JP2016182539A - Microcapsule, sheet, resin composition and liquid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel microcapsule which exhibits sufficient sustained release, suppresses decomposition caused by heat, and realizes high safety.SOLUTION: A compound (I) has one or more aromatic cyclic groups and three or more, in total, of hydroxy groups and/or groups represented by general formula -NHR(where Ris a hydrogen atom, or an optionally substituted alkyl group, aryl group, aralkyl group or amino group). A compound (II) has two or more isocyanate groups and one or more aromatic cyclic groups. A microcapsule comprises, as a film forming component, a polycondensation product obtained by polycondensation of at least the compound (I) and the compound (II).SELECTED DRAWING: None

Description

  The present invention relates to a novel microcapsule, and a sheet, a resin composition and a liquid composition using the microcapsule.

  Microcapsules containing various active ingredients that exhibit the desired action, including pharmaceuticals, bactericides, agricultural chemicals, etc., can effectively release the active ingredients in the target environment, or gradually release the active ingredients over time. Since the controlled release property can be adjusted, its use has been studied in various fields. In order to maximize such advantages, studies have been actively made on the material of the film-forming component of the microcapsules.

  For example, as a film forming component of a microcapsule exhibiting sustained release, polyurea and polyurethane are disclosed as those that can be produced by an interfacial polycondensation method (see Patent Document 1), and can be produced by an in-situ polymerization method. Melamine / formalin resin is disclosed (see Patent Document 2).

JP 2002-114947 A Japanese Patent No. 4121380

  However, as disclosed in Patent Document 1, a conventional microcapsule in which a film-forming component is produced by an interfacial polycondensation method has a sustained release property, but decomposes when exposed to high heat. There was a point.

  Moreover, the conventional microcapsules in which the film-forming components as disclosed in Patent Document 2 are produced by an in-situ polymerization method have a sufficient sustained release property and suppress discoloration even when exposed to high heat. Although it has the heat resistance, since formalin is required for producing the film-forming component, there is a problem that the safety is low and the use of the microcapsule is limited.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel microcapsule that has sufficient sustained release properties, suppresses thermal decomposition, and has high safety.

In order to solve the above-described problems, the present invention provides at least a general formula “—NHR ¹¹ (wherein R ¹¹ is a hydrogen atom, or an alkyl group, aryl group, aralkyl group or amino group which may have a substituent. Compound (I) having a total of three or more of either one or both of the group represented by “)” and the hydroxyl group, and having one or more aromatic cyclic groups, and two or more There is provided a microcapsule comprising, as a film-forming component, a polycondensate obtained by polycondensation of a compound (II) having an isocyanate group and one or more aromatic cyclic groups.
In the microcapsule of the present invention, the compound (I) is a compound represented by the following general formula (I) -1 or (I) -2, and the compound (II) is represented by the following general formula (II) -1. A compound represented by the formula or a trimethylolpropane adduct thereof is preferable.

（式中、Ｚ^１及びＺ^２は、それぞれ独立に、一般式「−ＮＨＲ^１１（式中、Ｒ^１１は、水素原子、又は置換基を有していてもよいアルキル基、アリール基、アラルキル基若しくはアミノ基である。）」で表される基、又は水酸基であり；３個のＺ^１は互いに同一でも異なっていてもよく；Ｒ^１２は、置換基を有していてもよいアルキル基、アリール基又はアラルキル基であり：ｎは３〜６の整数であり、複数個のＺ^２は互いに同一でも異なっていてもよく；ｍは６−ｎの整数であり、ｍが２又は３である場合、複数個のＲ^１２は互いに同一でも異なっていてもよい。）

(In the formula, Z ¹ and Z ² are each independently represented by the general formula “—NHR ¹¹ , wherein R ¹¹ is a hydrogen atom or an alkyl group, aryl group, or aralkyl group optionally having a substituent. Or a hydroxyl group; three Z ^{1 s} may be the same as or different from each other; R ¹² is an alkyl group that may have a substituent; An aryl group or an aralkyl group: n is an integer of 3 to 6, a plurality of Z ² may be the same or different from each other; m is an integer of 6-n, and m is 2 or 3 In this case, the plurality of R ¹² may be the same as or different from each other.)

（式中、Ｒ^２１は、置換基を有していてもよいアルキル基、アリール基又はアラルキル基であり：ｌは０〜４の整数であり、ｌが２〜４の整数である場合、複数個のＲ^２１は互いに同一でも異なっていてもよい。）

(In the formula, R ²¹ represents an alkyl group, an aryl group or an aralkyl group which may have a substituent: l is an integer of 0 to 4, and when l is an integer of 2 to 4, R ²¹ may be the same as or different from each other.)

Moreover, this invention provides the sheet | seat which has the said microcapsule which encloses an active ingredient.
Moreover, this invention provides the resin composition containing the said microcapsule which includes an active ingredient.
Moreover, this invention provides the liquid composition containing the said microcapsule which encloses an active ingredient.

  ADVANTAGE OF THE INVENTION According to this invention, the novel microcapsule which has sufficient sustained release property, the decomposition | disassembly by heat | fever is suppressed, and high safety | security is provided.

<Microcapsule>
The microcapsule of the present invention has at least the general formula “—NHR ¹¹ (wherein R ¹¹ is a hydrogen atom, or an alkyl group, aryl group, aralkyl group or amino group which may have a substituent. ) "And a compound (I) (hereinafter simply referred to as" compound (I) "having at least three or both of the hydroxyl group and one or both of the hydroxyl groups and having one or more aromatic cyclic groups. And a compound (II) having two or more isocyanate groups and one or more aromatic cyclic groups (hereinafter sometimes simply referred to as “compound (II)”), The polycondensation product obtained by polycondensation of and is used as a film-forming component.

