JP2011173055A - Method of manufacturing oil dispersion liquid of encapsulated material, and the oil dispersion liquid of the encapsulated material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an oil dispersion liquid of an encapsulated material having an excellent property such as having an unrestricted core substance. <P>SOLUTION: The method of manufacturing the oil dispersion liquid of the encapsulated material whose core material is coated by a wall material mainly composed of a polymer includes: a step (1) of adjusting an aqueous dispersion liquid containing an encapsulated material whose core material is coated by a wall material mainly composed of a polymer; and a step (2) of inverting a phase of the encapsulated material in an aqueous dispersion liquid into an oil layer and preparing the oil dispersion liquid of the encapsulated material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an oily dispersion of an encapsulated product, and an oily dispersion of an encapsulated product obtained by the method.

  Conventionally, various substances have been encapsulated in many industrial and technical fields. In the printing, paint, and ink industries, many encapsulations of pigments and pigments have been put into practical use. In the field of medicine and agricultural chemicals, many attempts have been made to encapsulate drugs for the purpose of enhancing efficacy, reducing toxicity, imparting stability, delaying effects, and the like. Encapsulation methods are generally phase separation (coacervation), submerged drying (interfacial precipitation), spray drying, pan coating, submerged curing coating, interfacial polymerization, interfacial inorganic reaction. In-situ polymerization method is known. However, in these methods, the core material is limited, it is difficult to freely design the thickness of the shell layer (core material coating layer), it is difficult to encapsulate one core material, and the functional group on the capsule surface is free It is difficult to design particles having a uniform surface state, it is not easy to encapsulate in nano-order, it is difficult to apply to relatively unstable compounds, and there is a solvent used in the preparation of the preparation. There are problems such as being easily mixed into the product, or the properties of the resulting capsules being unsatisfactory, and the encapsulated product obtained also has problems depending on the application.

  In addition, as an invention created by the present inventors, the core material is not limited, the thickness of the shell layer (core material coating layer) can be freely designed, one core material can be encapsulated, the core material and the shell material It is possible to produce particles having a uniform surface state, capable of separating functions, easy to encapsulate in the nano order, and producing particles having a uniform particle size. The purpose of the present invention is to provide an encapsulated material that satisfies the requirements such as being capable of being reduced in toxicity or detoxified by encapsulating a core material that is gentle and toxic, etc. A coated encapsulated product, wherein the polymer is in contact with the core substance via an ionic surfactant a having an ionic group and a hydrophobic group, and at least the ionic surfactant a repeating structural unit derived from an ionic polymerizable surfactant B and / or ionic monomer having an opposite charge to a, and an ionic group having the same or opposite charge as the ionic surfactant a An encapsulated product composed of repeating structural units derived from an ionic polymerizable surfactant C having a hydrophobic group and a polymerizable group is known (see Patent Document 34).

Japanese Patent Publication No. 7-94634 JP-A-8-59715 JP 2003-306661 A JP-A-5-339516 JP-A-8-302227 JP-A-8-302228 JP-A-8-81647 JP-A-5-320276 Japanese Patent Laid-Open No. 8-21815 JP-A-8-295837 JP-A-9-3376 JP-A-8-183920 Japanese Patent Laid-Open No. 10-46075 JP-A-10-292143 Japanese Patent Laid-Open No. 11-80633 JP-A-11-349870 JP 2000-7961 A JP-A-9-31360 JP-A-9-217019 JP 9-316353 A Japanese Patent Laid-Open No. 9-104834 Japanese Patent Laid-Open No. 9-151342 Japanese Patent Laid-Open No. 10-140065 JP-A-11-152424 JP-A-11-166145 Japanese Patent Application Laid-Open No. 11-199783 JP-A-11-209672 JP-A-9-286939 JP 2000-44852 A JP 2000-53897 A JP 2000-53898 A JP 2000-53899 A JP 2000-53900 A International Publication No. 2006/043571 Pamphlet

The present invention has been made in view of the above-mentioned problems, and the object of the present invention is to provide an oily dispersion of an encapsulated product that can exhibit various functions in various industries and technical fields. It is in providing the manufacturing method of.
More specifically, in the present invention, (1) the core material is not limited, (2) the thickness of the shell layer (core material coating layer) can be designed freely, (3) one core material can be encapsulated, (4) The function can be separated between the core substance and the shell substance, (5) the particles having a uniform surface state can be produced, (6) the nano-order encapsulation is easy, (7) Particles having a uniform particle size can be produced, (8) Environment friendly, (9) Toxic or detoxification is possible by encapsulation of a core material having toxicity, etc. (10) An object of the present invention is to provide a method for producing an oil dispersion of an encapsulated product that satisfies all of the above (1) to (10), wherein the polymer of the encapsulated product can have both flexibility and strength. It is what.

  As a result of intensive studies, the inventor has found the following technical configuration and completed the present invention.

1. A method for producing an oily dispersion of an encapsulated material in which a core substance is coated with a wall material mainly composed of a polymer,
(1) a step of producing an aqueous dispersion of an encapsulated material in which a core material is coated with a wall material mainly composed of a polymer;
(2) Inverting the encapsulated product into an oil layer, and producing an oily dispersion of the encapsulated product,
The above step (1)
(A) Ionic surfactant a having an ionic group and a hydrophobic group on the surface of the core substance and / or ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group Adsorbing and
(B) The ionic surfactant a and / or the ionic surfactant b having an opposite charge to the ionic polymerizable surfactant A, the ionic polymerizable surfactant B, and the ionic monomer are selected. Mixing and adsorbing one or more of
(C) adding and mixing a hydrophobic monomer;
(D) adding the ionic surfactant c and / or the ionic polymerizable surfactant C having the same or opposite charge as the ionic surfactant a and / or the ionic polymerizable surfactant A; Mixing, and
(E) adding a polymerization initiator to this and polymerizing,
The above step (2)
(F) The ionic surfactant c and / or the ionic polymerization in an aqueous dispersion of an encapsulated product in which the core substance obtained in the step (1) is coated with a wall material mainly composed of a polymer. Adding an ionic surfactant f having an opposite charge to the ionic surfactant C;
(G) a step of adding a non-polar oily solvent dropwise to the mixture obtained in step (f) and mixing,
(H) leaving the mixed solution obtained in step (g), separating the oil phase and the aqueous phase containing the encapsulated product, and removing the aqueous phase;
(Li) A method for producing an oily dispersion of an encapsulated product, comprising the step of removing water from the oil phase.

  2. The method for producing an oil dispersion of an encapsulated product as described above, wherein the nonpolar oily solvent in the step (g) is an aliphatic hydrocarbon solvent or silicone oil.

  3. The method for producing an oily dispersion of an encapsulated product as described above, wherein in the step (c), urethane acrylate is further added and mixed.

  4). The polymer has a repeating structural unit derived from an ionic monomer having the same kind of charge as the ionic polymerizable surfactant C together with a repeating structural unit derived from the ionic polymerizable surfactant C. A process for producing an oily dispersion of an encapsulated product as described above.

  5. The method for producing an oily dispersion of an encapsulated product as described above, which comprises a step of irradiating ultrasonic waves after mixing in the step (b).

  6). An encapsulated oil dispersion obtained by the method for producing an encapsulated oil dispersion described above.

  According to the method for producing an oil dispersion of an encapsulated product of the present invention, the polymer of the core material coating layer can be freely designed according to the intended function. In particular, an oily dispersion of an encapsulated product having excellent physical properties can be obtained from an encapsulated product having a coating polymer rich in flexibility to an encapsulated product having a coating polymer having rigidity and high chemical resistance.

  The encapsulated product in the oily dispersion of the encapsulated product of the present invention can use either an inorganic material or an organic material as its core substance. Specifically, inorganic particles, organic particles, polymer particles and the like can be used, and the core substance is not limited. Moreover, it is possible to reduce the toxicity or detoxify by encapsulating a toxic core material.

  The encapsulated product in the oil dispersion of the encapsulated product of the present invention can be freely designed in the thickness of the shell layer (core material coating (polymer) layer), and the function is separated between the core material and the shell material. can do. In addition, particles having a uniform surface state can be produced.

Moreover, the manufacturing method of the oil-based dispersion liquid of the encapsulated product of the present invention can encapsulate one core substance, and can be easily encapsulated in nano order.
Moreover, the manufacturing method of the oil-based dispersion liquid of the encapsulated product of the present invention can manufacture particles having a uniform particle size.
In addition, the method for producing an oily dispersion of the encapsulated product of the present invention provides an encapsulated product having excellent physical properties from an encapsulated product having a flexible coating polymer to an encapsulated product having a rigid and chemical-resistant coating polymer. Oily dispersions can be produced.
Furthermore, when a coloring material (pigment) is used as the core material of the encapsulated product of the oil dispersion of the encapsulated product obtained by the method for producing an oily dispersion of the encapsulated product of the present invention, the dispersion stability is excellent. An oily dispersion of a color material (pigment) encapsulated product can be obtained. The oil-based ink using the encapsulated oil-based dispersion can provide a recorded material excellent in fastness and abrasion resistance. Further, when such oil-based ink is used as an ink for ink jet recording, a recorded matter having excellent ejection stability from the recording head and excellent image quality can be obtained.

It is a figure which shows the outline of the process (1) in embodiment of this invention. An anionic surfactant having a negative charge adsorbed on the surface of the core material and a cationic polymerizable surfactant having a positive charge (not shown, but a cation having a positive charge instead of the above cationic polymerizable surfactant) And a cationic monomer having at least a polymerizable group and a polymerizable group.), And a schematic diagram showing a state in which a negatively charged anionic polymerizable surfactant and a hydrophobic monomer coexist. . An anionic polymerizable surfactant having a negative charge adsorbed on the surface of the core substance and a cationic polymerizable surfactant having a positive charge (instead of the cationic polymerizable surfactant, not shown) A cationic monomer having at least a cationic group having a polymerizable group and a polymerizable group.) And a schematic diagram showing a state in which a negatively charged anionic polymerizable surfactant and a hydrophobic monomer coexist. It is. FIG. 3 is a schematic diagram illustrating a state in which the state illustrated in FIG. 2 is encapsulated. FIG. 4 is a schematic diagram illustrating a state in which the state illustrated in FIG. 3 is encapsulated. The schematic diagram which shows the final state of encapsulation of this embodiment. The schematic diagram which shows the final state of encapsulation of this embodiment.

