JP6532009B2 - Microcapsule, sheet, resin composition and liquid composition - Google Patents

Description

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

  The microcapsules containing various active ingredients showing the intended action including drugs, bactericidal agents, pesticides etc. efficiently release the active ingredient in the intended environment, or gradually increase the active ingredient over time. Since the sustained release to be released can be controlled, its use is examined in various fields. And, in order to make the most of such advantage, the material of the film forming component of the microcapsule is also actively studied.

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

Unexamined-Japanese-Patent No. 2002-114947 Patent No. 4121380

  However, the conventional microcapsule as disclosed in Patent Document 1 in which the film-forming component is produced by the interfacial polycondensation method has a problem that although it has sustained release, it is decomposed when exposed to high heat. There was a point.

  In addition, conventional microcapsules in which a film-forming component is prepared by in-situ polymerization as disclosed in Patent Document 2 have sufficient sustained release and suppress discoloration even when exposed to high heat. Although it has heat resistance, it has problems of low safety and limited use of microcapsules since formalin is required for producing a film-forming component.

  The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a novel microcapsule which has a sufficient sustained release, suppresses discoloration due to heat, and has high safety.

In order to solve the above problems, the present invention relates to a compound represented by the general formula “—NHR ¹¹ (wherein R ¹¹ has a hydrogen atom or a substituent) which is bonded to at least a carbon atom of a carbonyl group A compound (i) in which the number of groups represented by the above is a good alkyl group, an aryl group, an aralkyl group or an amino group is 2 or more, an isocyanate group of 2 or more and a cyclic structure of 1 or more A polycondensate obtained by polycondensing a compound (ii) which is a trimethylolpropane adduct of a compound having the compound as a film-forming component, and the compound (i) is represented by the following general formula (i) -1 A microcapsule is provided, which is a compound represented .

（式中、Ｒ^１１は前記と同じであり、２個のＲ^１１は互いに同一でも異なっていてよく；Ｒ^１２は水素原子、又は置換基を有していてもよいアルキル基、アリール基若しくはアラルキル基であり：ｎは０又は１である。）
本発明のマイクロカプセルは、前記化合物（ｉｉ）が下記一般式（ｉｉａ）−１で表される環状多価イソシアネート化合物のトリメチロールプロパン付加体又は下記一般式（ｉｉａ）−２で表される環状多価イソシアネート化合物のトリメチロールプロパン付加体であるものが好ましい。

(Wherein, R ¹¹ is the same as the above, and two R ¹¹ may be the same or different from each other; R ¹² is a hydrogen atom, or an alkyl group which may have a substituent, an aryl group or an aralkyl) A group: n is 0 or 1)
In the microcapsule of the present invention, the compound (ii) is a trimethylolpropane adduct of a cyclic polyvalent isocyanate compound represented by the following general formula (iia) -1 or a cyclic group represented by the following general formula (iia) -2 Those which are trimethylolpropane adducts of polyvalent isocyanate compounds are preferred.

（式中、Ｒ^２１及びＲ^２２は、それぞれ独立に、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く；ｍは０〜１０の整数であり、ｍが２〜１０の整数である場合、複数個のＲ^２２は互いに同一でも異なっていてもよい。）

(Wherein, R ²¹ and R ²² are each independently an alkyl group, an aryl group or an aralkyl group which may have a substituent, and l is an integer of 0 to 4 and l is 2 to 4) When R is an integer of, the plurality of R ²¹ may be the same or different; m is an integer of 0 to 10, and when m is an integer of 2 to 10, the plurality of R ²² is the same But it may be different.)

The present invention also provides a sheet having the above-mentioned microcapsule containing an active ingredient.
The present invention also provides a resin composition containing the above-mentioned microcapsule containing an active ingredient.
The present invention also provides a liquid composition containing the above-mentioned microcapsule containing an active ingredient.

  According to the present invention, there is provided a novel microcapsule which has a sufficient sustained release, suppresses discoloration due to heat, and is highly safe.

<Microcapsule>
The microcapsule of the present invention has a general formula “—NHR ¹¹ (wherein R ¹¹ represents a hydrogen atom or a substituent) bonded to at least a carbon atom of a carbonyl group (—C (= O) —) Compound (i) (hereinafter simply referred to as “compound (i)”) in which the number of groups represented by the alkyl group, the aryl group, the aralkyl group or the amino group which may be possessed is two or more Compound (ii) (hereinafter simply referred to simply as “compound (ii)”) which is a trimethylolpropane adduct of a compound having two or more isocyanate groups and one or more cyclic structures, which may be abbreviated And polycondensate obtained by polycondensation are used as a film forming component.

  The microcapsules of the present invention can be obtained by using an oligomer or a polymer obtained by polycondensation of at least these compounds as a film-forming component, by selecting the compound (i) and the compound (ii) each in a specific range. It has sufficient sustained release, and discoloration due to heat is suppressed. In addition, since the microcapsules of the present invention do not need to use raw materials with low safety such as formalin as described above, they have high safety and can be used in a wide range of fields.