  By selecting compounds (I) and compounds (II) in specific ranges, and using at least an oligomer or polymer obtained by polycondensation of these compounds as a film-forming component, the microcapsules of the present invention It has sufficient sustained release properties and suppresses thermal decomposition. Moreover, since the microcapsule of the present invention does not require the use of a low-safety raw material such as formalin as described above, it is highly safe and can be used in a wide range of fields.

[Compound (I)]
Compound (I) has the general formula “—NHR ¹¹ (wherein R ¹¹ is a hydrogen atom, or an alkyl group, aryl group, aralkyl group, or amino group optionally having a substituent)”. It has 3 or more in total in any one or both of the group represented, and a hydroxyl group (-OH), and has 1 or more aromatic cyclic groups.

The alkyl group in R ¹¹ 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 those exemplified above as the alkyl group for R ¹¹ .

  From the viewpoint of reactivity with the compound (II), the alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

The aryl group in R ¹¹ 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 or the alkyl group in R ¹¹ . There are also things. The aryl group having these substituents preferably has 6 to 15 carbon atoms including the substituents.
From the viewpoint of reactivity with compound (II), the aryl group preferably has 6 to 10 carbon atoms.

As the aralkyl group in R ¹¹ , for example, one hydrogen atom of the alkyl group in R ¹¹ such as benzyl group (phenylmethyl group), phenethyl group (phenylethyl group) or the like is substituted with the aryl group in R ¹¹ . And a monovalent group.
The carbon number of the aralkyl group in R ¹¹ is preferably 7-20, and more preferably 7-11 from the viewpoint of reactivity with the compound (II).

The alkyl group, aryl group, aralkyl group and amino group in R ¹¹ may have a substituent. Here, “having a substituent” means that one or more hydrogen atoms of these groups are substituted with a group other than a hydrogen atom (substituent).
The number of substituents possessed by the alkyl group, aryl group, aralkyl group and amino group is not particularly limited, and is determined by the number of hydrogen atoms that can be substituted, and may be one, two or more, and all hydrogens. An atom may be substituted with a substituent.
When the number of substituents is 2 or more, these substituents may all be the same, all may be different, or only a part may be the same.
The position of the substituent in the alkyl group, aryl group, aralkyl group and amino group is not particularly limited.

The substituent which the alkyl group, aryl group, aralkyl group or amino group in R ¹¹ may have is not particularly limited as long as the effects of the present invention are not impaired.

  Preferred examples of the substituent that the alkyl group, aryl group, or aralkyl group may have include a halogen atom, a hydroxyl group, an amino group, and a cyano group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Preferred examples of the substituent that the amino group may have include, for example, an alkyl group, an aryl group, an aralkyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a halogen atom, a hydroxyl group, An amino group, a cyano group, etc. are mentioned.
The alkyl group, aryl group and aralkyl group in the substituent which the amino group may have are the same as the alkyl group, aryl group and aralkyl group in R ¹¹ .
Examples of the alkylamino group in the substituent that the amino group may have include those in which one hydrogen atom of the amino group is substituted with the alkyl group in R ¹¹ .
Examples of the arylamino group in the substituent that the amino group may have include those in which one hydrogen atom of the amino group is substituted with the aryl group in R ¹¹ .
Examples of the aralkylamino group in the substituent that the amino group may have include those in which one hydrogen atom of the amino group is substituted with the aralkyl group in R ¹¹ .
Examples of the halogen atom in the substituent that the amino group may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ¹¹ is preferably a hydrogen atom or an optionally substituted alkyl group or amino group, more preferably a hydrogen atom, an alkyl group or an amino group, and particularly preferably a hydrogen atom. preferable.

The aromatic cyclic group in the compound (I) is a group formed by removing one or more hydrogen atoms from an aromatic compound, and the aromatic compound is any of an aromatic hydrocarbon and an aromatic heterocyclic compound. But you can.
In the aromatic compound, the number of hydrogen atoms removed may be one or two or more. When at least one of the group represented by the general formula “—NHR ¹¹ ” and the hydroxyl group is bonded to the aromatic cyclic group, the number of hydrogen atoms removed depends on the number of bonds of these groups. receive. For example, the compound (I) has a total of three or any one or both of the group represented by the general formula “—NHR ¹¹ ” and the hydroxyl group, and these three are all in the aromatic cyclic group. In the case of bonding, the number of hydrogen atoms removed in the aromatic compound is 3 or more.
In the aromatic compound, the position of the hydrogen atom to be removed is not particularly limited.

The aromatic hydrocarbon may be either monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms, and examples thereof include benzene, naphthalene, toluene, xylene, and the like. There may be mentioned those in which one or more hydrogen atoms are further substituted with the alkyl group or aryl group. The aromatic hydrocarbon having these substituents preferably has 7 to 10 carbon atoms including the substituents.
From the viewpoint of reactivity with compound (II), the aromatic hydrocarbon preferably has 6 to 10 carbon atoms.