Hereinafter, an embodiment of a method for producing an oil dispersion of an encapsulated product of the present invention will be described in detail.
The method for producing an oil dispersion of an encapsulated product according to this embodiment is a method for producing an oil-based dispersion of an encapsulated material in which a core substance is coated with a wall material mainly composed of a polymer.
(1) a step of producing an aqueous dispersion of an encapsulated material in which a core material is coated with a wall material mainly composed of a polymer;
(2) Inverting the encapsulated product into an oil layer, and producing an oily dispersion of the encapsulated product,
The above step (1)
(A) Ionic surfactant a having an ionic group and a hydrophobic group on the surface of the core substance and / or ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group Adsorbing and
(B) selected from ionic surfactant b, ionic polymerizable surfactant B, and ionic monomer having an opposite charge to ionic surfactant a and / or ionic polymerizable surfactant A Mixing and adsorbing one or more kinds; and
(C) adding and mixing a hydrophobic monomer;
(D) Addition and mixing of ionic surfactant c and / or ionic polymerizable surfactant C having the same or opposite charge as ionic surfactant a and / or ionic polymerizable surfactant A And a process of
(E) adding a polymerization initiator to this and polymerizing,
The above step (2)
(F) The ionic surfactant c and / or the ionic polymerizable interface is added to the aqueous dispersion of the encapsulated material in which the core material obtained in the step (1) is coated with a wall material mainly composed of a polymer. Adding an ionic surfactant f having an opposite charge to Activator C;
(G) a step of adding a non-polar oily solvent dropwise to the mixture obtained in step (f) and mixing,
(H) leaving the mixed solution obtained in step (g), separating the oil phase and the aqueous phase containing the encapsulated product, and removing the aqueous phase;
(Li) a step of removing moisture from the oil phase.

[Step (1) of this embodiment: Step of preparing an aqueous dispersion of an encapsulated product]
The encapsulated product (an aqueous dispersion thereof) produced in the step (1) in the method for producing an encapsulated oil dispersion according to this embodiment will be described.

  The encapsulated product is prepared by adsorbing an ionic surfactant a having an ionic group and a hydrophobic group and / or an ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group. The substance is an encapsulated material coated with a coating layer containing a polymer as a main component, the ionic surfactant a and / or the ionic polymerizable surfactant A adsorbed on the core material, and (i) One or more selected from ionic surfactant b, ionic polymerizable surfactant B, and ionic monomer having an opposite charge to ionic surfactant a and / or ionic polymerizable surfactant A And (ii) an ionic surfactant c and / or ionic polymerization having the same or opposite charge as the ionic surfactant a and / or ionic polymerizable surfactant A. sex And repeating structural units derived from a surface active agent C, derived from a hydrophobic monomer, and is characterized by comprising the repeating structural units existing between the (i) and (ii).

  Such an encapsulated product is obtained by adding an ionic surfactant a and / or ionic polymerizable property to an aqueous dispersion of a core material on which the ionic surfactant a and / or ionic polymerizable surfactant A is adsorbed. One or more selected from ionic surfactant b, ionic polymerizable surfactant B, and ionic monomer having opposite charges to surfactant A are added and mixed, and then a hydrophobic monomer is added and mixed. Thereafter, the ionic surfactant c and / or the ionic polymerizable surfactant C having the same or opposite charge as the ionic surfactant a and / or the ionic polymerizable surfactant A adsorbed on the core substance In addition, after mixing and emulsifying, a polymer coating layer can be formed and produced by adding a polymerization initiator and polymerizing in water.

  The present inventor has a step of adsorbing the ionic surfactant a and / or the ionic polymerizable surfactant A on the surface of the core substance, the ionic surfactant a and / or the ionic polymerizable surfactant. A step of mixing and adsorbing at least one selected from ionic surfactant b having an opposite charge to A, ionic polymerizable surfactant B and ionic monomer, a step of adding a hydrophobic monomer and mixing, Adding and mixing the ionic surfactant c and / or ionic polymerizable surfactant C having the same or opposite charge as the ionic surfactant a and / or ionic polymerizable surfactant A; And an ionic surfactant having an opposite charge to the ionic surfactant a and / or ionic polymerizable surfactant A by a production method including a step of polymerizing by adding a polymerization initiator thereto A repeating structural unit derived from one or more selected from agent b, ionic polymerizable surfactant B, and ionic monomer, and the same kind as ionic surfactant a and / or ionic polymerizable surfactant A Or a repeating structural unit derived from an ionic surfactant c and / or an ionic polymerizable surfactant C having opposite charges and a hydrophobic monomer and present between the two repeating structural units It has been found that a polymer having a repeating structural unit that contacts with a core substance via the ionic surfactant a and / or ionic polymerizable surfactant A can coat the core substance. .

  By using the above-described polymerization method, the ionic surfactant a and / or the ionic surfactant b having an opposite charge to the ionic group of the ionic polymerizable surfactant A adsorbed on the core substance, ionic polymerization 1 or more selected from the ionic surfactant B and the ionic monomer are ionically bonded, and the ionic surfactant b, the ionic polymerizable surfactant B, and the ionic monomer that are ionically bonded are selected. Ionic surfactant c and / or ionic polymerization having the same or opposite charge as the ionic surfactant a and / or ionic polymerizable surfactant A adsorbed on the core substance, of at least a kind of hydrophobic group The structure is formed in which the hydrophobic groups of the ionic surfactant C face each other, and the ionic surfactant c and / or the ionic groups of the ionic polymerizable surfactant C are oriented toward the aqueous phase. Was Polymer layer onto the core material by the polymerization reaction remain state is formed.

  That is, before the polymerization reaction, the arrangement form of the ionic surfactant, ionic polymerizable surfactant, ionic monomer, hydrophobic monomer, etc. existing around the core substance is extremely highly controlled, and in the outermost shell, A state in which the ionic groups are oriented toward the aqueous phase is formed. Then, the ionic polymerizable surfactant, ionic monomer, hydrophobic monomer and the like are converted into a polymer by the polymerization reaction in this highly controlled form, and a polymer layer is formed on the core substance. Thereby, the structure of the encapsulated product manufactured in the step (1) of the present embodiment is controlled with extremely high accuracy.

  The state before encapsulation of the encapsulated product according to the present embodiment described above and the state after encapsulation will be described below with reference to the drawings.

FIG. 1 is a diagram showing an outline of an encapsulated product in step (1) of the present embodiment.
FIG. 2 shows an anionic surfactant 2 ′ (ionic surfactant a) having an anionic group 21 having a negative charge and a hydrophobic group 22 adsorbed on the surface of a core substance 1, and a positive charge. Cationic polymerizable surfactant 3 (ionic polymerizable surfactant B) having a cationic group 31 having hydrophobicity, a hydrophobic group 32 and a polymerizable group 33 (not shown, but having a positive charge instead of B) A cationic monomer having at least a cationic group and a polymerizable group.), An anionic polymerizable surface activity having a negatively charged anionic group 41, a hydrophobic group 42, and a polymerizable group 43. It is a figure showing the state where the agent 4 (ionic polymerizable surfactant C) and the hydrophobic monomer 5 coexist.
The cationic polymerizable surfactant 3 is arranged so that its cationic group 31 faces the anionic group 21 of the anionic surfactant 2 ′ adsorbed on the core substance 1, and adsorbs with a strong ionic bond. . The hydrophobic group 32 and the polymerizable group 33 of the cationic polymerizable surfactant 3 are hydrophobically interacted with the hydrophobic group 42 and the polymerizable group 43 of the anionic polymerizable surfactant 4. The anionic groups 41 of the anionic polymerizable surfactant 4 are present in the direction in which the aqueous solvent is present, that is, in the direction farthest from the core substance 1. The hydrophobic monomer 5 is formed by the hydrophobic group 32 and the polymerizable group 33 of the cationic polymerizable surfactant 3 and the hydrophobic group 42 and the polymerizable group 43 of the anionic polymerizable surfactant 4 facing each other. Exists in the phase.

  FIG. 3 shows an anionic surfactant 2 (ionic polymerizable surfactant A) having a negatively charged anionic group 21, a hydrophobic group 22, and a polymerizable group 23 adsorbed on the surface of the core material 1. , A cationic polymerizable surfactant 3 (ionic polymerizable surfactant B) having a positively charged cationic group 31, a hydrophobic group 32 and a polymerizable group 33, and a negatively charged anionic group 41. FIG. 6 is a diagram illustrating a state in which an anionic polymerizable surfactant 4 (ionic polymerizable surfactant C) having a hydrophobic group 42 and a polymerizable group 43 coexists with a hydrophobic monomer 5. The cationic polymerizable surfactant 3 is arranged so that the cationic group 31 faces the anionic group 21 of the anionic polymerizable surfactant 2 adsorbed on the core substance 1, and adsorbs with a strong ionic bond. To do. The hydrophobic group 32 of the cationic polymerizable surfactant 3 faces the hydrophobic group 42 of the anionic polymerizable surfactant 4 by hydrophobic interaction, and the anionic polymerizable surfactant. The anionic group 41 of 4 is present in the direction in which the aqueous solvent exists, that is, in the direction farthest from the core substance 1. The hydrophobic monomer 5 exists in the hydrophobic phase formed by the hydrophobic group 32 of the cationic polymerizable surfactant 3 and the hydrophobic group 42 of the anionic polymerizable surfactant 4 facing each other.

  As shown in FIG. 4, a polymerization initiator is added to the mixed solution of FIG. 2, and a cationic polymerizable surfactant 3 (not shown, but a cation having at least a positively charged cationic group and a polymerizable group). The core material 1 is coated with the polymer layer 60 by polymerizing the anionic polymerizable surfactant 4 and the hydrophobic monomer 5, and the encapsulated product 100 is generated. Here, since the anionic groups 41 are regularly and densely present on the surface of the polymer layer 60 toward the aqueous phase side, the encapsulated product 100 is very well dispersed in the aqueous solvent. Similarly, FIG. 5 shows the case where the core material 1 is coated with the polymer layer 60 ″ and polymerized by adding a polymerization initiator to the mixed solution of FIG. 3 to produce an encapsulated material 100 ″.