[Compound (i)]
Compound (i) has a general formula “—NHR ¹¹ (wherein R ¹¹ is a hydrogen atom, or an alkyl group which may have a substituent, an aryl group, or the like) bonded to a carbon atom of a carbonyl group And the number of groups represented by “)” is 2 or more.

The alkyl group for 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, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 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 Group, 2,4-dimethyl pentyl group, 3, 3-dimethyl pentyl group, 3-ethyl pentyl group, 2, 2, 3- trimethyl butyl group, n-octyl , Isooctyl group, 2-ethylhexyl group, nonyl group, decyl group.

The cyclic alkyl group preferably has 3 to 10 carbon atoms, and as the alkyl group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group And cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group, etc. Further, one or more hydrogen atoms of these cyclic alkyl groups are linear or branched. Those substituted with a linear or cyclic alkyl group can be mentioned. Here, as the linear, branched or cyclic alkyl group for substituting a hydrogen atom, the above-mentioned ones as the alkyl group in R ¹¹ can be mentioned.

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

The aryl group for R ¹¹ may be either monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl and o-tolyl, m- tolyl group, p- tolyl group, xylyl group (dimethylphenyl group), with one or more hydrogen atoms of these aryl groups may further and these aryl groups substituted with the alkyl group in R ¹¹ The thing is also mentioned. The aryl group having these substituents preferably has 6 to 15 carbon atoms including the substituents.
It is preferable that carbon number of the said aryl group is 6-10 from a reactive viewpoint with compound (ii).

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

The alkyl group, the aryl group, the aralkyl group and the amino group (-NH ₂ ) in R ¹¹ may have a substituent. Here, "having a substituent" means that one or more hydrogen atoms of these groups are substituted by a group (substituent) other than a hydrogen atom.
The number of substituents which the alkyl group, the aryl group, the aralkyl group and the amino group have is not particularly limited, and is determined by the number of hydrogen atoms that can be substituted, and may be one or two or more, and all hydrogens The atom may be substituted by a substituent.
When the number of substituents is 2 or more, these substituents may be all the same, all may be different, or only some may be the same.
The positions of substituents on the alkyl group, aryl group, aralkyl group and amino group are not particularly limited.

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

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

Preferred examples of the substituent which the amino group may have include 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, and the like. A cyano group etc. are mentioned.
Alkyl group at the amino group is the substituent group which may have, aryl group and aralkyl group are the same as the alkyl group, aryl group and aralkyl group in R ^11.
The alkylamino group in or the substituent of the amino group, for example, those in which one of the hydrogen atoms of the amino group is substituted with the alkyl group in R ^11.
The arylamino group in or the substituent of the amino group, for example, those in which one of the hydrogen atoms of the amino group is substituted with the aryl group in R ^11.
The aralkylamino group in or the substituent of the amino group, for example, those in which one of the hydrogen atoms of the amino group is substituted with the aralkyl group in R ^11.
As a halogen atom in the said substituent which an amino group may have, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

R ¹¹ is preferably a hydrogen atom, or an alkyl or amino group which may have a substituent, more preferably a hydrogen atom, an alkyl group or an amino group, a hydrogen atom or an amino group Is particularly preferred.

In the compound (i), the number of the carbonyl group to which the group represented by the general formula “—NHR ¹¹ ” is bonded at a carbon atom is not particularly limited, and may be one or two or more. , 1 to 3 is preferable, and 1 or 2 is more preferable.
In the compound (i), the position of the carbonyl group to which a group represented by the above-mentioned general formula "-NHR ¹¹ " is bonded at a carbon atom is not particularly limited.

In the compound (i), the group represented by the general formula "-NHR ¹¹ " may be bonded to only one carbon atom or two carbon atoms of one carbonyl group.
In the compound (i), the number of groups represented by the above-mentioned general formula “—NHR ¹¹ ” which is bonded to a carbon atom of a carbonyl group is not particularly limited as long as it is 2 or more. Some are preferable, 2 to 5 are more preferable, 2 to 4 are more preferable, and 2 or 3 are particularly preferable.
The groups represented by two or more of the general formula “—NHR ¹¹ ” in the compound (i) may be all identical, all may be different, or only some may be identical. .

Preferred examples of the compound (i) include urea and urea derivatives.
In the present specification, the term "derivative" means that one or more hydrogen atoms of the original compound are substituted with a group other than a hydrogen atom.

  More preferable examples of the compound (i) include those represented by the following general formula (i) -1 (hereinafter sometimes abbreviated as "compound (i) -1").

