WO2019181668A1

WO2019181668A1 - Microcapsule-containing composition, laundry composition, daycare composition and haircare composition

Info

Publication number: WO2019181668A1
Application number: PCT/JP2019/010130
Authority: WO
Inventors: 田中　智史
Original assignee: 富士フイルム株式会社
Priority date: 2018-03-23
Filing date: 2019-03-13
Publication date: 2019-09-26
Also published as: JP2021088505A

Abstract

Provided is a microcapsule-containing composition produced by making sustained-release microcapsules having a high break strength. This microcapsule-containing composition includes microcapsules having a shell and a core containing a fragrance, wherein i) at least either one selected from a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound is contained in the amount of 10 to 70 mass% with respect to the total mass of the shell material constituting the shell, and ii) the shell thickness is 0.3 to 2.0 μm.

Description

Microcapsule-containing composition, laundry composition, day care composition and hair care composition

The present disclosure relates to a microcapsule-containing composition, a laundry composition, a day care composition, and a hair care composition.

In recent years, microcapsules have added new value to customers by including and protecting functional materials such as fragrances, dyes, heat storage materials, and pharmaceutical ingredients, and releasing functional materials in response to stimuli. It is attracting attention because there is a possibility that it can be provided.

When encapsulating a fragrance in a microcapsule, for example, by mixing a microcapsule encapsulating a fragrance (hereinafter also referred to as a fragrance microcapsule) with a softening agent, washing clothes using the softening agent, When the microcapsules contained in the softening agent adhere to the clothes and the microcapsules are broken by pressure or the like, the contained fragrance is released, and the fragrance by the fragrance can be continuously generated.
At present, the shell material used in perfume microcapsules is mainly a reaction product of aldehyde and amine (for example, melamine formaldehyde resin).

As an example of using a melamine formaldehyde resin for a shell, Patent Document 1 uses a resin containing a fragrance as a core material and a wall material (shell material) containing a reaction product of an aldehyde (for example, formaldehyde) and an amine (for example, melamine). Microcapsules that have been described are described.

In addition, a microcapsule using polyurethane or polyurea as a shell has been proposed.
For example, Patent Document 2 describes a polyurea microcapsule including a polyurea wall (polyurea wall) containing a reaction product of polymerization of polyisocyanate and polyamine, and a fragrance encapsulated in the polyurea wall.

JP 2017-122235 A Special table 2013-530825 gazette

However, since the microcapsules as described above use pressure responsiveness to release the encapsulated component to the outside, for example, when used as a perfume microcapsule, the capsule breaks due to pressure being applied to the clothing. The fragrance by the fragrance is diffused. Therefore, in the state where no pressure is applied to the capsule, the fragrance is held in the capsule and cannot be continuously obtained.

The problem to be solved by one embodiment of the present invention is to provide a microcapsule-containing composition by forming microcapsules having sustained release properties and high breaking strength.

Specific means for solving the above problems includes the following aspects.
<1>
A microcapsule-containing composition comprising a microcapsule having a shell and a core containing a fragrance, i) from a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound Microcapsule-containing composition having at least one selected structure of 10% by mass to 70% by mass with respect to the total mass of the shell material forming the shell, and ii) the thickness of the shell is 0.3 to 2.0 μm object.
<2>
The microcapsule-containing composition according to <1>, wherein the microcapsule has a breaking strength of 16 MPa or more.
<3>
The microcapsule-containing composition according to <1> or <2>, wherein the shell material contains at least one of polyurethane and polyurea or melamine formaldehyde resin.
<4>
The microcapsule-containing composition according to any one of <1> to <3>, wherein the shell material includes at least one of polyurethane and polyurea having a structure derived from a polyisocyanate compound.
<5>
At least one structure selected from a structure derived from a trifunctional or higher functional aliphatic isocyanate compound, a structure derived from a bifunctional aliphatic isocyanate compound, and a structure derived from a bifunctional aromatic isocyanate compound; <4> The microcapsule-containing composition according to <4>, comprising polyurethane or polyurea.
<6>
The microcapsule-containing composition according to any one of <1> to <3>, wherein the shell material includes a melamine formaldehyde resin having a structure derived from a melamine formaldehyde prepolymer compound.
<7>
The shell material has a structure derived from a melamine formaldehyde prepolymer compound, a structure derived from a bifunctional aliphatic isocyanate compound, and at least one structure selected from a structure derived from a bifunctional aromatic isocyanate compound. The microcapsule-containing composition according to <6>, comprising a formaldehyde resin.
<8>
A laundry composition, day care composition or hair care composition comprising the microcapsule-containing composition according to any one of <1> to <7>.

According to one embodiment of the present disclosure, a microcapsule-containing composition having sustained release properties is provided by forming microcapsules having sustained release properties and high breaking strength.

Hereinafter, an embodiment of the microcapsule-containing composition of the present disclosure will be described in detail.

In the present specification, a numerical range indicated using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value, respectively. In a numerical range described in stages in the present disclosure, an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In this specification, “shell” refers to a wall of a microcapsule, and “core” refers to a portion enclosed in the shell.
In the present disclosure, a material for forming the shell is referred to as “shell material”. The components contained in the core are collectively referred to as “core material”.
In the microcapsule of the present disclosure, the “encapsulation” refers to a state in which an object is covered and confined by the shell of the microcapsule.

