxy compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

As said amine compound for manufacturing polyamide, the same thing as the said amine compound for forming the above-mentioned polyurea is mentioned except not having a carboxy group, for example.
Examples of the amine compound for producing polyamide include aliphatic polyvalent amine compounds such as hexamethylenediamine, nonanediamine, methylpentadiamine, and diethylenetriamine.

  The number of amino groups in one molecule of the amine compound for producing the polyamide is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, preferably 2 to 5. Is more preferable, 2 to 4 is more preferable, and 2 or 3 is particularly preferable.

  The amine compound for producing the polyamide may be used singly or in combination of two or more, and when two or more are used in combination, their combination and ratio are arbitrarily selected. it can.

The carboxylic acid for producing the polyamide does not have an amino group.
The number of carboxy groups in one molecule of the carboxylic acid is not particularly limited as long as it is 2 or more, but is preferably 2-6, more preferably 2-5, The number is more preferably 4, and particularly preferably 2 or 3.

  Examples of the carboxylic acid include adipic acid (hexanedioic acid), sebacic acid (decanedioic acid), terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), and the like. Organic polyvalent carboxylic acid (aliphatic polyvalent carboxylic acid, aromatic polyvalent carboxylic acid) and the like.

  The carboxylic acid chloride for producing polyamide is obtained by substituting one or two or more carboxy groups of the carboxylic acid with chlorocarbonyl groups, and all the carboxy groups of the carboxylic acid are chlorocarbonyl groups. It may be substituted with.

  The carboxylic acid and the carboxylic acid chloride for producing the polyamide may be used singly or in combination of two or more, when two or more are used in combination, The ratio can be arbitrarily selected.

  Among the above, the polycondensate is preferably obtained by using an isocyanate compound, and more preferable examples include polyurea and polyurethane.

  The polycondensation may be performed by a known method, and the conditions may be appropriately selected in consideration of the type of raw material compound used.

  For example, when interfacial polycondensation is performed, microcapsules encapsulating the formaldehyde reactant can be obtained at once by subjecting the raw material compounds to polycondensation in the presence of the encapsulated formaldehyde reactant. Hereinafter, a method for forming the film-forming component by interfacial polycondensation as described above and producing the microcapsule of the present invention will be described.

  The amount of the essential two groups of raw material compounds to be polycondensed may be appropriately adjusted according to the polycondensation method and the kind of the raw material compounds. Here, the “essential two groups of raw material compounds to be polycondensed” means components essential for constituting the main skeleton of the polycondensate that is a film forming component, and when the polycondensate is polyurea. Means the isocyanate compound and amine compound, and when the polycondensate is polyurethane, it means the isocyanate compound and hydroxy compound, and when the polycondensate is polyamide, the carboxylic acid or carboxylic acid chloride and amine are used. Means a compound.

  For example, when polyurea is obtained by interfacial polycondensation using the isocyanate compound and amine compound, the amount of the isocyanate compound and amine compound used is [number of moles of amino groups in the amine compound]: [in isocyanate compound] The molar ratio of the number of moles of isocyanate groups] is preferably 10:90 to 60:40, and more preferably 20:80 to 40:60. When the number of moles of amino groups in the amine compound is set to be smaller than the number of moles of isocyanate groups in the isocyanate compound, a higher quality microcapsule can be obtained.

  For example, when a polyurethane is obtained by interfacial polycondensation using the isocyanate compound and the hydroxy compound, the amount of the isocyanate compound and hydroxy compound used is [number of moles of hydroxyl groups in the hydroxy compound]: [in the isocyanate compound The molar ratio of the number of moles of isocyanate groups] is preferably 10:90 to 60:40, and more preferably 20:80 to 40:60. When the number of moles of hydroxyl groups in the hydroxy compound is set to be smaller than the number of moles of isocyanate groups in the isocyanate compound, higher quality microcapsules can be obtained.

  So far, the polycondensate has been described as one obtained by polycondensation of any of the isocyanate compound, amine compound, hydroxy compound, carboxylic acid and carboxylic acid chloride. It may be obtained by polycondensation of other compounds not corresponding to any of isocyanate compounds, amine compounds, hydroxy compounds, carboxylic acids and carboxylic acid chlorides.