Next, the constituent components of the encapsulated product will be described in detail.
[Core material]
The core material of the encapsulated material is not particularly limited, and examples thereof include coloring materials, inorganic materials, organic materials, inorganic-organic composite particles, inorganic colloids, polymer particles, and metal oxides (silica, titania, etc.).
For example, when a dangerous chemical or the like is intended as the organic substance, the encapsulated product has an effect of improving the handling of such a dangerous chemical or the like.
The inorganic colloid can be used for a highly transparent hard coat layer.
When colorant particles are used as the core substance, examples thereof include pigments such as inorganic pigments and organic pigments that can develop a desired color, and dyes that are insoluble or hardly soluble in water such as disperse dyes and oil-soluble dyes.
Further, when the color material is encapsulated by the method of the present embodiment, it can also be used as a colorant such as paint, pigment ink, or toner.
In the above-mentioned encapsulated material, the above core materials can be used alone or in combination of two or more.

[Ionic surfactant]
The ionic surfactant used in the present embodiment is not particularly limited as long as it has an ionic group and a hydrophobic group. The ionic group may be either an anionic group or a cationic group, and is appropriately selected according to the use of the encapsulated product.
Among the ionic surfactants used in the present embodiment, those having an anionic group are anionic surfactants and those having a cationic group are cationic surfactants.

  As the anionic group, a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and those selected from the group of these salts are suitable. Can be illustrated. Examples of the salt include Na salt, K salt, Ca salt, and organic amine salt.

As the cationic group, a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, and a quaternary ammonium cation is preferable. The primary ammonium cation is a monoalkylammonium cation (RNH ₃ ⁺ ), the secondary ammonium cation is a dialkylammonium cation (R ₂ NH ₂ ⁺ ), and the tertiary ammonium cation is a trialkylammonium cation (R ₃ NH). ⁺ ) And the like, and examples of the quaternary ammonium cation include (R ₄ N ⁺ ). Here, R is a hydrophobic group, and examples thereof include the following. Examples of the counter anion of the cationic group include Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ^{—, and the} like.

  The hydrophobic group is preferably one or more selected from the group consisting of an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and the alkyl group and the aryl group in the molecule. It is also possible to have both.

(Ionic polymerizable surfactant)
The ionic polymerizable surfactant used in the present embodiment is an ionic surfactant having the ionic group, the hydrophobic group, and a polymerizable group. The polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization, and specifically selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. It is preferred that Among these, an allyl group, a methacryloyl group, and an acryloyl group are particularly preferable.

The hydrophobic group is preferably one or more selected from the group consisting of an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and the alkyl group and the aryl group in the molecule. It is also possible to have both.
The ionic group may be either an anionic group or a cationic group, and is appropriately selected according to the use of the encapsulated product.

  The ionic polymerizable surfactant is referred to as an anionic polymerizable surfactant and a cationic polymerizable surfactant, respectively, depending on whether the ionic group has an anionic group or a cationic group.

[Anionic polymerizable surfactant]
The anionic polymerizable surfactant used in the present embodiment is an anionic surfactant having an anionic group, a hydrophobic group, and a polymerizable group.

  As the anionic group, a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and those selected from the group of these salts are suitable. Can be illustrated. Examples of the salt include Na salt, K salt, Ca salt, and organic amine salt.

  The hydrophobic group is preferably one or more selected from the group consisting of an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and the alkyl group and the aryl group in the molecule. It is also possible to have both.

  The polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization, and specifically selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. It is preferred that Among these, an allyl group, a methacryloyl group, and an acryloyl group are particularly preferable.

  Specific examples of the anionic polymerizable surfactant include an anionic allyl derivative as described in JP-B-49-46291, JP-B-1-24142, or JP-A-62-104802. Anionic propenyl derivatives as described in JP-A-62-221431, anionic acrylics as described in JP-A-62-34947 or JP-A-55-11525 Examples thereof include acid derivatives and anionic itaconic acid derivatives described in JP-B-46-34898 or JP-A-51-30284.

  An anionic polymerizable surfactant used in the present embodiment is, for example, a compound represented by the following general formula (31).

［式中、Ｒ²¹及びＲ³¹は、それぞれ独立して、水素原子又は炭素数１〜１２の炭化水素基であり、Ｚ¹は、炭素−炭素単結合又は式：
−ＣＨ₂−Ｏ−ＣＨ₂−
で表される基であり、ｍは２〜２０の整数であり、Ｘは式−ＳＯ₃Ｍ¹で表される基であり、Ｍ¹はアルカリ金属、アンモニウム塩、又はアルカノールアミンである。］

[Wherein, R ²¹ and R ³¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z ¹ represents a carbon-carbon single bond or a formula:
—CH ₂ —O—CH ₂ —
M is an integer of 2 to 20, X is a group represented by the formula —SO ₃ M ¹ , and M ¹ is an alkali metal, an ammonium salt, or an alkanolamine. ]

  Alternatively, for example, a compound represented by the following general formula (32) is preferable.

［式中、Ｒ²²及びＲ³²は、それぞれ独立して、水素原子又は炭素数１〜１２の炭化水素基であり、Ｄは、炭素−炭素単結合又は式：
−ＣＨ₂−Ｏ−ＣＨ₂−
で表される基であり、ｎは２〜２０の整数であり、Ｙは式−ＳＯ₃Ｍ²で表される基であり、Ｍ²はアルカリ金属、アンモニウム塩、又はアルカノールアミンである。］

[Wherein, R ²² and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and D represents a carbon-carbon single bond or a formula:
—CH ₂ —O—CH ₂ —
N is an integer of 2 to 20, Y is a group represented by the formula —SO ₃ M ² , and M ² is an alkali metal, an ammonium salt, or an alkanolamine. ]

  Examples of the anionic polymerizable surfactant represented by the formula (31) include compounds described in JP-A-5-320276 or JP-A-10-316909. By appropriately adjusting the value of m in the formula (31), it is possible to adjust the hydrophilicity of the surface of the encapsulated color material particles obtained by encapsulating the color material particles. Preferable polymerizable surfactants represented by the formula (31) include compounds represented by the following formula (310), and more specifically, the following formulas (31a) to (31d) The compound represented by these can be mentioned.

［式中、Ｒ³¹、ｍ、及びＭ¹は式（３１）で表される化合物と同様である。］

[Wherein, R ³¹ , m and M ¹ are the same as those in the compound represented by formula (31). ]

A commercial item can also be used as said anionic polymerizable surfactant. Adeka Soap SE-10N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound represented by formula (310) in which M ¹ is NH ₄ , R ³¹ is C ₉ H ₁₉ , and m = 10. Adeka Soap SE-20N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound represented by the formula (310) in which M ¹ is NH ₄ , R ³¹ is C ₉ H ₁₉ , and m = 20.
Moreover, as an anionic polymerizable surfactant used in this embodiment, the compound represented by General formula (33) is preferable, for example.

［式中、ｐは９又は１１であり、ｑは２〜２０の整数であり、Ａは−ＳＯ₃Ｍ³で表わされる基であり、Ｍ³はアルカリ金属、アンモニウム塩又はアルカノールアミンである。］
式（３３）で表される好ましいアニオン性重合性界面活性剤としては、以下の化合物を挙げることができる。

[In the formula, p is 9 or 11, q is an integer of 2 to 20, A is a group represented by —SO ₃ M ³ , and M ³ is an alkali metal, an ammonium salt or an alkanolamine. ]
Preferred examples of the anionic polymerizable surfactant represented by the formula (33) include the following compounds.

［式中、ｒは９又は１１、ｓは５又は１０である。］

[Wherein, r is 9 or 11, and s is 5 or 10. ]

  A commercial item can also be used as said anionic polymerizable surfactant. Examples of commercially available products include Aqualon KH series (Aqualon KH-5 and Aqualon KH-10) (above, trade names) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like. Aqualon KH-5 is a mixture of a compound represented by the above formula (33) wherein r is 9 and s is 5, and a compound where r is 11 and s is 5. Aqualon KH-10 is a mixture of a compound represented by the above formula wherein r is 9 and s is 10, and a compound where r is 11 and s is 10.

  Moreover, as an anionic polymerizable surfactant used for this embodiment, the compound represented by following formula (34) is preferable.

［式中、Ｒは炭素数８〜１５のアルキル基であり、ｎは２〜２０の整数であり、Ｘは−ＳＯ₃Ｂで表わされる基であり、Ｂはアルカリ金属、アンモニウム塩又はアルカノールアミンである。］

[Wherein, R is an alkyl group having 8 to 15 carbon atoms, n is an integer of 2 to 20, X is a group represented by —SO ₃ B, and B is an alkali metal, an ammonium salt or an alkanolamine] It is. ]

A commercial item can also be used as said anionic polymerizable surfactant. As a commercial item, Asahi Denka Kogyo Co., Ltd. Adeka rear soap SR series (Adeka rear soap SR-10, SR-20, SR-1025) (above, a brand name) etc. can be mentioned, for example. The ADEKA rear soap SR series is a compound in which B is NH ₄ in the general formula (34), SR-10 is n = 10, and SR-20 is n = 20.
Moreover, as an anionic polymerizable surfactant used for this embodiment, the compound represented by a following formula (A) can also be used.

［上記式（Ａ）中、Ｒ⁴は水素原子又は炭素数１から１２の炭化水素基を表し、ｌは２〜２０の数を表し、Ｍ⁴はアルカリ金属、アンモニウム塩、又はアルカノールアミンを表す。］

[In the above formula (A), R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, l represents a number of 2 to 20, and M ⁴ represents an alkali metal, an ammonium salt, or an alkanolamine. . ]

A commercial item can also be used as said anionic polymerizable surfactant. As a commercial item, the Dai-Ichi Kogyo Seiyaku Co., Ltd. product Aqualon HS series (Aquaron HS-10, HS-20, and HS-1025) (above, a brand name) is mentioned, for example.
Moreover, as an anionic polymerizable surfactant used in this embodiment, the alkyl allyl sulfosuccinic-acid sodium salt represented by General formula (35) can be mentioned, for example.