≪Composition containing microcapsules≫
The microcapsule-containing composition of the present disclosure includes a microcapsule having sustained release properties and high breaking strength. The microcapsule has a shell and a core containing a fragrance.

As described above, conventionally known microcapsules generally retain the fragrance in the capsule when no pressure is applied, and the fragrance is released by the fragrance unless the capsule shell is broken. Has no function. However, the perfume microcapsules having pressure responsiveness are destroyed when force is applied in various processes during washing, particularly the dehydration process, and unevenness occurs in the perfume microcapsules attached to the clothes. On the other hand, even in a situation where the capsule is not broken, a perfume micro having a property that a slight aroma can be obtained and that the aroma can be maintained for a long time, that is, a perfume is gradually released naturally. There is a demand for capsules.
In view of the above, the inventor of the present invention pays particular attention to the characteristics of the shell material of the microcapsule, and includes a fragrance as a core material, and i) a structure derived from a bifunctional aliphatic isocyanate compound and a bifunctional aromatic isocyanate compound A microcapsule having at least one structure selected from the structures derived from (ii) having a mass of 10 to 70% by mass with respect to the total mass of the shell material and having a shell thickness of 0.3 to 2.0 μm. As a result, it has been found that the encapsulated components can be gradually released without being destroyed in the washing process of the microcapsules.

<Microcapsule>
The microcapsule in the present disclosure has a core and a shell enclosing the core, and i) at least selected from a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound. One structure has 10% by mass to 70% by mass with respect to the total mass of the shell material, and ii) the thickness of the shell is 0.3 to 2.0 μm.

(destruction strength)
The microcapsules in the present disclosure preferably have a breaking strength of 16 MPa or more. Accordingly, the microcapsules can be uniformly adhered to the fibers without being broken even in various processes during washing, particularly in the dehydration process. From the same viewpoint as described above, the breaking strength of the microcapsule is more preferably 18 to 35 MPa, and particularly preferably 20 to 30 MPa.

The breaking strength of the microcapsule can be measured by the following method.
The aqueous microcapsule dispersion was diluted 1000 times with water, dropped by 0.1 cc onto the slide glass, dried, and the breaking strength of the microcapsule having a diameter of about 20 μm on the slide glass was measured. For the measurement, a microhardness meter DUH-W201 (manufactured by Shimadzu Corporation) was used, and the size of the microcapsule was confirmed and measured using an attached microscope. A 50 μm planar indenter was used as the indenter. The destructive force of microcapsules is described in Zhang, Z. et al. Sun, G; “Mechanical Properties of Melamine-Formaldehyde microcapsules,” J .; Microencapsulation, vol 18, no. 5, pages 593-602, 2001. Next, calculate the breaking strength of each particle by dividing the breaking force (in Newtons) by the cross-sectional area of the corresponding microcapsule (πr ² , where r is the radius of the microcapsule before compression). did. For the breaking strength, the average value measured for 10 microcapsules was used.

The microcapsules in the present disclosure have sustained release properties. Sustained release is a property in which a slight fragrance is obtained even when the core fragrance does not break the microcapsules and the fragrance is maintained for a long time.
In the present disclosure, it is determined that the microcapsule has a sustained release property if the amount of the fragrance decreased after 48 hours at 25 ° C. of the cotton towel obtained by the following process is 5 to 30% by mass.
a) A step of putting 1.5 kg of a cotton towel of 36 cm in length and 36 cm in width into a washing machine b) Washing 10 parts by mass of the microcapsule-containing composition mixed with an unscented softener so as to be 1.0% by mass in terms of fragrance C) Step of putting 30 L of water into the washing machine d) Step of washing 10 minutes, rinsing 25 minutes, dehydration 10 minutes using the washing machine e) Cotton obtained above Step of drying towel In other words, after the microcapsule adheres to the fiber, the fragrance in the microcapsule is released, and the presence or absence of sustained release can be confirmed by decreasing the fragrance. When the fragrance reduction amount is 5% by mass or more, the released fragrance can be sufficiently felt, and when it is 30% by mass or less, the fragrance can be maintained for a long time.
From the same viewpoint as described above, the fragrance reduction amount is more preferably 8 to 25% by mass, and particularly preferably 10 to 20% by mass. In addition, a fragrance | flavor reduction | decrease amount can be measured by the method as described in sustained release evaluation by the fragrance | flavor reduction amount as described in the Example mentioned later, for example.

(shell)
The microcapsule in the present disclosure has a shell that encloses a core.
The shell material forming the shell in the present disclosure preferably has at least one of polyurethane and polyurea having a structure derived from a polyisocyanate compound, or a melamine formaldehyde resin having a structure derived from a melamine formaldehyde prepolymer compound.

-Polyurethane, Polyurea-
The microcapsule of the present disclosure includes a shell for enclosing the core material, and preferably includes polyurethane or polyurea as the shell material forming the shell.