（式中、Ｒ^１１は前記と同じであり、２個のＲ^１１は互いに同一でも異なっていてよく；Ｒ^１２は水素原子、又は置換基を有していてもよいアルキル基、アリール基若しくはアラルキル基であり：ｎは０又は１である。）

(Wherein, R ¹¹ is the same as the above, and two R ¹¹ may be the same or different from each other; R ¹² is a hydrogen atom, or an alkyl group which may have a substituent, an aryl group or an aralkyl) A group: n is 0 or 1)

In the formula, R ¹¹ is the same as R ^{11 in the} group represented by the above-mentioned general formula “—NHR ¹¹ ”, and two R ^{11 s} may be the same as or different from each other.

In the formula, R ¹² is a hydrogen atom or an alkyl group which may have a substituent, an aryl group or an aralkyl group, and the alkyl group which may have a substituent for R ¹² , an aryl group and an aralkyl group And R ¹¹ are the same as the optionally substituted alkyl, aryl and aralkyl groups for R ¹¹ .
R ¹² is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or an alkyl group.

In the formula, n is 0 or 1, and when it is 0, two groups represented by the general formula “—NHR ¹¹ ” are bonded to the carbon atom of the same carbonyl group.

[Compound (ii)]
The compound (ii) is a trimethylolpropane adduct of a compound having two or more isocyanate groups and one or more cyclic structures (hereinafter sometimes abbreviated as “cyclic polyhydric isocyanate compound”), and the compound (ii) is It does not correspond to i). The trimethylolpropane adduct is sometimes referred to as trimethylolpropane adduct.
The cyclic structure in the compound (ii) may be any of an aromatic cyclic group (aromatic ring) and an aliphatic cyclic group (aliphatic ring).

  The aromatic cyclic group in the compound (ii) is a group obtained 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. May be.

In the aromatic compound, the number of hydrogen atoms to be removed may be one or two or more. When the isocyanate group is bonded to the aromatic cyclic group, the number of hydrogen atoms to be removed is affected by the number of bonds of this group. For example, when the compound (ii) has two or more isocyanate groups, and all the two or more isocyanate groups are bonded to the aromatic cyclic group, hydrogen atoms 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 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, and one of these aromatic hydrocarbons is Those in which one or more hydrogen atoms are further substituted by the above alkyl group or aryl group are also included. The aromatic hydrocarbon having these substituents, including the substituents, preferably has 6 to 15 carbon atoms.
It is preferable that carbon number of the said aromatic hydrocarbon is 6-10 from a reactive viewpoint with a compound (i).

  The aromatic heterocyclic compound is not particularly limited as long as it has one or more hetero atoms as an atom constituting an 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 the aromatic heterocyclic ring is fused to an aromatic heterocyclic ring, and as the ring other than the aromatic heterocyclic ring, for example, an aliphatic hydrocarbon ring And hydrocarbon rings such as aromatic hydrocarbon rings; nonaromatic heterocycles (a ring having one or more hetero atoms as atoms constituting a ring skeleton and having no aromaticity) and the like. .

  The number of atoms constituting the aromatic heterocyclic ring in the aromatic heterocyclic compound 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 an aromatic heterocyclic ring is fused to an aromatic heterocyclic ring, the above-mentioned “atom constituting the aromatic heterocyclic ring” is an aromatic group. The atoms constituting the ring skeleton of the ring other than the aromatic heterocycle which is fused to the heterocycle are not included. Further, when the aromatic heterocyclic compound has a structure in which a plurality of polycyclic aromatic heterocycles are fused to each other, the above-mentioned “number of atoms constituting the aromatic heterocyclic skeleton” is fused to Means the number of atoms that make up the ring skeleton of each aromatic heterocycle.

Preferred examples of the hetero atom constituting the aromatic heterocyclic ring structure 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 hetero atoms constituting the aromatic heterocyclic ring is not particularly limited, but is preferably one or two, and more preferably one. When the number of hetero atoms constituting the aromatic heterocyclic ring structure is two or more, the plurality of hetero atoms may be all the same or all different, and only some of them may be the same. It may be.

The aliphatic cyclic group (aliphatic ring) in the compound (ii) is a group obtained by removing one or more hydrogen atoms from an aliphatic ring compound, and the aliphatic ring compound is a saturated aliphatic ring compound And any of unsaturated aliphatic ring compounds.
In the aliphatic ring compound, the number of hydrogen atoms to be removed is determined by the number of the isocyanate groups and the like, and may be one or two or more. Further, in the aliphatic ring compound, the position of the hydrogen atom to be removed is not particularly limited.

The saturated aliphatic ring compound may be either monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. For example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, Cyclodecane, norbornane, isobornane, adamantane, tricyclodecane and the like can be mentioned, and those in which one or more hydrogen atoms of these saturated aliphatic ring compounds are further substituted by the above-mentioned alkyl group can also be mentioned. The saturated aliphatic ring compound having such a substituent, including the substituent, preferably has 6 to 15 carbon atoms.
From the viewpoint of reactivity with the compound (i), the saturated aliphatic ring compound preferably has 6 to 10 carbon atoms.