  The aromatic heterocyclic compound is not particularly limited as long as it has one or more hetero atoms as atoms constituting the aromatic heterocyclic skeleton, and may be monocyclic or polycyclic. The aromatic heterocyclic compound may have, for example, a structure in which a ring other than an aromatic heterocyclic ring is condensed to an aromatic heterocyclic ring. Examples of the ring other than the aromatic heterocyclic ring include an aliphatic hydrocarbon ring. And hydrocarbon rings such as aromatic hydrocarbon rings; non-aromatic heterocycles (rings having one or more heteroatoms as atoms constituting the ring skeleton and not having aromaticity), etc. .

  In the aromatic heterocyclic compound, the number of atoms constituting the aromatic heterocyclic skeleton is preferably 3 to 10, and more preferably 4 to 8. When the aromatic heterocyclic compound has a structure in which a ring other than the aromatic heterocyclic ring is condensed to the aromatic heterocyclic ring, the above-mentioned “atoms constituting the aromatic heterocyclic skeleton” include aromatic Atoms constituting a ring skeleton of a ring other than an aromatic heterocyclic ring condensed to a heterocyclic ring are not included. In addition, when the aromatic heterocyclic compound is polycyclic and has a structure in which the aromatic heterocycles are condensed with each other, the above-mentioned “number of atoms constituting the aromatic heterocyclic skeleton” is the number of condensed rings. Means the number of atoms constituting the ring skeleton of each aromatic heterocyclic ring.

Preferable examples of the hetero atom constituting the aromatic heterocyclic skeleton of the aromatic heterocyclic compound include a sulfur atom, a nitrogen atom, an oxygen atom, a selenium atom, and a phosphorus atom.
The number of the heteroatoms constituting the aromatic heterocyclic skeleton is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 4. When the number of the heteroatoms constituting the aromatic heterocyclic skeleton is two or more, the plurality of heteroatoms may be all the same, all different, or only partly the same. There may be.

The aromatic cyclic group possessed by the compound (I) may be only one, or may be two or more, and when there are two or more, these aromatic cyclic groups may all be the same. , All may be different or only some may be the same.
The number of the aromatic cyclic group possessed by the compound (I) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Compound (I) only needs to have a total of three or more of either one or both of the group represented by the general formula “—NHR ¹¹ ” and the hydroxyl group, and may have three, You may have four or more.
The compound (I) may have three or more groups represented by the general formula “—NHR ¹¹ ” without having a hydroxyl group, or represented by the general formula “—NHR ¹¹ ”. May have 3 or more hydroxyl groups without having a group, and has both the group represented by the general formula “—NHR ¹¹ ” and the hydroxyl group, and has 3 or more in total. Also good.

In the compound (I), the group and the hydroxyl group represented by the general formula “—NHR ¹¹ ” may be bonded to an atom constituting the ring skeleton of the aromatic cyclic group, or the ring skeleton. May be bonded to an atom that does not constitute a ring, but is preferably bonded to an atom that constitutes the ring skeleton.
The larger the number of groups and hydroxyl groups represented by the general formula “—NHR ¹¹ ” bonded to the atoms constituting the ring skeleton, the more preferable, and all the general formulas “—NHR ¹¹ ” It is preferable that the group to be formed and the hydroxyl group are bonded to the atoms constituting the ring skeleton.

When the group represented by the general formula “—NHR ¹¹ ” and the hydroxyl group are not bonded to the atoms constituting the ring skeleton of the aromatic cyclic group, these groups are, for example, via an alkylene group. The alkylene group is preferably bonded to an atom constituting the ring skeleton, and the alkylene group preferably has 1 to 3 carbon atoms.

Preferred examples of the compound (I) include, for example, any one of a group represented by the general formula “—NHR ^11B ” and a hydroxyl group as a carbon atom constituting the ring skeleton of an aromatic hydrocarbon or aromatic heterocyclic compound. One or both are combined in a total of 3 or more.

  More preferable compounds (I) include a compound represented by the following general formula (I) -1 (hereinafter sometimes abbreviated as “compound (I) -1”), and the following general formula (I). -2 (hereinafter sometimes abbreviated as "Compound (I) -2").

（式中、Ｚ^１及びＺ^２は、それぞれ独立に、一般式「−ＮＨＲ^１１（式中、Ｒ^１１は、水素原子、又は置換基を有していてもよいアルキル基、アリール基、アラルキル基若しくはアミノ基である。）」で表される基、又は水酸基であり；３個のＺ^１は互いに同一でも異なっていてもよく；Ｒ^１２は、置換基を有していてもよいアルキル基、アリール基又はアラルキル基であり：ｎは３〜６の整数であり、複数個のＺ^２は互いに同一でも異なっていてもよく；ｍは６−ｎの整数であり、ｍが２又は３である場合、複数個のＲ^１２は互いに同一でも異なっていてもよい。）

(In the formula, Z ¹ and Z ² are each independently represented by the general formula “—NHR ¹¹ , wherein R ¹¹ is a hydrogen atom or an alkyl group, aryl group, or aralkyl group optionally having a substituent. Or a hydroxyl group; three Z ^{1 s} may be the same as or different from each other; R ¹² is an alkyl group that may have a substituent; An aryl group or an aralkyl group: n is an integer of 3 to 6, a plurality of Z ² may be the same or different from each other; m is an integer of 6-n, and m is 2 or 3 In this case, the plurality of R ¹² may be the same as or different from each other.)

In the formula, Z ¹ is a group or a hydroxyl group represented by the general formula “—NHR ¹¹ ”, and in the compound (I) -1, all three Z ¹ may be the same or all They may be different and only two may be the same.