The polyurethane and polyurea contained in the shell will be described in detail.
The polyurethane and polyurea in the present disclosure preferably have a structure derived from polyisocyanate from the viewpoint of storage stability. That is, the polyurethane and polyurea in the present disclosure are preferably polymers obtained using polyisocyanate from the viewpoint of storage stability. That is, the polyurethane and the polyurea preferably have a structure derived from an isocyanate compound. The structure derived from the isocyanate compound includes a structure derived from a tri- or higher functional aliphatic isocyanate compound and a bifunctional aliphatic isocyanate compound. It is preferably at least one structure selected from a structure derived from a structure derived from a bifunctional aromatic isocyanate compound.

The polyurethane or polyurea in the present disclosure includes polyurethane polyurea. In addition, as the polyurethane or polyurea in the present disclosure, polyurethane polyurea is more preferable.
In the present disclosure, the polyurethane, polyurea and polyurethane polyurea preferably have at least one structure selected from a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound.
The shell in the present disclosure has a sustained release property by using a bifunctional isocyanate compound in the formation of polyurethane or polyurea.

In the following, the bifunctional aliphatic isocyanate compound and the bifunctional aromatic isocyanate compound may be collectively referred to as “specific diisocyanate”.

-Specific diisocyanate-
The polyurethane or polyurea that is a shell material forming the shell is at least one selected from a structure derived from a specific diisocyanate, that is, a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound. It is preferable to have the following structure.
The structure derived from a bifunctional aliphatic isocyanate compound refers to a structure formed by a urethane reaction or a urea reaction of a bifunctional aliphatic isocyanate.
The structure derived from a bifunctional aromatic isocyanate compound refers to a structure formed by the reaction of urethane or urea with a bifunctional aromatic isocyanate.

Examples of the bifunctional aliphatic isocyanate compound include trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1, 3-diisocyanate, cyclohexylene-1,4-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane and 1,3-bis (isocyanatemethyl) cyclohexane, isophorone diisocyanate, lysine diisocyanate And hydrogenated xylylene diisocyanate.

Examples of the bifunctional aromatic isocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4, 4'-diisocyanate, 3,3'-dimethoxy-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4-chloroxyl Len-1,3-diisocyanate, 2-methylxylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenylhexafluoropropane diisocyanate, etc. It is.

Isocyanate compounds are described in “Polyurethane Resin Handbook” (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).

As a ratio of at least one structure selected from a structure derived from a specific diisocyanate, that is, a structure derived from a bifunctional aliphatic isocyanate and a structure derived from a bifunctional aromatic isocyanate, to the total mass of the shell material, The total mass ratio is preferably 10% by mass to 70% by mass, more preferably 10% by mass to 65% by mass, and still more preferably 12% by mass to 60% by mass.
When the proportion of the structure derived from the specific diisocyanate is 10% by mass or more, the crosslinking density of the shell is lowered, and the sustained release property of the core material to be included can be enhanced. Further, when the proportion of the structure derived from the specific diisocyanate is 70% by mass or less, and further 60% by mass or less, the flexibility of the shell can be easily maintained, and, for example, adhesion to fibers or hairs can be favorably maintained. .

-3 Functional or higher aliphatic isocyanate compounds
The polyurethane or polyurea which is a shell material forming the shell preferably has a structure derived from a tri- or higher functional aliphatic isocyanate compound. By having a structure derived from a trifunctional or higher functional aliphatic isocyanate compound, the flexibility and breaking strength of the shell can be increased, and adhesion to an object to be adhered such as fiber or hair can be obtained.
The structure derived from a trifunctional or higher functional aliphatic isocyanate compound refers to a structure formed by a urethane reaction or a urea reaction of a trifunctional or higher functional aliphatic isocyanate compound.

Examples of the trifunctional or higher functional aliphatic isocyanate compound include a bifunctional aliphatic isocyanate compound (a compound having two isocyanate groups in the molecule) and a compound having three or more active hydrogen groups in the molecule (for example, a trifunctional or higher functional group). As an adduct (adduct) with a polyol, polyamine, polythiol, etc.), a trifunctional or higher functional isocyanate compound (adduct type), a bifunctional aliphatic isocyanate compound trimer (biuret type or isocyanurate type) Can do.

A commercially available product may be used as the adduct type trifunctional or higher functional isocyanate compound. Examples of commercially available products include Takenate (registered trademark) D-120N (isocyanate number = 3.5 mmol / g), D-140N, D-160N (manufactured by Mitsui Chemicals, Inc.), Sumijoule (registered trademark). HT (manufactured by Bayer Corporation), Coronate (registered trademark) HL, HX (manufactured by Tosoh Corporation), Duranate P301-75E (manufactured by Asahi Kasei Co., Ltd.), Barnock (registered trademark) DN-950 (manufactured by DIC Corporation), etc. Can be mentioned.
Among them, as adduct type tri- or higher functional isocyanate compounds, Takenate (registered trademark) series (for example, Takenate D-110N, D-120N, D-140N, D-160N, etc.) manufactured by Mitsui Chemicals, Inc., and DIC stock More preferable is at least one selected from Vernock (registered trademark) D-750 manufactured by the company.