The other compound is not particularly limited as long as it can be polycondensed.
Only one kind of the other compound may be used, or two or more kinds thereof may be used, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

  For example, when polyurea is obtained by polycondensation of the other compound in addition to the isocyanate compound and amine compound, the amount of the other compound used is the total amount of the isocyanate compound and amine compound used. It is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less with respect to (number of moles).

  Similarly, when the polyurethane is obtained by polycondensation of the other compound in addition to the isocyanate compound and hydroxy compound, the amount of the other compound used is the total use of the isocyanate compound and hydroxy compound. It is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less with respect to the amount (number of moles).

  Similarly, when the polyamide is obtained by polycondensation of the other compound in addition to the carboxylic acid, carboxylic acid chloride and amine compound, the amount of the other compound used is It is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less, based on the total amount (mol number) of acid chloride and amine compound used.

  The amount of the formaldehyde reactant used during the polycondensation is not particularly limited, but is preferably 2 to 65 parts by mass with respect to 100 parts by mass of the total amount of the above-mentioned two essential raw material compounds to be polycondensed. 2 to 61 parts by mass, more preferably 2 to 57 parts by mass, for example, 2 to 50 parts by mass, 4 to 30 parts by mass, and 6 to 15 parts by mass. Also good.

(solvent)
The microcapsule of the present invention may contain a solvent in order to dissolve the formaldehyde reactant. In this case, the interfacial polycondensation is preferably performed by emulsifying the reaction solution in a mixed solvent of water and a hydrophobic solvent (plasticizer). In this way, microcapsules that encapsulate the formaldehyde reactant and the hydrophobic solvent can be obtained at once by polycondensation of the raw material compound in the presence of the formaldehyde reactant to be encapsulated and the hydrophobic solvent.
Moreover, when emulsifying a reaction liquid, you may use together the emulsifier mentioned later.

  Examples of the hydrophobic solvent include alcohol, amide, nitrile, ketone, ester, ether, hydrocarbon, halogenated hydrocarbon, phenol (a compound having a phenolic hydroxyl group), carbon sulfide, and carboxylic acid.

The hydrophobic solvent preferably has an SP value (solubility parameter) of 12 (cal / cm ³ ) ^1/2 or less. By using such a solvent, the reaction liquid at the time of interfacial polycondensation easily becomes an oil-in-water (O / W type) dispersion in which the oil component is dispersed in water, and the film-forming component And formation of microcapsules becomes easier.
That is, microcapsules enclosing a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less are particularly preferable among the microcapsules of the present invention.

The lower limit of the SP value of the hydrophobic solvent is not particularly limited, but is preferably 6.5 (cal / cm ³ ) ^1/2 . Such a hydrophobic solvent having an SP value is easily available.

Examples of the solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less include:
1-propanol (11.9), 2-propanol (11.5), 1-butanol (11.4), cyclohexanol (11.4), 2-methoxyethanol (10.8), 1-hexanol (10 .7), alcohols such as 2-methyl-2-propanol (10.6), 1-butoxy-2-propanol (10.4), 2-ethylhexanol (9.5);
Amides such as dimethylformamide (12.0);
Nitriles such as acetonitrile (11.8);
Ketones such as acetone (10.0), methyl ethyl ketone (9.3), methyl propyl ketone (8.7), methyl isopropyl ketone (8.5);
Di-n-butyl phthalate (9.4), ethyl acetate (9.1), bis (2-ethylhexyl) sebacate (8.7), n-butyl acetate (8.5), isopropyl acetate (8.4) ), Esters such as isobutyl acetate (8.3) (carboxylic acid esters);
Linear and cyclic ethers such as dioxane (9.9), tetrahydrofuran (9.1), diethyl ether (7.4), isopropyl ether (6.9);
Benzene (9.2), toluene (8.9), xylene (8.8), ethylbenzene (8.8), cyclohexane (8.2), n-octane (7.6), n-hexane (7. 3) aromatic and aliphatic hydrocarbons such as n-pentane (7.0);
Halogenated hydrocarbons (halogenated aliphatic hydrocarbons) such as methylene chloride (9.7), chloroform (9.3), trichlorethylene (9.2), carbon tetrachloride (8.6);
Carbon sulfide such as carbon disulfide (10.0);
Phenols such as phenol (11.5);
And carboxylic acids such as acetic acid (10.1). The numerical value in parentheses written in parallel with the solvent name means SP value ((cal / cm ³ ) ^1/2 ).