In the formula, n is an integer of 3 to 6, preferably 3 to 5, more preferably 3 to 4, and particularly preferably 3.
In the formula, Z ² is a group or a hydroxyl group represented by the general formula “—NHR ¹¹ ”, and all the n Z ^{2 s} may be the same or different from each other. May be the same.

In the formula, m is 6-n, that is, an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
In the formula, R ¹² is an alkyl group, aryl group or aralkyl group which may have a substituent, and the alkyl group, aryl group and aralkyl group which may have a substituent in R ¹² are R ¹¹ is the same as the alkyl group, aryl group and aralkyl group which may have a substituent. When m is 2 or 3, the plurality of R ¹² may be the same as or different from each other.
R ¹² is preferably an alkyl group which may have a substituent, and more preferably an alkyl group.

When m is 1 to 3, in Compound (I) -2, the bonding position of R ¹² is not particularly limited.
In Compound (I) -2, the bonding position of Z ² is not particularly limited, but the smaller the number of combinations of two carbon atoms to which Z ² is bonded to the adjacent one, the more preferable the combination Are particularly preferred, that is, those in which Z ² is bonded to the carbon atoms at the 1-position, 3-position and 5-position. Such particularly preferred compound (I) -2 is represented by the following general formula (I) -21.

（式中、Ｚ^２及びＲ^１２は前記と同じであり；ｍ’は０又は１であり、３個のｍ’は互いに同一でも異なっていてもよい。）

(In the formula, Z ² and R ¹² are the same as described above; m ′ is 0 or 1, and three m ′ may be the same or different from each other.)

In the formula, m ′ is 0 or 1, and is preferably 0.
Three m ′ may be the same or different from each other, all may be the same, or only two may be the same.

In addition to the above, the preferred compounds (I), those having a group represented by the general formula without a hydroxyl group "-NHR ^11" 3 or more, the formula "-NHR ^11" And those having 3 or more hydroxyl groups without having the group represented by formula (1).

[Compound (II)]
Compound (II) has two or more isocyanate groups and one or more aromatic cyclic groups, and does not correspond to compound (I).

The aromatic cyclic group in the compound (II) is a group formed by removing one or more hydrogen atoms from an aromatic compound, and the aromatic compound is any of an aromatic hydrocarbon and an aromatic heterocyclic compound. But you can.
The aromatic compound in the compound (II) is the same as the aromatic compound in the compound (I) except that the number of hydrogen atoms to be removed can be different.
For example, when two or more isocyanate groups are bonded to the aromatic cyclic group, the number of hydrogen atoms removed is affected by the number of bonds of these isocyanate groups. As an example, when the compound (II) has two isocyanate groups, and both of these are bonded to the aromatic cyclic group, a hydrogen atom to be removed in the aromatic compound The number of is two or more.
In the aromatic compound, the position of the hydrogen atom to be removed is not particularly limited.

The aromatic cyclic group possessed by the compound (II) may be only one, or may be two or more, and when there are two or more, these aromatic cyclic groups may all be the same. , All may be different or only some may be the same.
The number of the aromatic cyclic group possessed by the compound (II) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

  In the compound (II), the number of isocyanate groups is not particularly limited as long as it is 2 or more, but 2 to 6 is preferable, 2 to 5 is more preferable, and 2 to 4 is preferable. Is more preferable, and 2 or 3 is particularly preferable.

In compound (II), the isocyanate group may be bonded to an atom constituting the ring skeleton of the aromatic cyclic group, or may be bonded to an atom not constituting the ring skeleton. Is preferably bonded to an atom constituting the ring skeleton.
And it is so preferable that there are many isocyanate groups couple | bonded with the atom which comprises the said ring skeleton, and it is preferable that all the isocyanate groups are couple | bonded with the atom which comprises the said ring skeleton.

  When the isocyanate group is not bonded to an atom constituting the ring skeleton of the aromatic cyclic group, the isocyanate group is bonded to an atom constituting the ring skeleton through an alkylene group, for example. The alkylene group preferably has 1 to 3 carbon atoms.

The compound (II) preferably has no group and no hydroxyl group represented by the general formula “—NHR ¹¹ ” in the compound (I).

  Compound (II) may be a modified body, and a preferable modified body includes, for example, a trimethylolpropane adduct. The trimethylolpropane adduct may be referred to as a trimethylolpropane adduct.

  Preferable compounds (II) include, for example, compounds in which two or more isocyanate groups are bonded to the carbon atoms constituting the aromatic hydrocarbon ring skeleton.

  More preferable compound (II) is a compound represented by the following general formula (II) -1 (cyclic polyvalent isocyanate compound) and its trimethylolpropane adduct (hereinafter referred to as “compound ( II) -1 ").

（式中、Ｒ^２１は、置換基を有していてもよいアルキル基、アリール基又はアラルキル基であり：ｌは０〜４の整数であり、ｌが２〜４の整数である場合、複数個のＲ^２１は互いに同一でも異なっていてもよい。）

(In the formula, R ²¹ represents an alkyl group, an aryl group or an aralkyl group which may have a substituent: l is an integer of 0 to 4, and when l is an integer of 2 to 4, R ²¹ may be the same as or different from each other.)

In the formula, R ²¹ represents an alkyl group, an aryl group or an aralkyl group which may have a substituent, and is the same as the alkyl group, aryl group or aralkyl group which may have a substituent in R ¹¹ . Is.

In the formula, l is an integer of 0 to 4, and when l is an integer of 2 to 4, a plurality (2 to 4) of R ²¹ may all be the same or different. Alternatively, only a part may be the same.
l is preferably from 0 to 3, more preferably from 0 to 2.