As the isocyanurate-type trifunctional or higher functional isocyanate compound, a commercially available product may be used. Examples of commercially available products include Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N (manufactured by Mitsui Chemicals), Sumidur N3300, Death Module (registered trademark) N3600. N3900, Z4470BA (manufactured by Bayer Co., Ltd.), Coronate (registered trademark) HK (manufactured by Tosoh Corporation), Duranate (registered trademark) TPA-100, TKA-100 (manufactured by Asahi Kasei Corporation), Barnock (registered trademark) DN-980 (manufactured by DIC Corporation) and the like.

As the biuret type trifunctional or higher functional isocyanate compound, commercially available products may be used. For example, Takenate (registered trademark) D-165N, NP1200 (manufactured by Mitsui Chemicals), Desmodur (registered trademark) N3200A (Manufactured by Bayer Corporation), Duranate (registered trademark) 24A-100, 22A-75P (manufactured by Asahi Kasei Corporation) and the like.

The ratio of the structure derived from the trifunctional or higher aliphatic isocyanate compound to the total mass of the shell material is preferably 20% by mass to 95% by mass, and more preferably 20% by mass to 90% by mass. The content is preferably 35% by mass to 80% by mass.
When the proportion of the structure derived from the tri- or higher functional aliphatic isocyanate compound is 20% by mass or more, the shell can be provided with good flexibility and breaking strength. Moreover, when the ratio of the structure derived from the trifunctional or higher aliphatic isocyanate compound is 95% by mass or less, it is suitable for maintaining the sustained release property to the outside of the core material.

The ratio of the trifunctional aliphatic isocyanate compound to the specific diisocyanate is preferably from 95/5 to 20/80, more preferably from 90/10 to 30/70, and more preferably from 90/10 to 90/10. More preferably, it is 40/60.
When the ratio of the trifunctional aliphatic isocyanate compound to the specific diisocyanate is within the above range, the sustained release property of the core material is excellent.

-Other isocyanate compounds-
Polyurethane or polyurea, which is a shell material that forms a shell, may have a structure derived from other isocyanate compounds in addition to the trifunctional aliphatic isocyanate compound and the specific diisocyanate.
The structure derived from another isocyanate compound refers to a structure formed by the urethane reaction or urea reaction of another isocyanate compound.

Examples of other isocyanate compounds include trifunctional or higher functional aromatic isocyanate compounds.

Specific examples of the trifunctional or higher functional aromatic isocyanate compound include 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, or an adduct (adduct) of hexamethylene diisocyanate and trimethylolpropane, biuret or isocyanate. A nurate body etc. are mentioned.
Commercially available products marketed as trifunctional or higher functional aromatic isocyanate compounds may be used. Examples of commercially available products include Barnock (registered trademark) D-750 (manufactured by DIC Corporation), Takenate (registered trademark) D- 102, D-103, D-103H, D-103M2, D-110N, Olester (registered trademark) P49-75S (above, manufactured by Mitsui Chemicals, Inc.), Death Module (registered trademark) L75, IL-135-BA , HL-BA, Sumijoule (registered trademark) E-21-1 (manufactured by Bayer Co., Ltd.), Coronate (registered trademark) L, L-55, L-55E (manufactured by Tosoh Corporation), Bernock (registered trademark) D -750, D-800 (manufactured by DIC Corporation) and the like.

-Melamine formaldehyde resin-
The microcapsule of the present disclosure preferably includes a shell for enclosing the core material, and preferably includes a melamine formaldehyde resin as the shell material forming the shell.

The melamine formaldehyde resin contained in the shell will be described in detail.
The melamine formaldehyde resin in the present disclosure preferably has a structure derived from a melamine formaldehyde prepolymer compound from the viewpoint of storage stability. That is, the melamine formaldehyde resin in the present disclosure is preferably a polymer obtained using a melamine formaldehyde prepolymer compound from the viewpoint of storage stability.

The melamine formaldehyde resin in the present disclosure also includes an aminoplast resin in which a melamine formaldehyde prepolymer compound and a polyisocyanate are crosslinked.
In the present disclosure, the melamine formaldehyde resin is at least one structure selected from a structure derived from a melamine formaldehyde prepolymer, a structure derived from a bifunctional aliphatic isocyanate compound, and a structure derived from a bifunctional aromatic isocyanate compound; It is preferable to have.
In the formation of the melamine formaldehyde resin, the shell in the present disclosure has a sustained release property by using a melamine formaldehyde prepolymer compound and a bifunctional isocyanate compound. As the difunctional isocyanate compound, those described in the above-mentioned “specific diisocyanate” can be used as appropriate.

-Melamine formaldehyde prepolymer compound-
The melamine formaldehyde resin, which is a shell material that forms a shell, preferably has a structure derived from a melamine formaldehyde prepolymer compound. By having the structure derived from the melamine formaldehyde prepolymer compound, high stability in the washing process can be obtained.
The melamine formaldehyde prepolymer compound is an initial polymer obtained by reacting melamine and formaldehyde, and it is preferable to use the melamine formaldehyde prepolymer compound from the viewpoint of handling when forming the shell of the microcapsule.