  The said solvent may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  Although the usage-amount of the said solvent is not specifically limited, Usually, it is preferable that it is 200-5000 mass parts with respect to 100 mass parts of usage-amounts of a formaldehyde reagent, and it is more preferable that it is 300-4000 mass parts. 400 to 3000 parts by mass is particularly preferable.

(emulsifier)
The emulsifier may be a known one and is not particularly limited.
Preferred emulsifiers include, for example, polyvinyl alcohol (sometimes abbreviated as “PVA” in the present specification), carboxymethyl cellulose (sometimes abbreviated as “CMC” in the present specification), ethyl cellulose, methyl cellulose, and kaizen. , Gum arabic, gelatin, funnel oil, alkylbenzene sulfonate such as sodium benzenesulfonate, sodium dodecylbenzenesulfonate, polyoxyethylene sulfate, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, Examples include isobutylene-maleic anhydride copolymer and poly (meth) acrylic acid.
In this specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.

The said emulsifier may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
The usage-amount of the said emulsifier is not specifically limited, What is necessary is just to adjust suitably according to the kind.

In the present invention, the interfacial polycondensation temperature is usually preferably 60 to 110 ° C, more preferably 65 to 100 ° C, and particularly preferably 70 to 90 ° C.
The interfacial polycondensation time is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, and particularly preferably 1.5 to 3 hours.

After the polycondensation, for example, the microcapsules of the present invention are obtained as an aqueous dispersion.
The obtained microcapsules may be used as they are for the intended use, or may be used for the intended use after performing known post-treatment, purification, etc., if necessary, and the dispersion medium is removed. It may be used for the intended purpose.

When the microcapsule of the present invention contains, for example, one or more selected from the group consisting of polyurea, polyurethane and polyamide as a film-forming component, the polyurea, polyurethane and Any one or both of other oligomers and polymers that do not correspond to any polyamide may be used as a film-forming component.
As for said other oligomer and polymer, all may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

In the microcapsule of the present invention, the ratio of the total content of the other oligomer and polymer to the total content of the film-forming component is preferably 5% by mass or less, more preferably 3% by mass or less. 1% by mass or less is particularly preferable.
That is, in the microcapsule of the present invention, the ratio of the total content of polyurea, polyurethane and polyamide to the total content of film-forming components is preferably 95% by mass or more, more preferably 97% by mass or more. It is preferably 99% by mass or more.

The average particle size of the microcapsules of the present invention is not particularly limited, but is preferably 0.5 to 20 μm, more preferably 0.5 to 16 μm, and further preferably 0.5 to 13 μm. For example, any of 0.5-10 micrometers, 1-7 micrometers, and 1.5-4 micrometers may be sufficient.
In the present specification, “average particle diameter” means the median value D ₅₀ of the cumulative volume distribution measured by a method using a Coulter counter unless otherwise specified.

  In the microcapsule of the present invention, the thickness of the outer shell film enclosing the formaldehyde reagent is preferably 30 to 500 nm, and more preferably 50 to 300 nm.

  The microcapsule of the present invention may include other components in addition to the formaldehyde reactant and the solvent, reflecting the production method.

  The microcapsule of the present invention is obtained for the first time as containing a formaldehyde reactant. The microcapsules of the present invention can encapsulate the formaldehyde reactant because, for the film-forming component that is a polycondensate, the formaldehyde reactant to be encapsulated is selected to have no amino group or amino group salt-forming group. by. When a formaldehyde reagent having an amino group or an amino group salt-forming group is used, an essential raw material compound (for example, a polycondensate) is formed when forming a film-forming component that is a polycondensate during the production of microcapsules. It is speculated that the isocyanate compound, carboxylic acid, carboxylic acid chloride, etc.) reacts with a formaldehyde reactant having an amino group or an amino group salt-forming group to inhibit the formation of microcapsules. On the other hand, at the time of manufacturing the microcapsules of the present invention, it is speculated that the inhibition of the formation of such microcapsules may be suppressed by using a formaldehyde reagent having no amino group or amino group salt-forming group. Is done.

  The microcapsule of the present invention uses a polycondensate as a film-forming component and encapsulates a formaldehyde reagent that does not have an amino group or an amino group salt-forming group. Sustained release properties. Therefore, the microcapsules of the present invention can maintain the effect of removing formaldehyde for a long period of time, and are suitable as a component of a remover that removes formaldehyde that tends to stay indoors, for example.