The unsaturated aliphatic ring compound may be either monocyclic or polycyclic, and may have, for example, a structure in which a saturated aliphatic ring is fused to an unsaturated aliphatic ring.
The unsaturated aliphatic ring compound is, for example, a double bond (C = C) in which at least one single bond (C—C) between carbon atoms in the saturated aliphatic ring compound is an unsaturated bond (CCC) Or compounds substituted with triple bonds (C≡C).
In the unsaturated aliphatic ring compound, the number of unsaturated bonds may be only one, may be two or more, and when it is two or more, these unsaturated bonds may be only double bonds or triple bonds Only double bonds and triple bonds may be mixed.
In the unsaturated aliphatic ring compound, the position of the unsaturated bond is not particularly limited.

  The cyclic structure possessed by the compound (ii) may be only one, may be two or more, and when two or more, the cyclic structures may be all identical or all different. Well, only a part may be the same.

  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 Is more preferable, and 2 or 3 are particularly preferable.

  In the compound (ii), the isocyanate group may be bonded to an atom constituting the ring skeleton of the cyclic structure, or may be bonded to an atom not constituting the ring skeleton, but at least It is preferable that one isocyanate group is bonded to an atom constituting the ring skeleton. When the isocyanate group is not bonded to the atom constituting the ring skeleton of the cyclic structure, this isocyanate group may be bonded to the atom constituting the ring skeleton via, for example, an alkylene group. Preferably, the alkylene group has 1 to 3 carbon atoms.

It is preferable that the compound (ii) does not have a group represented by the above-mentioned general formula "-NHR ¹¹ " in the compound (i).

  Preferred examples of the cyclic polyvalent isocyanate compound in the compound (ii) include, for example, two or more isocyanate groups bonded to a carbon atom constituting the ring skeleton of an aromatic hydrocarbon directly or via the alkylene group. And compounds in which two or more isocyanate groups are bonded to a carbon atom constituting the ring skeleton of a saturated aliphatic ring compound directly or via the alkylene group.

  More preferable compound (ii) is a trimethylolpropane adduct of a cyclic polyvalent isocyanate compound represented by the following general formula (iia) -1 (hereinafter abbreviated as “compound (ii) -1” And trimethylolpropane adducts of cyclic polyvalent isocyanate compounds represented by the following general formula (iia) -2 (hereinafter sometimes abbreviated as "compound (ii) -2").

（式中、Ｒ^２１及びＲ^２２は、それぞれ独立に、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く；ｍは０〜１０の整数であり、ｍが２〜１０の整数である場合、複数個のＲ^２２は互いに同一でも異なっていてもよい。）

(Wherein, R ²¹ and R ²² are each independently an alkyl group, an aryl group or an aralkyl group which may have a substituent, and l is an integer of 0 to 4 and l is 2 to 4) When R is an integer of, the plurality of R ²¹ may be the same or different; m is an integer of 0 to 10, and when m is an integer of 2 to 10, the plurality of R ²² is the same But it may be different.)

In the formula, each of R ²¹ and R ²² independently represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and an alkyl group which may have a substituent for R ¹¹ , an aryl group It is the same as a group or an aralkyl group.

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

In the formula, when m is an integer of 0 to 10 and m is an integer of 2 to 10, a plurality (2 to 10) of R ²² may be all the same or all different. Also, only part of them may be identical.
m is preferably 0 to 8, more preferably 0 to 6, and particularly preferably 0 to 4.

In the compound (ii) -1, the bonding position of the two isocyanate groups is not particularly limited, but it is preferable that they be in the meta position with each other.
Also, if l is 1-4, in the compound (ii) ^-1, the bonding position of ^{R 21} is not particularly limited.

In the compound (ii) -2, the bonding position of the isocyanate group (—NCO) and the isocyanatomethyl group (—CH ₂ —NCO) is not particularly limited, but it is preferable that they be meta positions to each other.
Moreover, when m is 1-10, in the compound (ii) -2, the bonding position of R ²² is not particularly limited.

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

The interfacial polycondensation may be performed by a known method in the coexistence of the active ingredient to be contained, and the conditions may be appropriately selected in consideration of the types of the compound (i) and the compound (ii) to be used.
The interfacial polycondensation is preferably performed by emulsifying in a mixed solvent of water and a hydrophobic solvent (plasticizer).

  The compound (i) and the compound (ii) to be polycondensed may be either alone or in combination of two or more, and in the case of two or more, their combination and ratio can be arbitrarily selected.

The amount of the compound (i) and the compound (ii) to be used is [the number of moles of the group represented by the general formula "-NHR ¹¹ " bonded to the carbon atom of the carbonyl group in the compound (i)]: The molar ratio of the number of moles of the isocyanate group in the compound (ii) is preferably 10:90 to 60:40, and more preferably 20:80 to 40:60.
The number of moles of the group represented by the general formula “—NHR ¹¹ ” bonded to the carbon atom of the carbonyl group in the compound (i) is smaller than the number of moles of the isocyanate group in the compound (ii) When set, higher quality microcapsules can be obtained.