The melamine formaldehyde prepolymer compound can be produced from melamine and formaldehyde according to a conventional method. Moreover, what is marketed can be used suitably as a melamine formaldehyde prepolymer compound.
For example, becamine APM, becamine M-3, becamine M-3 (60), becamine MA-S, becamine J-101, becamine J-101LF (manufactured by DIC Corporation), nicalesin S-176, nicalesin S-260 ( As mentioned above, Nippon Carbide Co., Ltd.) etc. are mentioned.

The ratio of the melamine formaldehyde prepolymer compound to the specific diisocyanate is preferably 95/5 to 20/80, more preferably 90/10 to 30/70, more preferably 90/10 to 40 / More preferably, it is 60.
When the ratio of the melamine formaldehyde prepolymer compound to the specific diisocyanate is within the above range, the core material has excellent sustained release properties.

The thickness (wall thickness) of the shell (wall) of the microcapsule of the present disclosure is in the range of 0.3 μm to 2.0 μm. When the wall thickness of the microcapsule is 0.3 μm or more, the microcapsule can be prevented from cracking in the washing process, particularly the dehydration process, and the core material can be protected in the core. When the wall thickness of the microcapsule is 2.0 μm or less, the microcapsule can be provided with sustained release, and the scent can be released from the microcapsule attached to the fiber.
From the same viewpoint as described above, the wall thickness of the microcapsule is more preferably 0.4 μm to 1.7 μm, and still more preferably 0.4 μm to 1.5 μm.

The wall thickness refers to an average value obtained by averaging the individual wall thicknesses (μm) of five microcapsules with a scanning electron microscope (SEM).
Specifically, a microcapsule solution is applied on an arbitrary support and dried to form a coating film. A cross section of the obtained coating film is prepared, the cross section is observed using an SEM, arbitrary five microcapsules are selected, the cross section of each of the microcapsules is observed, and the wall thickness is measured. And calculating the average value.

The median diameter (D50) of the volume standard of the microcapsules is preferably 0.1 μm to 100 μm.
When the median diameter (D50) is 0.1 μm or more, the microcapsules can be prevented from becoming difficult to break due to entering the minute voids. When the median diameter (D50) is 100 μm or less, it is possible to prevent a decrease in adhesion.
From the above viewpoint, the volume standard median diameter (D50) of the microcapsules is more preferably 1 μm to 70 μm, and still more preferably 5 μm to 50 μm. In the present disclosure, the volume standard median diameter of the microcapsules can be preferably controlled by changing dispersion conditions.
Here, the median diameter of the volume standard of the microcapsule is the volume of the particle on the large diameter side and the small diameter side when the entire microcapsule is divided into two with the particle diameter at which the cumulative volume is 50% as a threshold value. The diameter is the same as the total.
In the present disclosure, the median diameter of the volume standard of the microcapsule is measured using Microtrac MT3300EXII (manufactured by Nikkiso Co., Ltd.).

With respect to the microcapsules of the present disclosure, “highly monodispersed” means that the range of particle size distribution is narrow (that is, there is little variation in particle size), and “lowly monodispersed” means It means that the range of the diameter distribution is wide (that is, there are many variations in particle diameter).
More specifically, the level of monodispersity of the microcapsules can be expressed using a CV value (coefficient of variation). Here, the CV value is a value obtained by the following formula.
CV value (%) = (standard deviation / volume average particle diameter) × 100
The lower the CV value, the higher the monodispersity of the microcapsules, and the higher the CV value, the lower the monodispersibility of the microcapsules.
In the present disclosure, the volume average particle diameter and the standard deviation are calculated using Microtrac MT3300EXII (manufactured by Nikkiso Co., Ltd.).

For example, “highly monodispersed” of the microcapsule means that the CV value of the particle size distribution of the microcapsule is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, particularly preferably. It means 25% or less. When the CV value is in the above range, since the monodispersity of the microcapsule particle size is high, handling of the microcapsules, control of function expression, and the like are facilitated. The lower limit of the CV value of the particle size distribution of the microcapsules is not limited, but is preferably 0% or more, and more preferably 5% or more.

The form of the microcapsule may be, for example, a microcapsule dispersion, preferably a microcapsule aqueous dispersion.

(core)
The microcapsule in the present disclosure preferably has a core encapsulated in a shell and includes a fragrance as a core material in the core.
The microcapsule according to the present disclosure adheres to clothes fibers or hair (hair etc.) without being destroyed even after a washing process, particularly a dehydration process, and includes a fragrance as a core material, thereby providing sustained release. It can be scented for a long time.

(Fragrance)
As the fragrance, synthetic fragrances, natural essential oils, and natural fragrances described in “Japan Patent Office, Well-known and commonly used technology (fragrance) Part III, cosmetic fragrances, pages 49-103, issued on June 15, 2001” Appropriate ones can be selected and used from animal and plant extracts.
Specific fragrances include monoterpenes such as D-limonene, pinene, myrcene, camphene and R-limonene, sesquiterpenes such as cedrene, caryophyllene and longifolene, 1,3,5-undecatriene, α-amylcinnamyl aldehyde Synthetic fragrances such as dihydrojasmon, methylionone, α-damascone, acetyl cedrene, methyl dihydrojasmonate, cyclopentadecanolide, and natural essential oils such as orange essential oil, lemon essential oil, bergamot essential oil, and mandarin essential oil.
The content of the fragrance with respect to the total mass of the core material is preferably 20 to 100% by mass, more preferably 30 to 95% by mass, and particularly preferably 40 to 85% by mass.