A commercial item can also be used as said anionic polymerizable surfactant. As a commercial item, Elyoinol JS-2 of Sanyo Chemical Industries Ltd. can be mentioned, for example, In the said General formula (35), it is a compound represented by m = 12.
Examples of the anionic polymerizable surfactant used in the present embodiment include methacryloyloxypolyoxyalkylene sulfate sodium salt represented by the general formula (36). In the following formula, n is 1-20.

A commercial item can also be used as said anionic polymerizable surfactant. As a commercial item, the Eleminol RS-30 of Sanyo Chemical Industries Ltd. can be mentioned, for example, In the said General formula (36), it is a compound represented by n = 9.
Moreover, as an anionic polymerizable surfactant used in this embodiment, the compound represented by General formula (37) can be used, for example.

A commercial item can also be used as said anionic polymerizable surfactant, and Antox MS-60 of Nippon Emulsifier Co., Ltd. corresponds to this.
The anionic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.

[Cationically polymerizable surfactant]
The cationic polymerizable surfactant used in the present embodiment is a cationic surfactant having a cationic group, a hydrophobic group, and a polymerizable group.
As the cationic group, a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, and a quaternary ammonium cation is preferable. The primary ammonium cation is a monoalkylammonium cation (RNH ₃ ⁺ ), the secondary ammonium cation is a dialkylammonium cation (R ₂ NH ₂ ⁺ ), and the tertiary ammonium cation is a trialkylammonium cation (R ₃ NH). ⁺ ) And the like, and examples of the quaternary ammonium cation include (R ₄ N ⁺ ). Here, R is a hydrophobic group, and examples thereof include the following.

The hydrophobic group is preferably one or more selected from the group consisting of an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and the alkyl group and the aryl group in the molecule. It is also possible to have both.
Examples of the counter anion of the cationic group include Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ^{—, and the} like.

  The polymerizable group is preferably an unsaturated hydrocarbon group capable of radical polymerization, and specifically selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. It is preferred that Among these, an allyl group, a methacryloyl group, and an acryloyl group are particularly preferable.

Examples of the cationic polymerizable surfactant include compounds represented by the general formula R _{[4- (l + m + n)]} R ¹ _l R ² _m R ³ _n N ⁺ .X ^−. (In the above general formula, R is a polymerizable group, R ¹ , R ² and R ³ are each an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and X ⁻ is Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ^— , and each of l, m and n is 1 or 0). Here, examples of the polymerizable group include those described above.

  Specific examples of the cationic polymerizable surfactant include dimethylaminoethyl octyl chloride methacrylate, dimethylaminoethyl cetyl chloride methacrylate, dimethylaminoethyl decyl chloride methacrylate, dimethylaminoethyl dodecyl chloride methacrylate, methacrylic acid methacrylate, Examples include acid dimethylaminoethyl tetradecyl chloride salt and the like. The cationic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.

(Ionic monomer)
The ionic monomer used in this embodiment is a compound having an ionic group and a polymerizable group, and is water-soluble.
The ionic group may be either an anionic group or a cationic group, and is appropriately selected according to the use of the encapsulated product.
As the anionic group, a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and those selected from the group of these salts are suitable. Can be illustrated. Examples of the salt include Na salt, K salt, Ca salt, and organic amine salt.

As the cationic group, a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, and a quaternary ammonium cation is preferable. The primary ammonium cation is a monoalkylammonium cation (RNH ₃ ⁺ ), the secondary ammonium cation is a dialkylammonium cation (R ² NH ₂ ⁺ ), and the tertiary ammonium cation is a trialkylammonium cation (R ₃ NH). ⁺ ) And the like, and examples of the quaternary ammonium cation include (R ₄ N ⁺ ). Here, R is a hydrophobic group, and examples thereof include the following. Examples of the counter anion of the cationic group include Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ^{—, and the} like.

Depending on whether the ionic group has an anionic group or a cationic group, they are referred to as an anionic water-soluble monomer and a cationic water-soluble monomer, respectively.
Preferred specific examples of the cationic water-soluble monomer that can be used in the present embodiment include dimethylaminoethyl methyl chloride methacrylate, dimethylaminoethyl benzyl methacrylate methacrylate, methacryloyloxyethyltrimethylammonium chloride salt, diallyldimethylammonium chloride salt, And 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride salt, and the like. A commercial item can also be used as said cationic water-soluble monomer, For example, Acryester DMC (Mitsubishi Rayon Co., Ltd.), Acryester DML60 (Mitsubishi Rayon Co., Ltd.), and C-1615 (Daiichi Kogyo Seiyaku) (Co., Ltd.)). The cationic water-soluble monomers exemplified above can be used alone or as a mixture of two or more.

  Preferable specific examples of the anionic water-soluble monomer that can be used in this embodiment include, as monomers having a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, propylacrylic acid, isopropylacrylic acid, 2-acryloyloxyethyl succinate. Examples include acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, itaconic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are preferable. Examples of the monomer having a sulfonic acid group include 4-styrene sulfonic acid and its salt, vinyl sulfonic acid and its salt, sulfoethyl acrylate and its salt, sulfoethyl methacrylate and its salt, sulfoalkyl acrylate and its salt, sulfoalkyl Methacrylate and its salt, sulfopropyl acrylate and its salt, sulfopropyl methacrylate and its salt, sulfoaryl acrylate and its salt, sulfoaryl methacrylate and its salt, butylacrylamide sulfonic acid and its salt, 2-acrylamido-2-methylpropanesulfone Examples include acids and salts thereof. Examples of the monomer having a phosphone group include phosphoric acid group-containing (meth) acrylates such as phosphoethyl methacrylate. The anionic water-soluble monomers exemplified above can be used alone or as a mixture of two or more.

  The ionic polymerizable surfactant A used in the present invention is used for the purpose of adsorbing to the core substance, and the ionic group may be either anionic or cationic.

  In addition, the ionic polymerizable surfactant A used in the present invention is described in the above-mentioned item of the ionic polymerizable surfactant, the item of the anionic polymerizable surfactant, and the item of the cationic polymerizable surfactant. Is the same.

(Hydrophobic monomer)
The hydrophobic monomer as used in the present embodiment refers to a polymerizable monomer having at least a hydrophobic group and a polymerizable group in its structure, and the hydrophobic group is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic group. Examples thereof include those selected from the group of group hydrocarbon groups.

  Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group, and examples of the alicyclic hydrocarbon group include a cyclohexyl group, a dicyclopentenyl group, a dicyclopentanyl group, and an isobornyl group. Examples of the group hydrocarbon group include a benzyl group, a phenyl group, and a naphthyl group.

As the polymerizable group of the hydrophobic monomer, the same group as described in the item of the ionic polymerizable surfactant can be used.
Specific examples of the hydrophobic monomer include styrene derivatives such as styrene, methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, t-butylstyrene, bromostyrene, and p-chloromethylstyrene; methyl acrylate, acrylic Ethyl isopropyl acrylate, n-butyl acrylate, butoxyethyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, benzyl acrylate, acrylic acid Phenyl, phenoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, Cyclopentenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, and isobornyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxy polyethylene glycol acrylate Monofunctional acrylic acid esters such as nonylphenol EO adduct acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl diglycol acrylate, octoxypolyethylene glycol polypropylene glycol monoacrylate, methyl methacrylate, Ethyl tacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate , Stearyl methacrylate, isodecyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, methoxydiethylene glycol methacrylate, polypropylene glycol monomethacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, tetrahydromethacrylate Furfuryl, t-butylcyclo Monofunctional methacrylates such as hexyl methacrylate, behenyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, butoxymethyl methacrylate, and isobornyl methacrylate, octoxy polyethylene glycol polypropylene glycol monomethacrylate, etc. Allyl compounds such as allylbenzene, allyl-3-cyclohexanepropionate, 1-allyl-3,4-dimethoxybenzene, allylphenoxyacetate, allylphenylacetate, allylcyclohexane, and polyvalent allyl carboxylate; fumaric acid, Unsaturated esters such as maleic acid and itaconic acid; radical polymerizable groups such as N-substituted maleimide and cyclic olefin Such as monomers and the like.

  As a monomer used for synthesizing a polymer that is a main component of the capsule wall material of the present embodiment, a monomer represented by the following general formula (2) can be used as long as the effects of the present embodiment are not impaired. .

［ただし、Ｒ¹は水素原子又はメチル基を表す。Ｒ²はｔ−ブチル基、脂環式炭化水素基、芳香族炭化水素基、又はヘテロ環基を表す。ｍは０〜３、ｎは０又は１の整数を表す。］

[However, R ¹ represents a hydrogen atom or a methyl group. R ² represents a t-butyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. m represents an integer of 0 to 3, and n represents an integer of 0 or 1. ]

In the general formula (2), examples of the alicyclic hydrocarbon group represented by R ² include a cycloalkyl group, a cycloalkenyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantane group. Examples of the heterocyclic group include a tetrahydrofuran group.
Specific examples of the monomer represented by the general formula (2) include the following.

By introducing the R ² group, which is a “bulky” group derived from the monomer represented by the general formula (2), into the polymer of the capsule wall material, the flexibility of the molecule of the polymer is reduced, that is, the molecular The mobility can be lowered to increase the mechanical strength and heat resistance of the polymer.
On the other hand, among the above-mentioned hydrophobic monomers, a polymer having a repeating structural unit derived from a monomer having a long-chain alkyl group has flexibility. Therefore, a repeating structural unit derived from a crosslinking monomer described below and / or a repeating structural unit derived from a monomer represented by the general formula (2) and a repeating structural unit derived from a monomer having a long-chain alkyl group, By appropriately adjusting the ratio, it is possible to synthesize a capsule wall material polymer having excellent mechanical strength and excellent solvent resistance in combination with preferable plasticity.

(Crosslinkable monomer)
By using the crosslinkable monomer together with the hydrophobic monomer, the mechanical strength and heat resistance of the polymer can be increased, and the shape maintenance of the capsule wall material is improved. In addition, swelling of the polymer by the organic solvent and penetration of the organic solvent into the polymer can be suppressed, and the solvent resistance of the capsule wall material can be improved.