The active ingredient to be contained is one that exerts its effect by the destruction of the microcapsule, 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, or may be a salt.
Preferred examples of the active ingredient include, for example, perfumes, masking agents, antibiotics, antibiotics, antibiotics and drugs other than antibiotics and insecticides, insecticides, insect repellents, fungicides, bactericides, bleachs, preservatives, Enzymes, herbicides, pesticides other than herbicides, fertilizers, adhesives, heat storage agents, foodstuffs, feeds, spices, metal powders, metal substances other than metal powders, etc. may be mentioned. By using these active ingredients, the microcapsules can be used, for example, as medicines and pesticides, building materials, hygiene agents, foods, catalysts, agricultural agents, livestock agents, marine agents and the like.
Preferred examples of the active ingredient include, for example, color formers, color developers, color formers, decolorizers, inks, inks, waxes, plasticizers, toners, pigments, dyes, dyes, indicators, liquid crystal substances. , Magnetic agents, electrophoretic agents and the like. By using these active ingredients, the microcapsules can be used, for example, as an image forming agent.

  The active ingredients may be used alone or in combination of two or more. When two or more are used in combination, their combination and ratio can be arbitrarily selected.

  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 the compound (ii) It is preferable, it is more preferable that it is 20-85 mass parts, and it is especially preferable that it is 30-70 mass parts.

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

Preferred examples of the above-mentioned plasticizer include, for example, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and diheptyl phthalate (DHP), in that porous microcapsules having good properties can be easily produced. 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) And phosphoric acid esters such as trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), xylenyl diphenyl phosphate (XDP), and 2-ethylhexyl diphenyl phosphate;
Trimellitic acid esters such as tri-2-ethylhexyl trimellitate, trioctyl trimellitate;
Benzoate 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 azetate, dimethyl Fatty acid esters such as sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate (bis (2-ethylhexyl) sebacate), methyl acetyl ricinolate;
Aliphatic dicarboxylic acid esters such as dibutyl fumarate, diethyl malonate, dimethyl oxalate;
Citric acid esters such as o-acetyl triethyl citrate;
Alkyl naphthalenes such as methyl naphthalene, dimethyl naphthalene, isopropyl naphthalene and diisopropyl naphthalene;
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-dimethyl lauryl amide;
Amide compounds of aromatic sulfonic acids 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, etc .; chlorinated paraffins;
(Meth) Acrylate Ester Polymerizable Compound (A Polymerizable Compound Having a (Meth) Acrylate Ester as a Monomer, a (Meth) Acrylamide Polymerizable Compound (A Polymerizable Compound Having a (Meth) Acrylamide as a Monomer), (Meta) ) Acrylic acid type polymerizable compounds (polymerizable compounds having (meth) acrylic acid as a monomer), maleic anhydride type polymerizable compounds (polymerizable compounds having maleic anhydride as a monomer), maleic acid ester type polymerizable compounds ( Polymerizable compound having a maleic acid ester as a monomer), styrene-based polymerizable compound (polymeric compound having a styrene as a monomer), vinyl ether-based polymerizable compound (a polymerizable compound having a vinyl ether as a monomer), vinyl ester-based polymerizable compound (Polymerizable compounds containing vinyl ester as a monomer), allyl ether Polymerizable compound (polymerizable compound allyl ether monomer) vinyl polymerizable compound such as and the like.

  When a hydrophilic / hydrophobic amphoteric substance is used, dimethyl phthalate (DMP), diethyl phthalate (DEP), butyl benzyl phthalate, ethyl phthalyl ethyl glycolate, trimethyl phosphate are more preferable as a plasticizer from the viewpoint of solubility etc. (TMP), tributyl phosphate (TBP), tricresyl phosphate, 2-ethylhexyl diphenyl phosphate and the like.

  A plasticizer may be used individually by 1 type, and 2 or more types may be used together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  The amount of the plasticizer used may be appropriately adjusted according to the purpose, but generally, it is preferably 200 to 5000 parts by mass, 300 to 2500 parts by mass with respect to 100 parts by mass of the active ingredient used. Is more preferable, and 400 to 1000 parts by mass is particularly preferable.

As described above, for the polycondensation, in addition to the compound (i) and the compound (ii), other compounds capable of polycondensation with these may be used.
The other compounds are not particularly limited.
The other compounds may be used alone or in combination of two or more, and in the case of two or more, their combination and ratio may 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 (mole number) of the compound (i) and the compound (ii) used. Preferably, it is 1 mol% or less.

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

After polycondensation, for example, the microcapsules of the present invention are obtained as a water dispersion.
The obtained microcapsules may be used as they are for the intended use, or may be used for the intended use after subjecting them to known post-treatment, purification, etc. if necessary, and the solvent components are removed. It may be used in the intended application.

  The polycondensation product is preferably a polycondensation product of the compound (i) -1 and the compound (ii) -1 or the compound (ii) -2.