(solvent)
The core may contain a solvent as an oil component.
Examples of the solvent include fatty acid ester compounds such as tri (capryl / capric acid) glyceryl and isopropyl myristate, alkylnaphthalene compounds such as diisopropylnaphthalene, diarylalkane compounds such as 1-phenyl-1-xylylethane, isopropylbiphenyl, and the like. Aromatic hydrocarbons such as alkylbiphenyl compounds such as triarylmethane compounds, alkylbenzene compounds, benzylnaphthalene compounds, diarylalkylene compounds, arylindane compounds; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffins; Examples include camellia oil, soybean oil, corn oil, cottonseed oil, rapeseed oil, natural animal and vegetable oils such as olive oil, coconut oil, castor oil, and fish oil; high-boiling fractions of natural products such as mineral oil.
The content of the solvent in the encapsulated component is preferably less than 50% by mass, more preferably 40% by mass or less, and particularly preferably 30% by mass or less with respect to the total mass of the encapsulated component.

(Co-solvent)
The encapsulated component may contain an auxiliary solvent as an oil phase component for enhancing the solubility of each material in the oil phase when producing the microcapsules, if necessary. The auxiliary solvent does not include the above solvent.
Examples of the auxiliary solvent include ketone compounds such as methyl ethyl ketone, ester compounds such as ethyl acetate, alcohol compounds such as isopropyl alcohol, and the like. Preferably, the auxiliary solvent has a boiling point of 130 ° C or lower.
The content of the auxiliary solvent in the encapsulated component is preferably less than 50% by mass, more preferably less than 40% by mass, and even more preferably less than 30% by mass with respect to the total mass of the encapsulated component.

(Additive)
For example, additives such as ultraviolet absorbers, light stabilizers, antioxidants, waxes, odor inhibitors and the like can be included in the microcapsules as necessary.
The additive can be contained, for example, in an amount of 0% by mass to 20% by mass, preferably 1% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass with respect to the total mass of the core.

<Dispersion medium>
The microcapsule-containing composition of the present disclosure preferably further contains a microcapsule dispersion medium.
By further containing a microcapsule dispersion medium, the microcapsule-containing composition can be easily blended when used in various applications.
The dispersion medium in the microcapsule-containing composition is appropriately selected according to the purpose of use of the composition. The dispersion medium is preferably a liquid component that does not affect the wall material of the microcapsule.
Preferred dispersion media include aqueous solvents, viscosity modifiers, stabilizers, and the like.
Examples of the aqueous solvent include water, water, alcohol and the like, and ion-exchanged water or the like can be used.
In addition, what is necessary is just to select suitably content of the dispersion medium in the microcapsule containing composition of this indication according to a use.

(Other ingredients)
The microcapsule-containing composition of the present disclosure can further contain other components in addition to the microcapsule and the dispersion medium that is a combination component.
There is no restriction | limiting in particular in another component, What is necessary is just to select suitably according to the objective or necessity.
Examples of other components include a surfactant, a crosslinking agent, a lubricant, an ultraviolet absorber, an antioxidant, and an antistatic agent.

The microcapsule-containing composition of the present disclosure preferably has an embodiment in which the microcapsule has an anionic charge on the surface and further contains a cationic surfactant.
Thereby, an interaction is obtained between the microcapsule and the cationic surfactant, and a positive charge of the cationic surfactant can be imparted around the microcapsule. As a result, it becomes possible to improve the adhesion property of the microcapsule to an attachment object (for example, hair or fiber) having an anionic charge.

It can be confirmed that the microcapsule has an anionic charge on the surface by measuring the zeta potential when the microcapsule is dispersed in water. When the zeta potential is negative, it indicates that the surface of the microcapsule is covered with an anionic charge.

The zeta potential of the microcapsule, when dispersed in water, is preferably −80 meV to −5 meV, more preferably −80 meV to −11 meV, and further preferably −50 meV to −10 meV. preferable.

“Zeta potential” (z) means the apparent electrostatic potential generated by a charged object in solution, measured by a special measurement technique. A detailed discussion of the logical basis and actual relevance of the zeta potential is, for example, “Colloid Science: Zeta Potential in Colloid Sciences: Principles and Applications” (Hunter Robert J. 1981; p 1988). The zeta potential of an object is measured at some distance from the surface of the object and generally does not exceed the electrostatic potential at the surface itself. However, the value can be a good measure of the ability of an object to establish an electrostatic interaction with other objects in solution, particularly molecules having multiple binding sites.

The zeta potential is a relative measurement value, and the value tends to depend on the measurement method. In the present disclosure, the zeta potential is a value measured by the following method.
a. The apparatus uses ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.).
b. The device settings are as follows.
c. The sample preparation procedure is as follows.
(I) The slurry containing the target capsule is added to water so that the capsule concentration is 0.5% by mass, and the slurry is diluted. The measurement concentration is adjusted as necessary so that the measurement rate falls within a preferable range by automatic detection.
(Ii) The zeta potential of the diluted sample is measured without filtering the sample.
(Iii) The filtered slurry is poured into a standard cell unit (manufactured by Otsuka Electronics Co., Ltd.), and the cell is inserted into the apparatus. Set the test temperature to 25 ° C.
(Iv) Start the measurement after the temperature has stabilized (usually after 3 to 5 minutes). Each sample is set to measure 5 times and measured.
d. The zeta potential in the present disclosure is a value measured in units of “mV” as an average of three measured values for each slurry.
Based on the above, the zeta potential of the microcapsule can be measured using ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.).