  The microcapsule of the present invention can be improved in strength against water (sometimes referred to as “water resistance” in the present specification) by selecting a constituent material having a specific range. Microcapsules with high water resistance are advantageous in that the sustained release properties of formaldehyde reagents when coexisting with water can be maintained for a longer period of time. For example, in an aqueous dispersion in which microcapsules are dispersed in water, which corresponds to a liquid composition to be described later, due to the high water resistance of the microcapsules, the release of the formaldehyde reagent from the inside of the microcapsules into the water is further improved. Highly suppressed. Therefore, when this aqueous dispersion is used for the intended purpose, the sustained-release property of the formaldehyde reactant can be maintained for a longer period, so that the effect of removing formaldehyde can be continuously obtained for a longer period.

  The water resistance of the microcapsules is, for example, by preparing an aqueous dispersion of microcapsules or a mixture in which the aqueous dispersion is further added to water, and after a certain period of time, in the aqueous dispersion or mixture, from inside the microcapsules. This can be confirmed by quantifying the amount of formaldehyde reactant released (extracted) and present in the water. It can be said that the smaller the amount of formaldehyde reactant in water, the higher the water resistance of the microcapsule.

In terms of improving the water resistance of the microcapsule, preferred formaldehyde reagents include, for example, the 1,2,3-triazole compounds and salts thereof, the 1,2,4-triazole compounds and salts thereof, and the above. Examples thereof include compounds having a triazole skeleton such as 1,2,3-benzotriazole compounds and salts thereof.
The 1,2,3-triazole compound is preferably 1,2,3-triazole.
The 1,2,4-triazole compounds include 1,2,4-triazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3, 5-Di-n-butyl-1,2,4-triazole or 3,5-diphenyl-1,2,4-triazole is preferred.
The 1,2,3-benzotriazole-based compound is preferably 1,2,3-benzotriazole, 4-methyl-1H-benzotriazole, or 5-methyl-1H-benzotriazole.

In terms of improving the water resistance of the microcapsules, the preferable solvent is, for example, an SP value of 6.5 (cal / cm ³ ) ^1/2 or more and less than 10.4 (cal / cm ³ ) ^1/2. And more specifically,
Alcohols such as 2-ethylhexanol (9.5);
Ketones such as acetone (10.0), methyl ethyl ketone (9.3), methyl propyl ketone (8.7), methyl isopropyl ketone (8.5);
Di-n-butyl phthalate (9.4), ethyl acetate (9.1), bis (2-ethylhexyl) sebacate (8.7), n-butyl acetate (8.5), isopropyl acetate (8.4) ), Esters such as isobutyl acetate (8.3) (carboxylic acid esters);
Linear and cyclic ethers such as dioxane (9.9), tetrahydrofuran (9.1), diethyl ether (7.4), isopropyl ether (6.9);
Benzene (9.2), toluene (8.9), xylene (8.8), ethylbenzene (8.8), cyclohexane (8.2), n-octane (7.6), n-hexane (7. 3) aromatic and aliphatic hydrocarbons such as n-pentane (7.0);
Halogenated hydrocarbons (halogenated aliphatic hydrocarbons) such as methylene chloride (9.7), chloroform (9.3), trichlorethylene (9.2), carbon tetrachloride (8.6);
Carbon sulfide such as carbon disulfide (10.0);
And carboxylic acids such as acetic acid (10.1).
Among these, as for the said solvent, what has SP value of 6.5-9.5 (cal / cm < ³ >) < ^1/2 > is more preferable.

In terms of improving the water resistance of the microcapsules, a preferable film-forming component is, for example, polyurea.
The polyurea is selected from the group consisting of isophorone diisocyanate, a derivative of isophorone diisocyanate (provided that the isocyanate group is not substituted), and a trimethylolpropane adduct of isophorone diisocyanate as the isocyanate compound as a raw material compound. What was obtained using the seed | species or 2 or more types is preferable.

  In terms of improving the water resistance of the microcapsules, preferable examples of the emulsifier include carboxymethylcellulose.

<How to use microcapsules>
[Resin composition]
The microcapsule of the present invention is suitable, for example, as a component contained in the resin composition. Such a resin composition is not particularly limited as long as it contains the microcapsules and the resin of the present invention, and can be in any form.