The microcapsules of the present invention may be any one or both of other oligomers and polymers other than the polycondensate of the compound (i) and the compound (ii), as long as the effects of the present invention are not impaired. It may be used as a film forming component.
Any other oligomer and polymer may be used alone or in combination of two or more, and in the case of two or more, their combination and ratio can be optionally selected.

The ratio of the total content of the other oligomers and polymers to the total amount of the film-forming component is preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 1% by mass or less preferable.
That is, the content ratio of the polycondensate obtained by polycondensation of at least the compound (i) and the compound (ii) with respect to the total amount of the film forming component is preferably 95% by mass or more, It is more preferable that it is 97 mass% or more, and it is especially preferable that it is 99 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.
Incidentally, the "average particle size", as used herein, unless otherwise noted, were measured by a method using a Coulter counter, it means a median D ₅₀ of the cumulative volume distribution.

  The microcapsules of the present invention may contain components other than the active component such as a plasticizer, for example, in addition to the active component, reflecting the production method.

<Sheet>
The sheet of the present invention has the above-mentioned microcapsule of the present invention, which contains the active ingredient.
The sheet is not particularly limited as long as it has the microcapsules of the present invention, and can be in any form.

  What is preferable as the above-mentioned sheet is, for example, one provided with a layer containing the microcapsule of the present invention (hereinafter sometimes abbreviated as “microcapsule-containing layer”) on a substrate.

As said sheet at the time of using a paper base material as said base material, a pharmaceutical sheet (patch), an agrochemical sheet (patch), a slip, a slip, a record, a recording paper, a toy, communication paper, securities, a gold ticket, a ticket, for example , Posters, releasable sheets provided with a pressure-sensitive adhesive layer, wallpaper, and the like.
Examples of the paper of the paper base include high-quality paper, art paper, coated paper, cast-coated paper, resin-coated paper, synthetic paper and the like.

As said sheet | seat at the time of using the resin base material as said base material, a pharmaceutical sheet (patch), an agrochemical sheet (patch), a toy, a poster, a removable sheet, wallpaper etc. are mentioned, for example.
Examples of the resin of the resin base 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 polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, and synthetic resins such as polyimide.

The substrate may be made of one kind of material or may be made of two or more kinds of materials, and when it 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 glass epoxy resin, a polymer alloy, etc. is mentioned, for example.
Further, the substrate may be composed of a single layer, or may be composed of a plurality of layers of two or more layers, and when composed of a plurality of layers, the combination and ratio thereof can be arbitrarily selected.

The sheet can be made into various sheets as described above by making the microcapsule-containing layer a composition suitable for the application of the sheet.
For example, as a microcapsule-containing layer on a base material, a color former and a developer are included, and by providing a layer containing a microcapsule including at least one of these, a color former or a color developer encapsulated with the passage of time The agent is gradually released from the microcapsule and can be colored to form a sheet capable of displaying the desired information. The sheet further includes a layer containing microcapsules containing a desensitizing agent as a microcapsule-containing layer separately as a lower layer than the above-mentioned microcapsule-containing layer, whereby the desensitizer incorporated with the passage of time. Is gradually released from the microcapsules to reach the coloring site, so that the sheet can be configured to erase (extinguish) the displayed information. Such sheets are useful, for example, as slips, forms, recording paper, toys, communication paper, securities, cash vouchers, tickets, posters, and the like.

  Also, for example, by providing a layer containing microcapsules containing a perfume as a microcapsule-containing layer on a substrate, and an adhesive having pressure-sensitive adhesiveness and removability, it is possible to have an aromaticity at the time of opening. It can be used as a releasable sheet such as a pressure-sensitive crimped postcard shown.

The sheet can be produced, for example, by depositing a liquid raw material composition containing the microcapsules on the substrate and drying it.
The composition can be deposited on the substrate by a known method such as, for example, a printing method, a coating method, or an immersion method.
Examples of the printing method include screen printing, flexographic printing, offset printing, dip printing, ink jet printing, dispenser printing, gravure printing, gravure offset printing, pad printing and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, blade coaters, roll coaters, gate roll coaters, gate coaters, bar coaters, rod coaters, rod coaters, gravure coaters, and other wire coaters. It can be illustrated.

  Here, as the sheet of the present invention, the sheet provided with the microcapsule-containing layer on a substrate is described, but by using a sheet that can be permeated with a liquid component such as a specific paper substrate as the substrate. The sheet containing the microcapsules is obtained not only on the substrate but also in the substrate.

  However, the sheet of the present invention mentioned here is just an example, and the sheet of the invention is not limited to these.

<Resin composition>
The resin composition of the present invention contains the above-mentioned microcapsule of the present invention, which contains the active ingredient.
The resin composition is not particularly limited as long as it contains the microcapsules of the present invention and a resin, and can be in any form.

Preferred examples of the resin composition include those for resin molded articles containing the microcapsules.
The resin can be optionally selected according to the purpose, and for example, those mentioned as the resin of the resin base, polybutadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, ethylene Examples of the rubber include synthetic rubbers such as rubber, propylene rubber and silicone rubber.