In compound (II) -1, the bonding position of the two isocyanate groups is not particularly limited, but it is preferable that they are in the meta position.
In addition, when l is 1 to 4, the bonding position of R ²¹ is not particularly limited in Compound (II) -1.

[Film forming component]
The microcapsule of the present invention uses a polycondensate obtained by polycondensation of at least the compound (I) and the compound (II) as a film-forming component, and this polycondensate is usually a polyurea. In the present invention, the “film-forming component” is a component that forms a film of an outer shell that encloses an active ingredient.
The polycondensation is preferably performed by an interfacial polycondensation method. By adopting this method, microcapsules of excellent quality can be obtained.

Interfacial polycondensation may be performed by a known method in the presence of an active ingredient to be encapsulated, and the conditions may be appropriately selected in consideration of the types of the compound (I) and compound (II) to be used.
Interfacial polycondensation is preferably carried out by emulsifying in a mixed solvent of water and a hydrophobic solvent (plasticizer).

  As for the said compound (I) and compound (II) to polycondense, 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.

The amount of the compound (I) and compound (II) used is [total number of moles of group and hydroxyl group represented by the general formula “—NHR ¹¹ ” in compound (I)]: [isocyanate in compound (II) The molar ratio of the number of moles of the group is preferably 10:90 to 60:40, and more preferably 20:80 to 40:60.
When the total number of moles of the group represented by the general formula “—NHR ¹¹ ” and the hydroxyl group in the compound (I) is set to be smaller than the number of moles of the isocyanate group in the compound (II), higher quality is achieved. Microcapsules are obtained.

The active ingredient to be encapsulated exhibits its effect by the destruction of the microcapsules, and may be appropriately selected according to the purpose, and is not particularly limited.
The active ingredient may be either an organic compound or an inorganic compound, and may be a salt.
Examples of preferable active ingredients include, for example, fragrances, masking agents, antibiotics, antibacterial agents, drugs other than antibiotics and antibacterial agents, insecticides, insecticides, fungicides, fungicides, bleaching agents, preservatives, Enzymes, herbicides, agricultural chemicals other than herbicides, fertilizers, adhesives, heat storage agents, foodstuffs, feeds, spices, metal powders, metal substances other than metal powders, and the like. By using these active ingredients, the microcapsules can be used as, for example, medical pesticides, building materials, sanitary agents, foods, catalysts, agricultural agents, livestock agents, marine products agents and the like.
Examples of preferable active ingredients include color formers, color developers, color formers, decolorizers, inks, inks, waxes, plasticizers, toners, pigments, dyes, dyes, display agents, and liquid crystal substances. , Magnetic agents, electrophoretic agents and the like. By using these active ingredients, the microcapsules can be used as, for example, an image forming agent.

  The said active ingredient 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 amount of the active ingredient used may be appropriately adjusted according to the purpose, but is usually 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the compound (I) and compound (II). It is preferably 20 to 85 parts by mass, and particularly preferably 30 to 70 parts by mass.

  In the present invention, a plasticizer may be used together in order to dissolve the active ingredient to be encapsulated. In this case, for example, a hydrophilic substance such as polyvinyl alcohol may be used together to emulsify the reaction solution.

Preferred examples of the plasticizer in that porous microcapsules having good characteristics can be easily produced include, for example, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and diheptyl phthalate (DHP). Phthalic acid esters such as di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate;
Trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tri-2-ethylhexyl phosphate (TOP), tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP ), Trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), xylenyl diphenyl phosphate (XDP), phosphate esters such as 2-ethylhexyl diphenyl phosphate;
Trimellitic acid esters such as tri-2-ethylhexyl trimellitate and trioctyl trimellitate;
Benzoic acid esters such as butyl benzoate and hexyl benzoate;
Salicylic acid esters such as isopentyl salicylate, benzyl salicylate, methyl salicylate, ethyl salicylate;
Dimethyl adipate (DMA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), di-2-ethylhexyl adipate (DOA), diisodecyl adipate, dibutyl diglycol adipate, dibutyl diglycol adipate, di-2-ethylhexyl azate, dimethyl Fatty acid esters such as sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate (bis (2-ethylhexyl sebacate)), methylacetylricinoleate;
Aliphatic dicarboxylic acid esters such as dibutyl fumarate, diethyl malonate, dimethyl oxalate;
citrate esters such as o-acetyltriethyl citrate;
Alkylnaphthalenes such as methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene;
alkyl diphenyl ethers such as o-methyl diphenyl ether, m-methyl diphenyl ether, p-methyl diphenyl ether;
Amide compounds of higher fatty acids such as N, N-dimethyllaurylamide;
An amide compound of an aromatic sulfonic acid such as N-butylbenzenesulfonamide;
Diarylmethanes (diarylalkanes) such as dimethyldiphenylmethane;
Diarylethanes (diarylalkanes) such as 1-phenyl-1-methylphenylethane, 1-dimethylphenyl-1-phenylethane, 1-ethylphenyl-1-phenylethane; chlorinated paraffin;
(Meth) acrylic acid ester-based polymerizable compound (polymerizable compound having (meth) acrylic acid ester as monomer), (meth) acrylamide-based polymerizable compound (polymerizable compound having (meth) acrylamide as monomer), (meta ) Acrylic acid-based polymerizable compound (polymerizable compound having (meth) acrylic acid as monomer), maleic anhydride-based polymerizable compound (polymerizable compound having maleic anhydride as monomer), maleic ester-based polymerizable compound ( Polymerizable compound having maleic acid ester as monomer), styrene-based polymerizable compound (polymerizing compound having styrene as monomer), vinyl ether-based polymerizable compound (polymerizable compound having vinyl ether as monomer), vinyl ester-based polymerizable compound (Polymerizable compound with vinyl ester as monomer), allyl ether Polymerizable compound (polymerizable compound allyl ether monomer) vinyl polymerizable compound such as and the like.