  As the crosslinkable monomer used in the present embodiment, a compound having two or more unsaturated hydrocarbon groups of at least one selected from vinyl group, allyl group, acryloyl group, methacryloyl group, propenyl group, vinylidene group, and vinylene group The thing which has is mentioned. Specific examples of the crosslinkable monomer include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, and bis (acryloxyethyl) hydroxyethyl isocyanurate. Bis (acryloxy neopentyl glycol) adipate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, 2-hydroxy-1 , 3-Diacryloxypropane, 2,2-bis [4- (acryloxy) phenyl] propane, 2,2- [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy polyethoxy) phenyl] propane , Hydroxybivalic acid neopentyl glycol diacrylate, 1,4-butanediol diacrylate, dicyclopentanyl diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tri Acrylate, tetrabromobisphenol A diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyania Rate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxy) phenyl] propane, 2 , 2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxydie) Toxi) phenyl] propane, 2,2-bis [4- (methacryloxyethoxypolyethoxy) phenyl] propane, tetrabromobisphenol A dimethacrylate, dicyclopentanyl dimethacrylate, dipentaerythritol hexamethacrylate, glycerol dimethacrylate, hydroxy Neopentyl glycol dimethacrylate, dipentaerythritol monohydroxypentamethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, triglycerol dimethacrylate, trimethylolpropane trimethacrylate, tris (methacryloxyethyl) ) Isocyanurate, allyl methacrylate, divinylben Emissions, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, and diethylene glycol bis allyl carbonate.

[Urethane acrylate]
In this embodiment, urethane acrylate can be used together with the above-described hydrophobic monomer. As a result, the polymer constituting the encapsulated product can be freely designed according to the intended function, so that it can be used from an encapsulated product having a flexible coating polymer to an encapsulated product having a rigid and chemical-resistant coating polymer. Encapsulated products excellent in the physical properties required for them and oily dispersions thereof can be obtained.

  The urethane acrylate as referred to in the present embodiment refers to those having a urethane bond and an acrylic group in the structure, and a diisocyanate and a diol are subjected to an addition reaction, and the remaining isocyanate group further has an active hydrogen group such as a hydroxyl group (meth). It can be synthesized by further addition reaction of acrylate.

  Examples of the diisocyanate compound include hexamethylene diisocyanate (HDI), 1,3-diisocyanatomethylcyclohexane (H6 XDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), xylylene diisocyanate (XDI), 4,4 ′. -Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, etc. Among these, it is preferable to select one of HDI, H6 XDI, and IPDI as a countermeasure against yellowing of the final composite (the coating polymer of the encapsulated product of the present embodiment).

  Examples of the diol include polyester polyols such as pivalic acid neopentyl glycol ester and polycaprolactone polyol; polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol; polycarbonate polyols such as polyhexamethylene carbonate glycol; ethylene glycol, Propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, methylpentanediol, neopentyl glycol, 3,3-dimethylolheptane, carbon number 7-22 alkanediol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, charcoal 17-20 alkane-1,2-diol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, There are 2,2-bis (hydroxymethyl) -3-butanol, other aliphatic triols having 8 to 24 carbon atoms, tetramethylolmethane, and the like. Among these, polyester polyols such as polycaprolactone polyol and polyether polyols such as polyethylene glycol and polypropylene glycol can be preferably used.

  Furthermore, examples of the (meth) acrylate having an active hydrogen group such as a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

  The urethane acrylate is preferably selected in terms of the number of functional groups depending on the physical properties (flexible to high strength) required for the encapsulated polymer of the present embodiment, and more preferably bifunctional or higher. Moreover, it is preferable that the molecular weight of urethane acrylate is 100-5,000, and it is more preferable that it is 400-2,000.

  As urethane acrylates, commercially available products are EBECRYL8402 (viscosity: 12,500 mPa · s, bifunctional, molecular weight: 1,000), 9270 (viscosity: 7,500 mPa · s, bifunctional, molecular weight: 1,000), The same 4858 (viscosity: 7,000 mPa · s, bifunctional, molecular weight: 450) (manufactured by Daicel-Cytec Co., Ltd.) can be suitably used.

  In addition to the film formability of the encapsulated product of the present embodiment, the strength of the coating film, chemical resistance, water resistance, light resistance, weather resistance, optical properties, physical properties and chemical properties include hydrophobic monomers, crosslinkable monomers, It depends on the structure of the urethane acrylate and the structure of the copolymer composed of these. Therefore, an optimal hydrophobic monomer, hydrophobic monomer, or urethane acrylate is selected according to the performance required for the encapsulated product. For example, the film formability of the encapsulated material, the strength of the coating film, and the chemical resistance can be controlled by controlling the glass transition point (Tg) of the copolymer (copolymer) covering the core material. Generally, in polymer solids, especially amorphous polymer solids, when the temperature is raised from a low temperature to a high temperature, a state where a large amount of deformation occurs with a small force from a state where a very large force is required for slight deformation (glass state). A phenomenon that suddenly changes to a temperature occurs, and the temperature at which this phenomenon occurs is called the glass transition point (or glass transition temperature). Generally, in the differential heat curve obtained by temperature rise measurement with a differential scanning calorimeter, the intersection of the base line when the tangent line is drawn from the bottom of the endothermic peak toward the end point of the endotherm. Temperature is taken as the glass transition point. In addition, it is known that other physical properties such as elastic modulus, specific heat, and refractive index also change abruptly at the glass transition point, and it is known that the glass transition point is also determined by measuring these physical properties. ing. Furthermore, the glass transition point can be calculated by the Fox formula from the weight fraction of the monomer used in synthesizing the copolymer and the glass transition point of the homopolymer obtained by homopolymerizing the monomer.

（上記式中、Ｔｇ_[p]は得られるポリマーのガラス転移温度、ｉは種類の異なるモノマーごとに付した番号、Ｔｇ_[hp]iは重合に用いるモノマーｉのホモポリマーのガラス転移温度、ｘ_iは重合するモノマーの重量総計に対するモノマーｉの重量分率を表す。）

(In the above formula, Tg _[p] is the glass transition temperature of the resulting polymer, i is the number assigned to each of the different types of monomers, Tg _{[hp] i} is the glass transition temperature of the homopolymer of monomer i used for polymerization, x _i represents the weight fraction of monomer i with respect to the total weight of monomers to be polymerized.)

  That is, when the temperature environment where the encapsulated product of this embodiment is placed is higher than the glass transition point of the copolymer covering the core material of the encapsulated product of this embodiment, the copolymer has a small force. In this state, a large deformation occurs, and when it reaches the melting point, it melts. At this time, if another encapsulated product is present in the vicinity, the encapsulated products are fused to form a film. Further, even when the environmental temperature does not reach the melting point, the copolymer molecules covering the encapsulated materials can be entangled with each other when the encapsulated materials are contacted with each other by a strong force. If the conditions are adjusted, the copolymers (copolymers) may be fused together.

(Polymerization initiator)
As described above, the polymer constituting the capsule wall material of the encapsulated product of the present embodiment is obtained by polymerizing an ionic polymerizable surfactant, an ionic monomer, and a hydrophobic monomer. This polymerization reaction can be performed using a known polymerization initiator, and it is particularly preferable to use a radical polymerization initiator. In this embodiment, it is preferable to use a polymerization initiator suitable for the polymerization method employed in producing the encapsulated product. In the case of using the emulsion polymerization method and the miniemulsion polymerization method, the polymerization initiator is preferably a water-soluble polymerization initiator, for example, persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, Examples thereof include water-soluble azo compound-based initiators such as 2,2-azobis- (2-methylpropionamidine) dihydrochloride and 4,4-azobis- (4-cyanovaleric acid). Also, a redox that combines an oxidizing agent such as potassium persulfate, ammonium persulfate, sodium persulfate, and hydrogen peroxide with a reducing agent such as sodium sulfite, sodium hyposulfite, ferrous sulfate, ferrous nitrate, and thiourea. A system initiator can also be used. In the case of using the suspension polymerization method and the miniemulsion polymerization method, dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2,4-dimethylvaleronitrile), Oil-soluble azo compound initiators such as 2,2′-azobis (2-methylbutyronitrile), dilauroyl peroxide, disuccinic acid peroxide, 1,1,3,3-tetramethylbutyl (peroxy) It is preferable to use an oil-soluble polymerization initiator such as a peroxide such as 2-ethylhexanoate) or 2,5-dimethyl-2,5-di (2-etahexanoylperoxy) hexane.

[Other ingredients]
The encapsulated product of the present embodiment is obtained by coating a core material with a material containing a polymer as a main component. In addition to the above-described raw materials, the encapsulated material absorbs ultraviolet rays as long as the effects of the present embodiment are not impaired. Other components such as an agent, a light stabilizer, an antioxidant, a flame retardant, a plasticizer, and a wax can be contained in the polymer.

[Polymerization method of capsules]
The capsule wall material of the encapsulated product of this embodiment is synthesized by a polymerization reaction in the step (1), and this polymerization reaction includes an ultrasonic generator, a stirrer, a reflux condenser, a dropping funnel, and a temperature controller. It is preferable to use a reaction vessel.
The manufacturing method of the encapsulated material in step (1) of the present embodiment will be described below.

Specifically, the encapsulated material according to the embodiment of the present embodiment is preferably produced by the following procedure.
(I) First, an ionic surfactant a having an ionic group and a hydrophobic group on the surface of the core substance and / or an ionic polymerizable surface activity having an ionic group, a hydrophobic group and a polymerizable group Agent A is adsorbed. Specifically, when the core substance is solid, ion exchange in which the ionic surfactant a and / or the ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group is dissolved. After the core substance is put into water and mixed, this mixed solution is put into a general dispersing machine such as a ball mill, roll mill, Eiger mill, or jet mill for dispersion treatment, and the ionic surfactant a and / or ion It is preferable that the ionic polymerizable surfactant A having a functional group, a hydrophobic group, and a polymerizable group is sufficiently adsorbed on the core substance. As described above, the substance adsorbed on the core substance may be at least having an ionic group. In consideration of improvement in dispersibility of the core substance in the dispersion medium, a nonionic surfactant may be used in combination, and the nonionic surfactant may have a polymerizable group. .