Preferred examples of the resin composition include those for resin molded products containing the microcapsules.
The resin can be arbitrarily selected according to the purpose. For example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, Examples thereof include synthetic resins such as polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, and polyimide.
Examples of the resin include polybutadiene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, synthetic rubber such as ethylene rubber, propylene rubber, and silicon rubber.

Examples of the resin molded product include constituent materials such as building interior materials and furniture.
The shape of the resin molded product can be arbitrarily selected according to the purpose, and can be, for example, a sheet shape, a plate shape (plate shape), a block shape, or the like.

  However, the resin composition mentioned here is only one example using the microcapsule of the present invention, and the resin composition using the microcapsule of the present invention is not limited to these.

  The resin composition can be produced, for example, by blending the microcapsules of the present invention, a resin, and other components such as a curing agent and a solvent as necessary. And the obtained resin composition should just be shape | molded by the well-known method suitable according to the compounding component and the objective.

[Liquid composition]
The microcapsule of the present invention is suitable as a component contained in a liquid composition, for example. Such a liquid composition is not particularly limited as long as it contains the microcapsules of the present invention and a solvent (dispersion medium), and may be a solution, a dispersion, or any form. It can be.

As a preferable thing in the said liquid composition, the coating material containing the said microcapsule is mentioned, for example. Such a paint can be used for adhering to an object to be removed of formaldehyde, such as an interior material (for example, wallpaper) or furniture of a building, furniture, or a constituent material of the interior material or furniture.
Here, the coating material containing the microcapsules may be a known one, and examples thereof include oil-based coatings, alcoholic coatings, cellulose coatings, synthetic resin coatings, water-based coatings, lacquer coatings, rubber coatings, and the like. An aqueous dispersion obtained by dispersing in an aqueous solution may be used, and may be appropriately selected according to the purpose.

  However, the liquid composition mentioned here is only one example using the microcapsule of the present invention, and the liquid composition using the microcapsule of the present invention is not limited thereto.

  The liquid composition can be produced, for example, by blending the microcapsules, a liquid medium such as a solvent (dispersion medium), and other components as necessary. And the obtained liquid composition should just be used by the well-known method suitable according to the compounding component and the objective.

The liquid composition can be attached to a target object by a known method such as a printing method, a coating method, or a dipping method.
Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, gravure printing method, gravure offset printing method, pad printing method and the like. It is done.
Examples of the coating method include various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, a gravure coater, and a wire bar. A method is mentioned.
What is necessary is just to dry the said liquid composition made to adhere as needed.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

[Example 1]
<Manufacture of microcapsules>
1-butoxy-2-propanol (manufactured by Kanto Chemical Co., Inc., 50 g) and an ethyl acetate solution of trimethylolpropane adduct of tolylene-2,4-diisocyanate having a concentration of 75% by mass ("Takenate D-" manufactured by Mitsui Chemicals, Inc.) 103H ", 25 g, and solid content 18.75 g), 5,5-dimethylhydantoin (manufactured by Tokyo Chemical Industry Co., Ltd., 2 g) was added and dissolved. Next, the obtained mixture was added to a polyvinyl alcohol aqueous solution (150 g, solid content: 7.5 g) having a concentration of 5% by mass, and using an emulsifier (manufactured by PRIMIX Co., Ltd.), the rotation speed was 12000 rpm and the time was 10 minutes. Emulsified under conditions. Melting melamine (manufactured by Tokyo Chemical Industry Co., Ltd., 2.44 g) in distilled water (30 g), then adding the entire amount of this melamine aqueous solution to the emulsion obtained above and stirring at 80 ° C. for 2 hours. Then, interfacial polycondensation was performed.
As described above, a polycondensate of melamine and a trimethylolpropane adduct of tolylene-2,4-diisocyanate (hereinafter sometimes abbreviated as “TDI-TMP adduct”) is used as a film-forming component, and formaldehyde reaction 5,5-dimethylhydantoin as an agent, 1-butoxy-2-propanol (SP value: 10.4 (cal / cm ³ ) ^1/2 ) and ethyl acetate (SP value: 9.1 (cal / cm) as a solvent ³ ) A microcapsule encapsulating ^1/2 ) was obtained as an aqueous dispersion.