  In the case of using a hydrophilic / hydrophobic amphoteric substance, from the viewpoint of its solubility and the like, more preferred plasticizers are dimethyl phthalate (DMP), diethyl phthalate (DEP), butyl benzyl phthalate, ethyl phthalyl ethyl glycolate, trimethyl phosphate. (TMP), tributyl phosphate (TBP), tricresyl phosphate, 2-ethylhexyl diphenyl phosphate and the like.

  A plasticizer 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 a plasticizer should just be adjusted suitably according to the objective, Usually, it is preferable that it is 200-5000 mass parts with respect to 100 mass parts of usage-amounts of the said active ingredient, 300-2500 mass parts. It is more preferable that it is 400-1000 mass parts.

As described above, in addition to the compound (I) and the compound (II), other compounds capable of polycondensation with these may be used for the polycondensation.
The other compound is not particularly limited.
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.

  The amount of the other compound used is preferably 5 mol% or less, more preferably 3 mol% or less, based on the total amount (in moles) of the compound (I) and compound (II). It is preferably 1 mol% or less.

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 purpose, or may be used for the intended purpose after performing known post-treatment, purification, etc., if necessary, and the solvent component is removed. It may be used for the intended purpose.

  The polycondensate is preferably a polycondensate of the compound (I) -1 or (I) -2 and the compound (II) -1 or a trimethylolpropane adduct thereof.

As long as the microcapsules of the present invention do not impair the effects of the present invention, any one or both of other oligomers and polymers other than the polycondensate of the compound (I) and the compound (II), It may be used as a film forming component.
As for another oligomer and a 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.

The ratio of the total content of the other oligomer and polymer to the total amount of the film-forming component is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. preferable.
That is, the ratio of the content of the polycondensate obtained by polycondensation of at least the compound (I) and the compound (II) with respect to the total amount of film-forming components is preferably 95% by mass or more. It is more preferably 97% by mass or more, and particularly 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 10 μm, more preferably 1 to 7 μm, and particularly preferably 1.5 to 4 μm.
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.

  The microcapsule of the present invention may include components other than the active ingredient such as a plasticizer in addition to the active ingredient, reflecting the production method.

<Sheet>
The sheet | seat of this invention has the above-mentioned microcapsule of this invention which includes an active ingredient.
If the said sheet | seat has the microcapsule of this invention, it will not specifically limit, It can be set as arbitrary forms.

  A preferable example of the sheet includes a sheet provided with a layer containing the microcapsule of the present invention (hereinafter sometimes abbreviated as “microcapsule-containing layer”).

Examples of the sheet when a paper base material is used as the base material include a pharmaceutical sheet (patch), an agrochemical sheet (patch), a slip, a form, a recording paper, a toy, a communication paper, a securities, a cash voucher, and a ticket. , Posters, releasable sheets with pressure sensitive adhesive layers, wallpaper, and the like.
Examples of the paper of the paper base include fine paper, art paper, coated paper, cast coated paper, resin coated paper, and synthetic paper.

Examples of the sheet when a resin base material is used as the base material include pharmaceutical sheets (patch), agrochemical sheets (patch), toys, posters, releasable sheets, wallpaper, and the like.
Examples of the resin base resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, Examples thereof include synthetic resins such as polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, and polyimide.

The base material may be made of one kind of material, or may be made of two or more kinds of materials. When the base material is made of two or more kinds of materials, the combination and ratio thereof can be arbitrarily selected. As a base material which consists of 2 or more types of materials, the base material which consists of a glass epoxy resin, a polymer alloy, etc. is mentioned, for example.
Moreover, the said base material may consist of a single layer, may consist of two or more layers, and when it consists of multiple layers, those combinations and ratios can be selected arbitrarily.

The said sheet | seat can be set as the above various sheets by making the said microcapsule content layer into a composition suitable for the use of a sheet | seat.
For example, as a microcapsule-containing layer on a substrate, a color former and a developer are contained, and a layer containing a microcapsule that contains at least one of these is provided, so that the color former or developer encapsulated over time The sheet can be configured such that the agent is gradually released from the microcapsules and develops color to display the target information. In this sheet, a layer containing a microcapsule containing a desensitizer is further provided as a microcapsule-containing layer below the above-described microcapsule-containing layer, so that the desensitizer contained over time is provided. Is gradually released from the microcapsule and reaches the color development site, so that the displayed information can be erased. Such sheets are useful, for example, as slips, forms, recording paper, toys, communication paper, securities, cash vouchers, tickets, posters, and the like.

  In addition, for example, as a microcapsule-containing layer on a substrate, by providing a layer containing a microcapsule enclosing a fragrance and an adhesive having pressure-sensitive adhesiveness and removability, the aromaticity can be obtained at the time of opening. It can be set as a releasable sheet such as a pressure-sensitive pressure-sensitive postcard shown.