  Further, the ionic surfactant a and / or the ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group that are not adsorbed to the core material may be removed by ultrafiltration or the like. preferable. If a large amount of unadsorbed ionic surfactant remains, the amount of polymer particles as a by-product increases and encapsulation of the core substance becomes insufficient. However, since the dispersion of the core substance may become unstable if too much is removed, it is preferable to appropriately determine the degree of ultrafiltration or the like in view of the dispersion stability and the state of encapsulation.

  (II) Next, the ionic surfactant a and / or ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group is adsorbed onto the dispersion of the core substance. Ionic surfactant b having an opposite charge to ionic surfactant a and / or ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group, and ionic polymerizable surfactant One or more selected from Agent B and ionic monomer are added and mixed. At this time, at least one ionic group selected from ionic surfactant b, ionic polymerizable surfactant B, and ionic monomer is ionic surfactant a and / or ionic group and hydrophobic group. It is preferable to irradiate the mixture with ultrasonic waves so as to easily bind ionically to the ionic group of the ionic polymerizable surfactant A having a polymerizable group.

  The ionic surfactant a and / or the ionic surfactant a and / or the dispersion of the core material adsorbing the ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group. Or from ionic surfactant b, ionic polymerizable surfactant B, and ionic monomer having an opposite charge to ionic polymerizable surfactant A having ionic group, hydrophobic group and polymerizable group The addition amount of one or more selected is the total number of ionic groups of the ionic surfactant A and / or the ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group ( That is, it is preferably in the range of 0.5 to 2 times mol, and 0.8 to 1.2 times mol of the ionic group amount [mol / g] existing on the surface of 1 g of the core substance used. More preferably, it is the range. With respect to the total molar amount of the ionic surfactant a and / or ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group adsorbed on the surface of the core substance, these By adding 0.5 times mole or more of the ionic polymerizable surfactant B and / or ionic monomer having an opposite charge to the above, an encapsulated product having good dispersibility can be obtained by the subsequent polymerization reaction. it can. This is presumably because the core substance can be sufficiently covered with the ionic polymerizable surfactant B and / or the ionic monomer. On the other hand, by reducing the addition amount of the ionic polymerizable surfactant B and / or the ionic monomer to 2 times or less, it is possible to suppress the generation of polymer particles having no core substance (particles made of only a polymer). it can.

  (III) Further, a hydrophobic monomer is added. The timing of adding the hydrophobic monomer may be after (IV). In addition, as above-mentioned, when physical properties, such as mechanical strength of the coating polymer of an encapsulated material, chemical resistance, water resistance, etc. are requested | required, it is preferable to add a crosslinkable monomer and urethane acrylate with a hydrophobic monomer. It is preferable to use urethane acrylate by dissolving it in a hydrophobic monomer or a crosslinkable monomer.

  (IV) Next, the ionic surfactant c having the same or opposite charge as the ionic surfactant a and / or the ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group. And / or ionic polymerizable surfactant C is added and mixed. Here, the addition amount of the ionic surfactant c and / or the ionic polymerizable surfactant C is one or more selected from the ionic surfactant b, the ionic polymerizable surfactant B, and the ionic monomer. On the other hand, the range is preferably 0.5 times to 10 times mol, and more preferably 0.5 times to 5 times mol. By making the addition amount 0.5 times mole or more, the aggregation of the encapsulated product can be suppressed, and an encapsulated aqueous dispersion having excellent dispersion stability can be obtained. Moreover, by making the said addition amount 10 times mole or less, the quantity of the ionic polymerizable surfactant C which does not contribute to encapsulation of a core substance can be reduced, and generation | occurrence | production of a polymer particle can be suppressed.

  Through the above steps, the ionic surfactant a and / or the surface of the core substance adsorbed with the ionic polymerizable surfactant A having an ionic group, a hydrophobic group, and a polymerizable group is adsorbed to the ionic surfactant. a and / or an ionic surfactant b having an opposite charge to the ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group, an ionic polymerizable surfactant B, an ion One or more types selected from the ionic monomer are electrostatically attached, the hydrophobic monomer (and the crosslinkable monomer and urethane acrylate) are localized on the outer side, and the ionic surfactant a and / or the outer side. The ionic surfactant c and / or the ionic polymerizable interface having the same or opposite charge as that of the ionic group of the ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group Activator C is the Io Sex group is estimated to be oriented toward the aqueous phase side to form a admicell (admicell). In addition, even if it does not perform ultrasonic irradiation in said process, when formation of an admicel is obtained, ultrasonic irradiation is not necessarily required.

  (V) Next, a polymerization initiator is added to the mixed solution prepared as described above to perform a polymerization reaction. The polymerization initiator may be added all at once or divided at a temperature at which the polymerization initiator is activated, or may be added continuously. Moreover, after adding a polymerization initiator, you may heat the said liquid mixture to the temperature by which a polymerization initiator is activated. In this embodiment, emulsion polymerization and miniemulsion polymerization are preferably carried out by dropping an aqueous solution obtained by dissolving a water-soluble polymerization initiator in ion-exchanged water into an aqueous dispersion in a reaction vessel at a predetermined dropping rate. can do. Moreover, when using an oil-soluble polymerization initiator in miniemulsion polymerization, it can carry out suitably by adding as it is or melt | dissolving in a hydrophobic monomer, and adding. The activation of the polymerization initiator can be suitably carried out by raising the temperature to a temperature at which the polymerization initiator is cleaved and initiator radicals are generated. The added polymerization initiator is cleaved to generate an initiator radical, which causes a polymerization reaction by attacking the polymerizable group of the ionic polymerizable surfactant and the polymerizable group of the ionic monomer and the hydrophobic monomer. . Although the polymerization temperature and the polymerization reaction time vary depending on the type of polymerization initiator used and the type of the above-described polymerizable compound, it is easy to appropriately set preferable polymerization conditions. In general, the polymerization temperature is preferably in the range of 40 ° C to 90 ° C, and the polymerization time is preferably 3 hours to 12 hours.

  In the polymerization reaction, the ionic surfactant a and / or the ionic polymerizable surfactant A having the ionic group, the hydrophobic group, and the polymerizable group, the ionic polymerizable surfactant B, and the ion Each of the polymerizable polymerizable surfactant C, the hydrophobic monomer, the crosslinkable monomer, and the urethane acrylate can be used alone or in combination of two or more. Moreover, since said polymerization reaction is performed using an ionic polymerizable surfactant, the emulsified state of the mixed solution is often good without using an emulsifier. Therefore, it is not always necessary to use an emulsifier, but at least one selected from the group consisting of known anionic, nonionic, and cationic emulsifiers may be used as necessary.

  After completion of the polymerization, it is preferable to adjust the pH of the obtained aqueous dispersion of the encapsulated product of the present embodiment to a range of 7.0 to 9.0 and further perform filtration. Filtration is preferably ultrafiltration.

  According to the above-described polymerization method, the arrangement form of the ionic polymerizable surfactant and polymerizable monomer molecules existing around the core substance is extremely highly controlled, and the ionic group (anionic group or cationic group) is formed in the outermost layer. In the outermost layer of the encapsulated product, the ionic group (anionic group or cationic group) is highly oriented toward the aqueous phase side. Form.

[Step (2) of this Embodiment: Step of Producing Oil-Based Dispersion Containing Encapsulated Product]
The manufacturing method of the oil-based dispersion liquid of the encapsulated product of the present embodiment is characterized by having a step (2) after the step (1) described above. This step (2)
(F) The ionic surfactant c and / or the ionic polymerizable interface is added to the aqueous dispersion of the encapsulated material in which the core material obtained in the step (1) is coated with a wall material mainly composed of a polymer. Adding an ionic surfactant f having an opposite charge to Activator C;
(G) a step of adding a non-polar oily solvent dropwise to the mixture obtained in step (f) and mixing,
(H) leaving the mixed solution obtained in step (g), separating the oil phase and the aqueous phase containing the encapsulated product, and removing the aqueous phase;
(Li) a step of removing moisture from the oil phase.

The final state of the encapsulated product of the present embodiment manufactured in the step (2) of the present embodiment described above will be described below with reference to the drawings. FIGS. 6 and 7 illustrate the step (2) of the present embodiment. It is a figure which shows the outline of an encapsulated material. That is, the ionic surfactant having an opposite charge to the ionic surfactant c and / or the ionic polymerizable surfactant C in the aqueous dispersion of the encapsulated product obtained in the step (1) of the present embodiment. After adding a non-polar oily solvent dropwise to the mixed solution to which the agent f has been added, the mixture is allowed to stand to separate the oil phase containing the encapsulated product from the aqueous phase, and after removing the aqueous phase, water is removed from the oil phase. 6 and 7 can be obtained in the final state of the encapsulated product.

<Ionic surfactant f>
The ionic surfactant f used in the present embodiment has a charge opposite to that of the ionic groups of the ionic surfactant c and the ionic polymerizable surfactant C.
The ionic surfactant f used in the present embodiment is not particularly limited as long as it has an ionic group and a hydrophobic group. Among the ionic surfactants used in the present embodiment, those having an anionic group are anionic surfactants and those having a cationic group are cationic surfactants.

  As the anionic group, a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and those selected from the group of these salts are suitable. Can be illustrated. Examples of the salt include Na salt, K salt, Ca salt, and organic amine salt.

As the cationic group, a cationic group selected from the group consisting of a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, and a quaternary ammonium cation is preferable. The primary ammonium cation is a monoalkylammonium cation (RNH ₃ ⁺ ), the secondary ammonium cation is a dialkylammonium cation (R ₂ NH ₂ ⁺ ), and the tertiary ammonium cation is a trialkylammonium cation (R ₃ NH). ⁺ ) And the like, and examples of the quaternary ammonium cation include (R ₄ N ⁺ ). Here, R is a hydrophobic group, and examples thereof include the following. Examples of the counter anion of the cationic group include Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ^{—, and the} like.

  The hydrophobic group is preferably one or more selected from the group consisting of an alkyl group having 8 to 16 carbon atoms and an aryl group such as a phenyl group and a phenylene group, and the alkyl group and the aryl group in the molecule. It is also possible to have both.