The method for imparting an anionic charge to the microcapsule surface is not particularly limited, for example, a method for binding an anionic group-imparting agent to the shell, a method for imparting an anionic charge to the microcapsule surface using a surface anionizing agent, etc. Is mentioned. Among these, from the viewpoint of work efficiency, a method of imparting an anionic charge to the microcapsule surface using a surface anionizing agent is preferable.

As a method for bonding an anionic group to the surface of the shell using an anionic group-imparting agent, the following method can be given as an example.
That is, an oil phase is prepared by stirring and mixing the fragrance and the shell material. Subsequently, an aqueous solution containing an anionic group-imparting agent (for example, lysine) is prepared as an aqueous phase. The oil phase is added to the prepared aqueous phase to disperse and emulsify, and the resulting emulsion is heated and stirred and then cooled. After cooling, an aqueous solution of a base (for example, sodium hydroxide) is added to obtain an aqueous dispersion of microcapsules having an anionic group on the surface.
The aqueous solution containing the anionic group-imparting agent may be added after the emulsion is formed, or an aqueous base solution may be added to the aqueous phase in advance.
In addition, content of said each component can be changed suitably.

-Anionic group imparting agent-
There is no restriction | limiting in particular as an anionic group provision agent, For example, a lysine, aspartic acid, glutamic acid (above, Wako Pure Chemical Industries Ltd. make) etc. are mentioned.

There is no restriction | limiting in particular as a method of providing an anionic charge using a surface anionizing agent on the microcapsule surface, For example, the method of forming a protective colloid on the microcapsule surface using a surface anionizing agent is preferable.
The protective colloid means a colloid that can impart an anionic charge to the microcapsule surface by being present on the microcapsule surface.

-Surface anionizing agent-
The surface anionizing agent is not particularly limited as long as it can give an anionic charge to the microcapsule surface (anionic water-soluble polymers (anionic polysaccharides such as anion-modified polyvinyl alcohol, carboxymethyl cellulose, carrageenan, polyacrylic acid)). And copolymers with sodium and other monomers, copolymers with sodium polymaleate and other monomers) and anionic surfactants (sodium dodecyl sulfate, sodium lauryl sulfate, etc.).

The microcapsule in the microcapsule-containing composition of the present disclosure preferably has an anion-modified polyvinyl alcohol on at least a part of the surface from the viewpoint of imparting an anionic charge to the microcapsule surface.

Examples of the method for forming a protective colloid on the surface of the microcapsule using the surface anionizing agent include the following methods. However, the present disclosure is not limited to the following method.
First, an oil phase is prepared by stirring and mixing a solvent, a trifunctional aliphatic isocyanate and a specific diisocyanate which are shell materials. Subsequently, an aqueous solution containing a surface anionizing agent (for example, anion-modified polyvinyl alcohol) is prepared as an aqueous phase. The oil phase is added to the prepared aqueous phase and dispersed to emulsify, and the resulting emulsion is heated, stirred and cooled. After cooling, a base (for example, sodium hydroxide aqueous solution) is added to obtain an aqueous dispersion of microcapsules having a protective colloid on the surface.
In addition, content of each above-mentioned component can be changed suitably.

As the anion-modified polyvinyl alcohol, commercially available products can be used.
Examples of commercially available products are Kuraray Poval KM-618 (manufactured by Kuraray Co., Ltd.), Kuraray Poval KL-318 (manufactured by Kuraray Co., Ltd.), Gohsenol L-3266 (manufactured by Nippon Synthetic Chemical Co., Ltd.), Gohsenol T-330 (Japan) Synthetic Chemical Co., Ltd.). Among these, from the viewpoint of imparting anionic property, the anion-modified polyvinyl alcohol is preferably Kuraray Poval KM-618 or Gohsenol L-3266, and more preferably Kuraray Poval KM-618.

-Cationic surfactant-
The microcapsule-containing composition of the present disclosure preferably contains a cationic surfactant when an anionic charge is imparted to the microcapsule surface. Thereby, the anion charge (minus charge) of the microcapsule and the plus charge of the cationic surfactant attract each other due to the interaction, so that the plus charge of the cationic surfactant covers the microcapsule. As a result, a positive charge can be generated as a whole capsule, and the positive charge of the microcapsule attracts the negative charge of the attached object (for example, fiber or hair) to which the microcapsule adheres. Adhesion can be further improved.

The cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. For example, alkylamine salts, quaternary ammonium salts (for example, hexadecyltrimethylammonium chloride), polyoxyethylene alkylamine salts, polyethylene Examples include polyamine derivatives.