The resin molded product is, for example, a building material having an insecticidal action, a bactericidal action, an antifungal action, etc. if it contains microcapsules containing an insecticide, an insect repellent, an antifungal agent, a bactericidal agent, etc. can do.
Moreover, if the said resin molded product is a thing containing the microcapsule which contains a rodenticide, for example, it can be set as the coating material of the poisoning object of a rat, and an object can be protected from the eating damage of a rat. Various cables such as communication cables, power cables, and signal cables are particularly suitable as objects to be protected.
Further, the resin molded product can be formed into a sheet, for example, to form a sheet having the same shape as the sheet and containing the microcapsules in the base material.

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

  The said resin composition can be manufactured by mix | blending the said microcapsule which contains an active ingredient, resin, and other components, such as a hardening agent and a solvent, as needed, for example. The obtained resin composition may be molded by a known method suitable for the compounding components and purpose.

<Liquid composition>
The liquid composition of the present invention contains the above-mentioned microcapsule of the present invention, which contains the 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 may be in any form.

  Preferred examples of the liquid composition include a scented ink composition for a writing instrument, containing microcapsules containing a fragrance, a pigment or a dye, and a dispersion medium (solvent).

Moreover, as a preferable thing in the said liquid composition, the coating material containing the microcapsule which contains the rodenticide, for example is mentioned. By coating such a paint on a protection target such as various cables to form a protective layer, the target is not affected by eating damage to rats, as in the case of resin molded articles containing microcapsules containing the above-mentioned rodenticide. It can protect.
Here, the paint containing microcapsules may be a known paint, and examples thereof include oil-based paint, sake spirit paint, cellulose paint, synthetic resin paint, water-based paint, lacquer-based paint, rubber-based paint and the like, according to the purpose. It may be selected as appropriate.

  However, the liquid composition of the present invention mentioned here is just an example, and the liquid composition of the 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 may be used by the well-known method suitable according to the compounding component and the objective.

  In the above-mentioned sheet, resin composition and liquid composition, by using the above-mentioned microcapsule of the present invention, the active ingredient to be contained continuously exhibits its effect for a long time, and the discoloration due to heat is suppressed And safety is high.

  Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited at all to the examples shown below.

Example 1
<Manufacture of microcapsules>
3-iodo-2-propynyl butyl carbamate (manufactured by Sanai Oil Co., Ltd., 10 g), bis (2-ethylhexyl) sebacate (manufactured by Toyoko Oil Co., Ltd., 50 g) and trimethylolpropane adduct of tolylene-2,4-diisocyanate ( It was added to and dissolved in a mixture of Mitsui Chemicals "Takenate D-103H" (16.6 g). Next, the obtained mixture is added to an aqueous solution of polyvinyl alcohol (150 g, solid content 7.5 g) having a concentration of 5% by mass, and using an emulsifying machine (manufactured by PRIMIX Co., Ltd.), rotation speed 12000 rpm, time 10 minutes Emulsify under the conditions. After dissolving urea (1.2 g, manufactured by Tokyo Chemical Industry Co., Ltd.) in distilled water (30 g), add the whole amount of the aqueous urea solution to the emulsion obtained above, and stir at 80 ° C. for 2 hours. And interfacial polycondensation.
As described above, a polycondensate of urea and a trimethylolpropane adduct of tolylene-2,4-diisocyanate is used as a film-forming component, and a fungicide 3-iodo-2-propynylbutylcarbamate is included as an active component. The obtained microcapsules were obtained as a water dispersion.

  The microcapsule aqueous dispersion obtained above is coated on wood free paper using a bar coater, dried at 105 ° C. for 90 seconds, and then 5000 × magnification using an electron microscope (manufactured by Nippon Denshi Co., Ltd.) The coating and drying sites were observed with the above to confirm that the intended microcapsules were obtained. It was 2.57 micrometers when the average particle diameter of the obtained microcapsule was measured using the Coulter counter (made by Beckman Coulter Inc.).

<Evaluation of microcapsules>
(Thermal discoloration inhibitory property)
The microcapsule aqueous dispersion obtained above was coated on wood free paper using a bar coater, dried at 105 ° C. for 90 seconds, and then the coated paper was heat treated in an oven at 220 ° C. for 40 seconds Thereafter, it was taken out of the oven, and visually observed for the presence and degree of discoloration of the coated site. And heat discoloration inhibitory property was evaluated according to the following evaluation criteria. The results are shown in Table 2.
○: no or no discoloration.
X: Discoloration is remarkable.