  Moreover, it is preferable that the addition amount of the ionic surfactant f is an amount at which the aqueous dispersion obtained in the step (1) described above has an isoelectric point. Specifically, it is preferable to add the ionic surfactant f having an ionic group amount equimolar to the ionic group of the ionic surfactant c and / or the ionic polymerizable surfactant C.

<Non-polar oily solvent>
As the non-polar oily solvent used in the present embodiment, an aliphatic hydrocarbon solvent or silicone oil can be suitably used. As the aliphatic hydrocarbon solvent, an isoparaffin solvent is preferable.

  Commercially available non-polar oil solvents include Exxon's Isopar (registered trademark), Philips Petroleum's Saltor, Idemitsu Petrochemical's IP Solvent, and Petroleum Naphtha's Shell Petrochemical Co., Ltd. B. R, Shellzol (registered trademark), Pegasol of Mobil Oil Co., etc. can be suitably used.

The aspect ratio (long and short) of the encapsulated product of the present embodiment is 1.0 to 1.3, and the Zingg index is 1.0 to 1.3 (more preferably 1.0 to 1.2). is there. That is, when the short diameter of a particle is b, the long diameter is l, and the thickness is t (l ≧ b ≧ t> 0), the aspect ratio (long / shortness) is 1 / b (≧ 1), and the flatness is b / t (≧ 1), Zingg index = long / shortness / flatness = (l · t) / b 2. That is, the true sphere has an aspect ratio of 1 and a Zingg index of 1. When the Zingg index is larger than 1.3, the encapsulated product becomes flatter and the isotropic property is lowered. The method for setting the aspect ratio and the Zingg index within the above ranges is not particularly limited, but the encapsulated product according to the production method of the present embodiment can easily satisfy this condition.
In addition, in the encapsulated product produced by a method other than the emulsion polymerization method such as the acid precipitation method or the phase inversion emulsification method, the aspect ratio and the Zingg index are not easily within the above ranges.

[Ink composition]
In this embodiment, the encapsulated color material obtained when a color material is used as the core material can be used for the ink composition, and can also be used for ink for inkjet recording. In particular, the case where the color material particles are pigments is preferable. The ink composition for ink jet recording using the oil dispersion of the encapsulated product of the present embodiment is an oil-based ink composition, and the above encapsulated pigment is dispersed and contained in an oily medium. The content of the encapsulated pigment in the ink composition is preferably 1% by weight to 20% by weight and more preferably 3% by weight to 15% by weight with respect to the total weight of the ink composition. In particular, in order to obtain a high printing density and high color developability, the content is preferably 5% by weight to 15% by weight. As the oily solvent to be used, the following ones used for the oil-based dispersion of the encapsulated pigment of the above-described embodiment are preferably used.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the examples.
The anionic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku) used in this example is a compound represented by the following formula.

“Manufacture of oil dispersion“ MCP1 ”of encapsulated pigment”
<Step (1) Synthesis of encapsulated pigment and preparation of aqueous dispersion of capsule pigment>
50 g of anionic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 850 g of ion-exchanged water, and C.V. I. 100 g of Pigment Blue 15: 4 was added and mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling ratio of 70% and a rotation speed of 5000 rpm using a disperser Eiger Motor Mill M250 (manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration by a cross flow method was performed using an ultrafiltration apparatus, and the solid solution concentration was adjusted to 10% by mass until the permeated liquid disappeared. The obtained pigment dispersion was subjected to thermogravimetry, and the adsorption amount of the anionic polymerizable surfactant Aqualon KH-10 was determined from the weight loss value. As a result, KH-10 / pigment was 25.6 / 100.

  To 50 g of the obtained pigment dispersion, 0.3 g of dimethylaminoethyl methyl chloride methacrylate as a cationic water-soluble monomer was added and mixed, and then irradiated with ultrasonic waves for 30 minutes. Next, 19.2 g of benzyl methacrylate, 6.4 g of isobornyl methacrylate, and 6.4 g of lauryl methacrylate were added to and mixed with the obtained mixture, and then further dissolved in 50 ml of ion-exchanged water, 0.75 g The anionic polymerizable surfactant Adekari Soap SR-10 was added, and 380 ml of ion-exchanged water was further added and mixed. This mixed solution was adjusted to pH 9.0 with 1 mol / l potassium hydroxide aqueous solution.

  This mixed solution is put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, and a nitrogen introduction tube, and the internal temperature of the reaction vessel is raised to 80 ° C. An aqueous solution in which 0.75 g of potassium sulfate was dissolved in 100 g of ion-exchanged water was dropped, and a polymerization reaction was performed at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel. After completion of the polymerization, the pH was adjusted to 8 with a 1 mol / l aqueous potassium hydroxide solution, and then filtered through a membrane filter having a pore size of 1 μm to remove coarse particles. Next, using an ultrafiltration device, ultrafiltration by a crossflow method is performed, and the solid content concentration is set to 15% by mass to obtain an aqueous dispersion of the encapsulated pigment in step (1) of this embodiment. It was.

<Step (2) Preparation of Oil Dispersion of Encapsulated Pigment>
Cetyltrimethyl having an opposite charge to the anionic polymerizable surfactant Aqualon KH-10 used in the synthesis of the above step (1) was added to 200 g of the aqueous dispersion of encapsulated pigment obtained in the above step (1). After adding 0.19 g of ammonium chloride and mixing, with stirring, 30 g of Isopar H from Exxon was gradually added. When all of Isopar H was added dropwise, this solution was transferred to a separatory funnel at room temperature ( (25 ° C.), the encapsulated pigment was transferred to Isopar H in the oil layer. The separated lower aqueous layer in the separatory funnel was removed, and then dehydrated with silica gel to prepare an oily dispersion of encapsulated pigment.
The volume average particle size of the obtained dispersion was measured with a laser Doppler type particle size distribution meter Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co. As a result, it was 160 nm. The obtained dispersion is dried at room temperature, and the solid is subjected to thermal analysis using a thermal scanning calorimeter (Differential Scanning Calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Denshi Co., Ltd.). It was 33 degreeC when the glass transition temperature of the coating polymer of particle | grains was calculated | required.

“Manufacture of oil dispersion“ MCP2 ”of encapsulated pigment”
<Step (1) Synthesis of encapsulated pigment and preparation of aqueous dispersion of capsule pigment>
50 g of anionic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 850 g of ion-exchanged water, and C.V. I. 100 g of Pigment Blue 15: 4 was added and mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling ratio of 70% and a rotation speed of 5000 rpm using a disperser Eiger Motor Mill M250 (manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration by a cross flow method was performed using an ultrafiltration apparatus, and the solid solution concentration was adjusted to 10% by mass until the permeated liquid disappeared. The obtained pigment dispersion was subjected to thermogravimetry, and the adsorption amount of the anionic polymerizable surfactant Aqualon KH-10 was determined from the weight loss value. As a result, KH-10 / pigment was 25.6 / 100.

To 50 g of the obtained pigment dispersion, 0.3 g of dimethylaminoethyl methyl chloride methacrylate as a cationic water-soluble monomer was added and mixed, and then irradiated with ultrasonic waves for 30 minutes. Next, 18.0 g of benzyl methacrylate, 7.2 g of isobornyl methacrylate and 10.8 g of lauryl methacrylate were added to and mixed with the obtained mixed solution, and then further dissolved in 50 ml of ion-exchanged water, 0.75 g. The anionic polymerizable surfactant Adekari Soap SR-10 was added, and 380 ml of ion-exchanged water was further added and mixed. This mixed solution was adjusted to pH 9.0 with 1 mol / l potassium hydroxide aqueous solution.
This mixed solution is put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, and a nitrogen introduction tube, and the internal temperature of the reaction vessel is raised to 80 ° C. An aqueous solution in which 0.75 g of potassium sulfate was dissolved in 100 g of ion-exchanged water was dropped, and a polymerization reaction was performed at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel. After completion of the polymerization, the pH was adjusted to 8 with a 1 mol / l aqueous potassium hydroxide solution, and then filtered through a membrane filter having a pore size of 1 μm to remove coarse particles. Next, using an ultrafiltration device, ultrafiltration by a crossflow method is performed, and the solid content concentration is set to 15% by mass to obtain an aqueous dispersion of the encapsulated pigment in step (1) of this embodiment. It was.

<Step (2) Preparation of Oil Dispersion of Encapsulated Pigment>
Cetyltrimethyl having an opposite charge to the anionic polymerizable surfactant Aqualon KH-10 used in the synthesis of the above step (1) was added to 200 g of the aqueous dispersion of encapsulated pigment obtained in the above step (1). After adding 0.19 g of ammonium chloride and mixing, with stirring, 30 g of Isopar H from Exxon was gradually added. When all of Isopar H was added dropwise, this solution was transferred to a separatory funnel at room temperature ( (25 ° C.), the encapsulated pigment was transferred to Isopar H in the oil layer. The separated lower aqueous layer in the separatory funnel was removed, and then dehydrated with silica gel to prepare an oily dispersion of encapsulated pigment.
The volume average particle diameter of the obtained dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co. As a result, it was 145 nm. The obtained dispersion is dried at room temperature, and the solid is subjected to thermal analysis using a thermal scanning calorimeter (Differential Scanning Calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Denshi Co., Ltd.). It was 18 degreeC when the glass transition temperature of the coating polymer of particle | grains was calculated | required.

“Manufacture of oil dispersion“ MCP3 ”of encapsulated pigment”
<Step (1) Synthesis of encapsulated pigment and preparation of aqueous dispersion of capsule pigment>
50 g of anionic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 850 g of ion-exchanged water, and C.V. I. 100 g of Pigment Blue 15: 4 was added and mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling ratio of 70% and a rotation speed of 5000 rpm using a disperser Eiger Motor Mill M250 (manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration by a cross flow method was performed using an ultrafiltration device, and the permeate was treated until foaming disappeared. The solid content concentration was 14.3% by weight. The obtained pigment dispersion was subjected to thermogravimetry and the adsorption amount of the anionic polymerizable surfactant AQUALON KH-10 was determined from the weight loss value. As a result, KH-10 / pigment was 16.3 / 100.