The sheet can be produced, for example, by attaching a liquid raw material composition containing the microcapsules onto the substrate and drying it.
The said composition can be made to adhere on the said base material by well-known methods, such as a printing method, the apply | coating method, the immersion method, for example.
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.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, and other methods such as wire bars. It can be illustrated.

  Here, as the sheet of the present invention, the sheet provided with the microcapsule-containing layer on the base material has been described, but as the base material, a specific paper base material or the like capable of penetrating liquid components can be used. The sheet containing the microcapsules is obtained not only on the substrate but also in the substrate.

  However, the sheet | seat of this invention quoted here is only an example, and the sheet | seat of invention is not limited to these.

<Resin composition>
The resin composition of the present invention contains the above-described microcapsules of the present invention that contain an active ingredient.
If the said resin composition contains the microcapsule and resin of this invention, it will not be specifically limited, It can be set as arbitrary forms.

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, those listed as the resin base resin, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, ethylene Synthetic rubbers such as rubber, propylene rubber, and silicon rubber can be used.

The resin molded product is, for example, a building material having an insecticidal action, a bactericidal action, an antifungal action, etc., as long as it contains microcapsules containing an insecticide, an insecticide, a fungicide, a bactericidal agent, and the like. can do.
Moreover, if the said resin molded product contains the microcapsule which includes a rodenticide, for example, it can be used as the covering material of the object of a murine damage, and can protect an object from the damage of a mouse. Various cables such as a communication cable, a power cable, and a signal cable are particularly suitable as a protection target.
Moreover, the said resin molded product can be made into the sheet | seat which contains the said microcapsule in the base material of the shape similar to the said sheet | seat, for example by shape | molding in a sheet form.

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

  The resin composition can be produced, for example, by blending the microcapsules enclosing an active ingredient, 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 liquid composition of the present invention contains the above-described microcapsules of the present invention containing an active ingredient.
The liquid composition is not particularly limited as long as it contains the microcapsules of the present invention, and may be a solution or a dispersion, and can be in any form.

  Preferable examples of the liquid composition include a scented ink composition for a writing instrument, which contains a microcapsule enclosing a fragrance, a pigment or dye, and a dispersion medium (solvent).

Moreover, as a preferable thing in the said liquid composition, the coating material containing the microcapsule which includes a rodenticide is mentioned, for example. By coating such a paint on a protection object such as various cables to form a protective layer, the object can be protected from the damage of rats, as in the case of the resin molded product containing the microcapsule containing the rodenticide described above. Can protect.
Here, the paint containing the microcapsules may be a known one, and examples thereof include oil-based paints, alcoholic paints, cellulose paints, synthetic resin paints, aqueous paints, lacquer paints, rubber paints, and the like. What is necessary is just to select suitably.

  However, the liquid composition of the present invention mentioned here is only an example, and the liquid composition of the present invention is not limited to these.

  The liquid composition can be produced, for example, by blending the microcapsules, a liquid medium such as a dispersion medium (solvent), 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 above-described sheet, resin composition, and liquid composition use the above-described microcapsules of the present invention, so that the active ingredient contained therein exerts its effect continuously for a long period of time and suppresses discoloration due to heat. It is safe.

  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>
3-Iodo-2-propynylbutyl carbamate (manufactured by Sanai Oil Co., Ltd., 10 g) was added to trimethylolpropane adduct of bis (2-ethylhexyl) sebacate (manufactured by Toyokuni Seiyaku Co., Ltd., 50 g) and tolylene-2,4-diisocyanate ( It was added to a mixture of “Takenate D-103H” manufactured by Mitsui Chemicals, 25 g) 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. After dissolving melamine (manufactured by Tokyo Chemical Industry Co., Ltd., 2.44 g) in distilled water (30 g), the entire amount of this melamine aqueous solution is added to the emulsion obtained above and stirred at 80 ° C. for 2 hours. Interfacial polycondensation was performed.
As described above, a polycondensate of melamine and a trimethylolpropane adduct of tolylene-2,4-diisocyanate is used as a film-forming component, and an antifungal agent 3-iodo-2-propynylbutylcarbamate is included as an active ingredient. The obtained microcapsules were 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 size of the obtained microcapsules was measured using a Coulter counter (manufactured by Beckman Coulter) and found to be 2.47 μm.

<Evaluation of microcapsules>
(Thermal decomposition inhibition)
The microcapsule aqueous dispersion obtained above was coated on fine paper using a bar coater, and heated and dried at 105 ° C. for 2 hours. Next, 5 mg of the obtained dried product was weighed, and this weighed sample was heated at a heating rate of 2 ° C./min using a TG measuring machine (manufactured by TA), and the weight loss rate was measured. And in 220 degreeC and 230 degreeC, according to the following evaluation criteria, heat resistance was evaluated. The results are shown in Table 2.
○: The weight reduction rate is 10% or less.
X: The weight reduction rate exceeds 10%.

(Slow release)
The microcapsule aqueous dispersion (0.4 g) obtained above was added to distilled water (200 mL), and the mixture was stirred at 23 ° C. with a stirrer to maintain this stirring state. Then, samples (2 mL) were collected 1 day, 5 days, 8 days, and 14 days after the start of stirring, respectively, and analyzed by HPLC (apparatus: manufactured by Shimadzu Corporation, moving bed: acetonitrile / water) in water as a dispersion medium. The amount of 3-iodo-2-propynylbutyl carbamate released in was determined. In quantification, a calibration curve was prepared in advance and used. Then, for 3-iodo-2-propynylbutyl carbamate, the ratio of the above quantitative value to the total amount encapsulated in the microcapsule ([amount released into water] / [total amount encapsulated in the microcapsule] × 100 (%) ), That is, the release rate was calculated, and the sustained release was evaluated from the change over time in these release rates according to the following evaluation criteria. The results are shown in Table 2.
○: The release rate after 1 day is 10% or less, and the release rate after 14 days is 20% or less.
X: At least the release rate after 1 day is greater than 10%, or the release rate after 14 days is greater than 20%.