  The microcapsule aqueous dispersion obtained above was coated on fine paper using a bar coater, dried at 105 ° C. for 90 seconds, and then magnified 5000 times using an electron microscope (manufactured by JEOL Ltd.). Then, the coating and drying sites were observed to confirm that the desired microcapsules were obtained. The average particle diameter of the obtained microcapsules was measured using a Coulter counter (manufactured by Beckman Coulter, Inc.) and found to be 2.3 μm. These results are shown in Table 2.

[Example 2]
As shown in Table 1, in place of 5,5-dimethylhydantoin (2 g), 2-capsulidinone (manufactured by Tokyo Chemical Industry Co., Ltd., 2 g) was used except that microcapsules were used in the same manner as in Example 1. Manufactured.
It was confirmed that the intended microcapsules were obtained by the same method as in Example 1, and the average particle size of the microcapsules was measured. As a result, it was 2.1 μm. The results are shown in Table 2.

[Example 3]
As shown in Table 1, in the same manner as in Example 1, except that 3-methyl-5-pyrazolone (manufactured by Tokyo Chemical Industry Co., Ltd., 2 g) was used instead of 5,5-dimethylhydantoin (2 g). Microcapsules were produced.
It was confirmed that the intended microcapsules were obtained by the same method as in Example 1, and the average particle size of the microcapsules was measured. As a result, it was 2.3 μm. The results are shown in Table 2.

[Example 4]
As shown in Table 1, microcapsules were produced in the same manner as in Example 1 except that instead of melamine (2.44 g), the same number of moles of urea was used.
The obtained microcapsule has a polycondensate of melamine and TDI-TMP adduct as a film-forming component, 5,5-dimethylhydantoin as a formaldehyde reagent, 1-butoxy-2-propanol and ethyl acetate as solvents. , Each of which is an aqueous dispersion.
It was confirmed that the intended microcapsules were obtained by the same method as in Example 1, and the average particle size of the microcapsules was measured. As a result, it was 2.4 μm. The results are shown in Table 2.

[Example 5]
As shown in Table 1, instead of melamine (2.44 g), 1,3-bis (aminomethyl) cyclohexane having the same number of moles (manufactured by Tokyo Chemical Industry Co., Ltd., 2.75 g) was used, and the concentration was 75% by mass. In place of an ethyl acetate solution of TDI-TMP adduct (“Takenate D-103H” manufactured by Mitsui Chemicals, 25 g, solid content 18.75 g). Microcapsules were produced in the same manner as in Example 1, except that “Takenate D-140N” (21 g, solid content 15.75 g) was used. The number of moles of trimethylolpropane adduct of isophorone diisocyanate (hereinafter sometimes abbreviated as “IPDI-TMP adduct”) was the same as the number of moles of TDI-TMP adduct in Example 1.
The obtained microcapsule has a polycondensate of 1,3-bis (aminomethyl) cyclohexane and an IPDI-TMP adduct as a film-forming component, 5,5-dimethylhydantoin as a formaldehyde reagent, and as a solvent. An aqueous dispersion containing 1-butoxy-2-propanol and ethyl acetate, respectively.
It was confirmed that the intended microcapsules were obtained by the same method as in Example 1, and the average particle size of the microcapsules was measured. As a result, it was 2.4 μm. The results are shown in Table 2.

[Example 6]
Bis (2-ethylhexyl) sebacate (manufactured by Toyokuni Seiyaku Co., Ltd., 50 g) and IPDI-TMP adduct having a concentration of 75% by mass ("Takenate D-140N", Mitsui Chemicals, 21 g, solid content) 15.75 g), 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., 10 g) was added and dissolved. Subsequently, the obtained mixture was added to a carboxymethylcellulose aqueous solution (300 g, solid content 21.0 g) having a concentration of 7% by mass, and using an emulsifier (Primics Co., Ltd.), the rotational speed was 12000 rpm and the time was 10 minutes. Emulsified under conditions. After dissolving 1,3-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd., 2.75 g) in distilled water (30 g), the total amount of the 1,3-bis (aminomethyl) cyclohexane aqueous solution was Was added to the emulsified liquid obtained in Step 2 and stirred at 80 ° C. for 2 hours to carry out interfacial polycondensation.
As described above, a polycondensate of 1,3-bis (aminomethyl) cyclohexane and an IPDI-TMP adduct is used as a film forming component, 1,2,3-benzotriazole as a formaldehyde reagent, and sebacic acid as a solvent. Microcapsules each encapsulating bis (2-ethylhexyl) (SP value: 8.7 (cal / cm ³ ) ^1/2 ) and ethyl acetate were obtained as an aqueous dispersion.
It was confirmed that the intended microcapsules were obtained by the same method as in Example 1, and the average particle diameter of the microcapsules was measured. As a result, it was 11.4 μm. The results are shown in Table 2.