(Controlled release)
The microcapsule aqueous dispersion (0.4 g) obtained above was added to distilled water (200 mL), and this mixture was stirred using a stirrer at 23 ° C., and this stirring state was maintained. Then, a sample (2 mL) is collected 1 day, 4 days, 8 days and 14 days after the start of stirring, and in water as a dispersion medium by HPLC (apparatus: manufactured by Shimadzu Corporation, moving bed: acetonitrile / water) The 3-iodo-2-propynyl butyl carbamate released to For quantification, a calibration curve was prepared in advance and used. Then, for 3-iodo-2-propynyl butyl 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 (%) The release rate was calculated, and from the time-dependent change of the release rate, the sustained release was evaluated 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, microcapsules were produced and evaluated in the same manner as in Example 1, except that urea (1.2 g) was replaced by the same number of moles of burulet (imidodicarbondiamide). The results are shown in Table 2.

[Example 3]
As shown in Table 1, microcapsules were produced in the same manner as in Example 1 except that the same number of moles of carbohydrazide (1,3-diaminourea) was used instead of urea (1.2 g). evaluated. The results are shown in Table 2.

Example 4
As shown in Table 1, it is an example except using the trimethylolpropane adduct of isophorone diisocyanate of the same number of moles instead of the trimethylolpropane adduct of tolylene-2,4-diisocyanate (16.6 g). The microcapsules were manufactured and evaluated in the same way as 1. The results are shown in Table 2.

Comparative Example 1
As shown in Table 1, microcapsules were produced and evaluated in the same manner as in Example 1 except that urea (1.2 g) was replaced by the same number of moles of diethylenetriamine. The results are shown in Table 2.

Comparative Example 2
As shown in Table 1, microcapsules were produced and evaluated in the same manner as in Example 1 except that the same number of moles of 3,3'-diaminodipropylamine was used instead of urea (1.2 g). did. The results are shown in Table 2.

Comparative Example 3
As shown in Table 1, the procedure was carried out except that trimethylolpropane adduct of hexamethylene diisocyanate with the same number of moles was used instead of trimethylolpropane adduct of tolylene-2,4-diisocyanate (16.6 g). The manufacture of microcapsules was attempted in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 4
As shown in Table 1, except that the trimethylolpropane adduct of tolylene-2,4-diisocyanate (16.6 g) is replaced by an isocyanurate of tolylene-2,4-diisocyanate with the same number of moles. The manufacture of microcapsules was tried in the same manner as in Example 1. The results are shown in Table 2.

  As is clear from the above results, in the microcapsules of Examples 1 to 4 in which the polycondensate of compound (i) and compound (ii) is used as a film-forming component, thermal discoloration is suppressed, and the coating site is Remained white. Moreover, in these microcapsules, the release rate of the encapsulated 3-iodo-2-propynyl butyl carbamate gradually increased with time, and the sustained release was high.

On the other hand, in Comparative Examples 1 and 2, the microcapsules obtained by using a polyvalent amine compound other than the compound (i) instead of the compound (i) are not inhibited from the thermal discoloration, The working site turned from white to yellow. Moreover, in these microcapsules, the release rate of the encapsulated 3-iodo-2-propynyl butyl carbamate is already significantly higher at the stage after one day, and it can be judged at this stage that the sustained release is already low. The
Further, in Comparative Examples 3 and 4, microcapsules were not formed by using a polyvalent isocyanate compound other than the compound (ii) in place of the compound (ii). Therefore, the microcapsules could not be evaluated in these comparative examples.

  The present invention is applicable to microcapsules containing various active ingredients such as medicines, germicides, pesticides and the like.

Claims (5)

General formula “—NHR ¹¹ (wherein R ¹¹ is a hydrogen atom, or an alkyl group which may have a substituent, an aryl group, an aralkyl group or an amino group, which is bonded to a carbon atom of a carbonyl group) Compounds (i) in which the number of groups represented by
A polycondensate obtained by polycondensation of a compound (ii) which is a trimethylolpropane adduct of a compound having two or more isocyanate groups and one or more cyclic structures is used as a film forming component ,
The microcapsule whose said compound (i) is a compound represented by the following general formula (i) -1 .

( Wherein , R ¹¹ is the same as the above, and two R ¹¹ may be the same or different from each other; R ¹² is a hydrogen atom, or an alkyl group which may have a substituent, an aryl group or an aralkyl) A group: n is 0 or 1) Birds before the title compound (ii) is represented by the following general formula (iia) trimethylolpropane adduct of cyclic polyvalent isocyanate compound represented by -1 or the following general formula (iia) cyclic polyvalent isocyanate compound represented -2 The microcapsule according to claim 1, which is a methylolpropane adduct.

(Wherein, R ²¹ and R ²² are each independently an alkyl group, an aryl group or an aralkyl group which may have a substituent, and l is an integer of 0 to 4 and l is 2 to 4) When R is an integer of, the plurality of R ²¹ may be the same or different; m is an integer of 0 to 10, and when m is an integer of 2 to 10, the plurality of R ²² is the same But it may be different.)   The sheet | seat which has a microcapsule of Claim 1 or 2 which contains an active ingredient.   The resin composition containing the microcapsule of Claim 1 or 2 which contains an active ingredient.   The liquid composition containing the microcapsule of Claim 1 or 2 which contains an active ingredient.