  To 105 g of the obtained pigment dispersion, 0.67 g of a dimethylaminoethyl methyl chloride methacrylate salt of a cationic monomer dissolved in 10 ml of ion-exchanged water was added, mixed with stirring, and further irradiated with ultrasonic waves for 30 minutes. Next, 4.7 g of benzyl methacrylate, 16.3 g of dicyclopentenyloxyethyl acrylate (FANCRYL FA512A: manufactured by Hitachi Chemical Co., Ltd.), 1.5 g of octoxypolyethylene glycol polypropylene glycol monomethacrylate (Blemmer 50POEP) were obtained. -800B: manufactured by NOF), 0.9 g of ethoxylated polypropylene glycol # 700 dimethacrylate (NK ester 1206PE: manufactured by Shin-Nakamura Chemical Co., Ltd.) was added and mixed, and then 1.31 g dissolved in 50 ml of ion-exchanged water. An anionic polymerizable surfactant Adekari Soap SR-10 (manufactured by Adeka) was added, and 400 ml of ion-exchanged water was further added and mixed. This mixed solution was adjusted to pH 9.0 with 1 mol / l potassium hydroxide aqueous solution.

  This mixed solution is put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, and a nitrogen introduction tube, and the internal temperature of the reaction vessel is raised to 80 ° C. An aqueous solution in which 0.71 g of potassium sulfate was dissolved in 100 g of ion-exchanged water was dropped, and a polymerization reaction was performed at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel. After completion of the polymerization, the pH was adjusted to 8 with a 1 mol / l aqueous potassium hydroxide solution, and then filtered through a membrane filter having a pore size of 1 μm to remove coarse particles. Next, using an ultrafiltration device, ultrafiltration by a crossflow method is performed, and the solid content concentration is set to 15% by mass to obtain an aqueous dispersion of the encapsulated pigment in step (1) of this embodiment. It was.

<Step (2) Preparation of Oil Dispersion of Encapsulated Pigment>
Cetyltrimethyl having an opposite charge to the anionic polymerizable surfactant Aqualon KH-10 used in the synthesis of the above step (1) was added to 200 g of the aqueous dispersion of encapsulated pigment obtained in the above step (1). After adding 0.4 g of ammonium chloride and mixing, with stirring, 30 g of Exxon Isopar H was gradually added. When all of the Isopar H was added dropwise, this solution was transferred to a separatory funnel at room temperature ( (25 ° C.), the encapsulated pigment was transferred to Isopar H in the oil layer. The separated lower aqueous layer in the separatory funnel was removed, and then dehydrated with silica gel to prepare an oily dispersion of encapsulated pigment.
The volume average particle size of the obtained dispersion was measured with a laser Doppler type particle size distribution meter Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co. As a result, it was 100 nm. The obtained encapsulated pigment particles were subjected to thermogravimetric analysis, and the polymer conversion was determined to be 91%.

“Manufacture of oil dispersion“ MCP4 ”of encapsulated pigment”
<Step (1) Synthesis of encapsulated pigment and preparation of aqueous dispersion of capsule pigment>
50 g of anionic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 850 g of ion-exchanged water, and C.V. I. 100 g of Pigment Blue 15: 4 was added and mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling ratio of 70% and a rotation speed of 5000 rpm using a disperser Eiger Motor Mill M250 (manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration by a cross flow method was performed using an ultrafiltration device, and the permeate was treated until foaming disappeared. The solid content concentration was 14.3% by weight. The obtained pigment dispersion was subjected to thermogravimetry and the adsorption amount of the anionic polymerizable surfactant AQUALON KH-10 was determined from the weight loss value. As a result, KH-10 / pigment was 16.3 / 100.

  To 105 g of the obtained pigment dispersion, 0.67 g of a dimethylaminoethyl methyl chloride methacrylate salt of a cationic monomer dissolved in 10 ml of ion-exchanged water was added, mixed with stirring, and further irradiated with ultrasonic waves for 30 minutes. Next, 4.7 g of benzyl methacrylate, 16.3 g of dicyclopentenyloxyethyl acrylate (FANCRYL FA512A: manufactured by Hitachi Chemical Co., Ltd.), 1.5 g of octoxypolyethylene glycol polypropylene glycol monomethacrylate (Blemmer 50POEP) were obtained. -800B: manufactured by NOF), 0.9 g of ethoxylated polypropylene glycol # 700 dimethacrylate (NK ester 1206PE: manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2.7 g of urethane acrylate EBECRYL8402 (manufactured by Daicel Cytec) were added and mixed. Further, 1.31 g of an anionic polymerizable surfactant Adekari Soap SR-10 (manufactured by Adeka) dissolved in 50 ml of ion exchange water was added, and 400 ml of ion exchange water was further added and mixed. . This mixed solution was adjusted to pH 9.0 with 1 mol / l potassium hydroxide aqueous solution.

  This mixed solution is put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, and a nitrogen introduction tube, and the internal temperature of the reaction vessel is raised to 80 ° C. An aqueous solution in which 0.71 g of potassium sulfate was dissolved in 100 g of ion-exchanged water was dropped, and a polymerization reaction was performed at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel. After completion of the polymerization, the pH was adjusted to 8 with a 1 mol / l aqueous potassium hydroxide solution, and then filtered through a membrane filter having a pore size of 1 μm to remove coarse particles. Next, using an ultrafiltration device, ultrafiltration by a crossflow method is performed, and the solid content concentration is set to 15% by mass to obtain an aqueous dispersion of the encapsulated pigment in step (1) of this embodiment. It was.

<Step (2) Preparation of Oil Dispersion of Encapsulated Pigment>
Cetyltrimethyl having an opposite charge to the anionic polymerizable surfactant Aqualon KH-10 used in the synthesis of the above step (1) was added to 200 g of the aqueous dispersion of encapsulated pigment obtained in the above step (1). After adding 0.4 g of ammonium chloride and mixing, with stirring, 30 g of Exxon Isopar H was gradually added. When all of the Isopar H was added dropwise, this solution was transferred to a separatory funnel at room temperature ( (25 ° C.), the encapsulated pigment was transferred to Isopar H in the oil layer. The separated lower aqueous layer in the separatory funnel was removed, and then dehydrated with silica gel to prepare an oily dispersion of encapsulated pigment.
The volume average particle size of the obtained dispersion was measured with a laser Doppler type particle size distribution meter Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co. As a result, it was 100 nm. The obtained encapsulated pigment particles were subjected to thermogravimetric analysis, and the polymer conversion was determined to be 91%.

  In the case where a colorant is used as the core material of the encapsulated oil dispersion of the encapsulated product obtained by the production method of the present embodiment, the oily dispersion of the colorant (pigment) encapsulated product having excellent dispersion stability Available. In addition, the oil dispersion of the encapsulated product obtained by the production method of the present embodiment can be used as an oil-based ink capable of obtaining a recorded product excellent in fastness and abrasion resistance.

  DESCRIPTION OF SYMBOLS 1 ... Core substance, 2 '... Anionic surfactant a, 2 ... Anionic polymerizable surfactant A, 3 ... Cationic polymerizable surfactant B (or positively charged cationic group and polymerizable group) 4 ... anionic polymerizable surfactant C, 5 ... aqueous monomer, 7 ... thione surfactant f, 21, 41 ... nonionic group, 31 ... Thion group, 22, 32, 42, 72 ... aqueous group, 23, 33, 43, ... polymerizable group, 60, 60 "... polymer layer, 100, 100" ... encapsulated product.

Claims (6)

A method for producing an oily dispersion of an encapsulated material in which a core substance is coated with a wall material mainly composed of a polymer,
(1) a step of producing an aqueous dispersion of an encapsulated material in which a core material is coated with a wall material mainly composed of a polymer;
(2) Inverting the encapsulated product into an oil layer, and producing an oily dispersion of the encapsulated product,
The above step (1)
(A) Ionic surfactant a having an ionic group and a hydrophobic group on the surface of the core substance and / or ionic polymerizable surfactant A having an ionic group, a hydrophobic group and a polymerizable group Adsorbing and
(B) The ionic surfactant a and / or the ionic surfactant b having an opposite charge to the ionic polymerizable surfactant A, the ionic polymerizable surfactant B, and the ionic monomer are selected. Mixing and adsorbing one or more of
(C) adding and mixing a hydrophobic monomer;
(D) adding the ionic surfactant c and / or the ionic polymerizable surfactant C having the same or opposite charge as the ionic surfactant a and / or the ionic polymerizable surfactant A; Mixing, and
(E) adding a polymerization initiator to this and polymerizing,
The above step (2)
(F) The ionic surfactant c and / or the ionic polymerization in an aqueous dispersion of an encapsulated product in which the core substance obtained in the step (1) is coated with a wall material mainly composed of a polymer. Adding an ionic surfactant f having an opposite charge to the ionic surfactant C;
(G) a step of adding a non-polar oily solvent dropwise to the mixture obtained in step (f) and mixing,
(H) leaving the mixed solution obtained in step (g), separating the oil phase and the aqueous phase containing the encapsulated product, and removing the aqueous phase;
(Li) A method for producing an oily dispersion of an encapsulated product, comprising the step of removing water from the oil phase.   The method for producing an oil dispersion of an encapsulated product according to claim 1, wherein the nonpolar oily solvent in the step (g) is an aliphatic hydrocarbon solvent or silicone oil.   The method for producing an oily dispersion of an encapsulated product according to claim 1 or 2, wherein in the step (c), urethane acrylate is further added and mixed.   The polymer has a repeating structural unit derived from an ionic monomer having the same kind of charge as the ionic polymerizable surfactant C together with a repeating structural unit derived from the ionic polymerizable surfactant C. The manufacturing method of the oil-based dispersion liquid of the encapsulated material in any one of Claims 1-3 characterized by these.   The manufacturing method of the oil-based dispersion liquid of the encapsulated product in any one of Claims 1-4 including the process of irradiating an ultrasonic wave after mixing in the said (b) process.   An oily dispersion of an encapsulated product obtained by the method for producing an oily dispersion of an encapsulated product according to any one of claims 1 to 8.

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