[Example 7]
As shown in Table 1, Example 6 was used except that 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., 2 g) was used instead of 1,2,3-benzotriazole (10 g). Microcapsules were produced in the same way.
It was confirmed that the intended microcapsules were obtained by the same method as in Example 1, and the average particle size of the microcapsules was measured. As a result, it was 12.0 μm. The results are shown in Table 2.

[Comparative Example 1]
As shown in Table 1, microcapsules were produced in the same manner as in Example 1 except that adipic acid dihydrazide (manufactured by Tokyo Chemical Industry Co., Ltd., 2 g) was used instead of 5,5-dimethylhydantoin (2 g). Tried.
However, when the liquid after the reaction was observed in the same manner as in Example 1, it was confirmed that the desired microcapsules were not obtained. The results are shown in Table 2.

[Comparative Example 2]
As shown in Table 1, microcapsules were produced in the same manner as in Example 1 except that sebacic acid dihydrazide (manufactured by Tokyo Chemical Industry Co., Ltd., 2 g) was used instead of 5,5-dimethylhydantoin (2 g). Tried.
However, when the liquid after the reaction was observed in the same manner as in Example 1, it was confirmed that the desired microcapsules were not obtained. The results are shown in Table 2.

[Comparative Example 3]
As shown in Table 1, production of microcapsules was performed in the same manner as in Example 1 except that aminoethylethanol (Tokyo Chemical Industry Co., Ltd., 2 g) was used instead of 5,5-dimethylhydantoin (2 g). Tried.
However, when the liquid after the reaction was observed in the same manner as in Example 1, it was confirmed that the desired microcapsules were not obtained. The results are shown in Table 2.

<Evaluation of water resistance of microcapsules>
The water resistance of the microcapsules obtained in each of the above examples was evaluated by the following method.
That is, the microcapsule aqueous dispersion (0.4 g) obtained above was added to distilled water (200 g), the resulting mixture was allowed to stand at room temperature, and the microcapsule aqueous dispersion was added. Extracted from the inside of the microcapsule in the liquid after 24 hours (from the preparation of the mixture), in other words, in the mixed liquid of the water in the microcapsule aqueous dispersion and the distilled water The amount of the reactant was quantified by high performance liquid chromatography (hereinafter abbreviated as “HPLC”), and the extraction rate of the formaldehyde reactant was calculated by the following formula. The HPLC was performed using an apparatus manufactured by Shimadzu Corporation.
[Formaldehyde Reactant Extraction Rate (%)] = [Amount of Formaldehyde Reactant Extracted from Inside Microcapsule in Liquid] / [Amount of Formaldehyde Reactant Added During Microcapsule Production] × 100

And the water resistance of the microcapsule was evaluated from the calculated extraction rate of the formaldehyde reactant according to the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
A: The extraction rate of the formaldehyde reactant is less than 10%.
○: The extraction rate of the formaldehyde reactant is 10% or more and less than 30%.

As is clear from the above results, in Examples 1 to 7, the polycondensate was used as a film-forming component, and the formaldehyde reactant containing no amino group or amino group salt-forming group was used. The microcapsules can be formed without problems. Each of the microcapsules of Examples 1 to 7 contained a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less.

  Furthermore, the microcapsules of Examples 6 to 7 were superior in water resistance to the microcapsules of Examples 1 to 5 by using a specific range of constituent materials.

  In contrast, in Comparative Examples 1 to 3, the polycondensate was used as a film-forming component, but this formaldehyde reagent was used by using a formaldehyde reagent having an amino group or an amino group salt-forming group. A microcapsule to be encapsulated could not be formed.

  The present invention can be used for a formaldehyde remover.

Claims (4)

Using polycondensate as a film-forming component,
A microcapsule encapsulating a formaldehyde reagent that has reactivity with formaldehyde and does not have an amino group and a group in which the amino group forms a salt. The microcapsule according to claim 1, wherein the microcapsule further contains a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less.   The microcapsule according to claim 1 or 2, wherein the polycondensate is obtained using an isocyanate compound.   The liquid composition containing the microcapsule as described in any one of Claims 1-3.