<Manufacture and evaluation of microcapsules>
[Example 2]
As shown in Table 1, in place of melamine (2.44 g), the same method as in Example 1 was used except that the same number of moles of phloroglucinol (1,3,5-trihydroxybenzene) was used. Capsules were made and evaluated. The results are shown in Table 2.

[Comparative Example 1]
As shown in Table 1, in place of melamine (2.44 g), microcapsules were produced and evaluated in the same manner as in Example 1 except that the same number of moles of diethylenetriamine was used. The results are shown in Table 2.

[Comparative Example 2]
As shown in Table 1, in place of melamine (2.44 g), the same number of moles of xylenediamine (1,4-bis (aminomethyl) benzene) was used. Capsules were made and evaluated. The results are shown in Table 2.

[Comparative Example 3]
As shown in Table 1, microcapsules were produced and evaluated in the same manner as in Example 1 except that hydroquinone having the same number of moles was used instead of melamine (2.44 g). The results are shown in Table 2.

[Comparative Example 4]
As shown in Table 1, microcapsules were produced and evaluated in the same manner as in Example 1, except that 1,3,5-cyclohexanetriol having the same number of moles was used instead of melamine (2.44 g). . The results are shown in Table 2.

[Comparative Example 5]
As shown in Table 1, in place of the trimethylolpropane adduct of tolylene-2,4-diisocyanate (25 g), Example 1 was used except that the same number of moles of trimethylolpropane adduct of isophorone diisocyanate was used. Microcapsules were produced and evaluated in the same way. The results are shown in Table 2.

[Comparative Example 6]
As shown in Table 1, Example 1 except that a trimethylolpropane adduct of hexamethylene diisocyanate having the same number of moles was used instead of the trimethylolpropane adduct of tolylene-2,4-diisocyanate (25 g). Attempts were made to produce microcapsules by the same method. The results are shown in Table 2.

  As is clear from the above results, thermal decomposition was suppressed in the microcapsules of Examples 1 and 2 using a polycondensate of compound (I) and compound (II) as a film-forming component. Moreover, in these microcapsules, the release rate of the encapsulated 3-iodo-2-propynylbutyl carbamate gradually increased with time, and the sustained release property was high.

In contrast, in Comparative Examples 1 and 2, a polyvalent amine compound other than Compound (I) was used instead of Compound (I), and in Comparative Examples 3 and 4, Compound (I) was used instead of Compound (I). By using a polyhydric alcohol other than the above, the obtained microcapsules were not inhibited from thermal decomposition. Further, in the microcapsules of Comparative Example 1, the release rate of the encapsulated 3-iodo-2-propynylbutyl carbamate is already significantly high at the stage after 1 day, and the sustained release property is already low at this stage. I was able to judge.
In Comparative Example 5, the obtained microcapsules were not inhibited from thermal decomposition by using a polyvalent isocyanate compound other than the compound (II) instead of the compound (II).
In Comparative Example 6, a microcapsule was not formed by using a polyvalent isocyanate compound other than compound (II) instead of compound (II). Therefore, in these comparative examples, the microcapsules could not be evaluated.

  INDUSTRIAL APPLICABILITY The present invention can be used for microcapsules containing various active ingredients including pharmaceuticals, bactericides, agricultural chemicals and the like.

Claims (5)

At least a group represented by the general formula “—NHR ¹¹ (wherein R ¹¹ is a hydrogen atom, or an alkyl group, aryl group, aralkyl group or amino group optionally having a substituent)”. And a compound (I) having 3 or more in total and one or both of hydroxyl groups and having one or more aromatic cyclic groups,
A microcapsule comprising, as a film-forming component, a polycondensate obtained by polycondensation of a compound (II) having two or more isocyanate groups and one or more aromatic cyclic groups. The compound (I) is a compound represented by the following general formula (I) -1 or (I) -2, and the compound (II) is a compound represented by the following general formula (II) -1 or its tri The microcapsule according to claim 1, which is a methylolpropane adduct.

(In the formula, Z ¹ and Z ² are each independently represented by the general formula “—NHR ¹¹ , wherein R ¹¹ is a hydrogen atom or an alkyl group, aryl group, or aralkyl group optionally having a substituent. Or a hydroxyl group; three Z ^{1 s} may be the same as or different from each other; R ¹² is an alkyl group that may have a substituent; An aryl group or an aralkyl group: n is an integer of 3 to 6, a plurality of Z ² may be the same or different from each other; m is an integer of 6-n, and m is 2 or 3 In this case, the plurality of R ¹² may be the same as or different from each other.)

(In the formula, R ²¹ represents an alkyl group, an aryl group or an aralkyl group which may have a substituent: l is an integer of 0 to 4, and when l is an integer of 2 to 4, R ²¹ may be the same as or different from each other.)   The sheet | seat which has a microcapsule of Claim 1 or 2 which encloses an active ingredient.   The resin composition containing the microcapsule of Claim 1 or 2 which encloses an active ingredient.   The liquid composition containing the microcapsule of Claim 1 or 2 which encloses an active ingredient.