As the cationic surfactant, a commercially available product may be used. Examples of commercially available products include cation EQ-01D (NOF Corporation), cation SF-10 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), cation SF-75PA (manufactured by Sanyo Kasei Kogyo Co., Ltd.), and Adecamin SF-108 (stock) The company ADEKA).

<Method for producing microcapsules>
Although the microcapsule of this indication can be manufactured with the following method, for example, it is not limited to the following method.
When the shell is formed of at least one of polyurethane and polyurea, the microcapsule manufacturing method of the present disclosure disperses an oil phase containing a fragrance and a polyisocyanate as a shell material in an aqueous phase containing an emulsifier. The step of preparing an emulsified liquid (emulsification step) and the step of polymerizing the shell material at the interface between the oil phase and the aqueous phase to form a shell and forming microcapsules enclosing a fragrance (encapsulation step) Including interfacial polymerization methods can be used as appropriate.
When the shell is formed from a melamine formaldehyde resin, an oil phase containing a fragrance is dispersed in an aqueous phase containing an emulsifier to prepare an emulsion (emulsification step), and a shell material is added to the aqueous phase to emulsify A coacervation method including a step (encapsulation step) of forming a microcapsule encapsulating a fragrance by forming a polymer layer formed of a shell material on the surface of the droplet can be used as appropriate.

[Emulsification process]
When the shell is formed of at least one of polyurethane and polyurea, the microcapsule manufacturing method of the present disclosure disperses an oil phase containing a fragrance and a polyisocyanate as a shell material in an aqueous phase containing an emulsifier. And a step of preparing an emulsion (emulsification step). When the shell is formed from a melamine formaldehyde resin, it includes a step (emulsification step) of preparing an emulsion by dispersing an oil phase containing a fragrance in an aqueous phase containing an emulsifier.

~ Emulsified liquid ~
The emulsified liquid of the present disclosure is formed by dispersing an oil phase containing a fragrance and, if necessary, a polyisocyanate which is a shell material in an aqueous phase containing an emulsifier.

(Oil phase)
The oil phase of the present disclosure includes at least a fragrance. If necessary, the shell material may further include components such as polyisocyanate, a solvent, a co-solvent, and / or an additive. Such solvents, cosolvents, and additives are as described in the section <Microcapsules>.

-solvent-
The solvent used in the production method of the present disclosure is as described in the section <Microcapsule>.

-Shell material-
The shell material in the present disclosure can include a polyisocyanate or a melamine formaldehyde prepolymer. Furthermore, it is preferable that specific diisocyanate is included.

The shell material is, for example, more than 0.1% by mass and 20% by mass or less, preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 5% by mass with respect to the total mass of the oil phase. Contained in
The concentration of the shell material can be appropriately adjusted in view of the size of the microcapsules, the wall thickness, and the like.

(Water phase)
The aqueous phase of the present disclosure includes at least an aqueous medium and an emulsifier.

-Aqueous medium-
Examples of the aqueous medium of the present disclosure include water and a mixed solvent of water and a water-soluble organic solvent, preferably water. “Water-soluble” means that the amount of the target substance dissolved in 100% by mass of water at 25 ° C. is 5% by mass or more.
The aqueous medium is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% by mass with respect to the total mass of the emulsion that is a mixture of an oil phase and an aqueous phase. ~ 60% by mass.

-emulsifier-
The emulsifier includes a dispersant, a surfactant, or a combination thereof.

Examples of the dispersant include polyvinyl alcohol and modified products thereof, polyacrylic acid amide and derivatives thereof, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene- Mention may be made of maleic anhydride copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivatives, gum arabic and sodium alginate. Polyvinyl alcohol is preferred.
These dispersants preferably do not react with the shell material or are extremely difficult to react. For example, those having a reactive amino group in a molecular chain such as gelatin are preliminarily treated to lose the reactivity. It is necessary.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

The nonionic surfactant is not particularly limited, and a conventionally known nonionic surfactant can be used. For example, polyoxyethylene alkyl ether compounds, polyoxyethylene alkyl phenyl ether compounds, polyoxyethylene polystyryl phenyl ether compounds, polyoxyethylene polyoxypropylene alkyl ether compounds, glycerin fatty acid partial ester compounds, sorbitan fatty acid moieties Ester compounds, pentaerythritol fatty acid partial ester compounds, propylene glycol mono fatty acid ester compounds, sucrose fatty acid partial ester compounds, polyoxyethylene sorbitan fatty acid partial ester compounds, polyoxyethylene sorbitol fatty acid partial ester compounds, polyethylene glycol Fatty acid ester compounds, polyglycerin fatty acid partial ester compounds, polyoxyethylenated castor oil compounds Polyoxyethylene glycerin fatty acid partial ester compound, fatty acid diethanolamide compound, N, N-bis-2-hydroxyalkylamine compound, polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol And a copolymer of polyethylene glycol and polypropylene glycol.

The anionic surfactant is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salt, abietic acid salt, hydroxyalkane sulfonate, alkane sulfonate, dialkyl sulfosuccinate ester salt, linear alkyl benzene sulfonate, branched alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl phenoxy poly Oxyethylenepropyl sulfonate, polyoxyethylene alkylsulfophenyl ether salt, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated beef oil, fatty acid alkyl ester Sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester, fatty acid monoglyceride sulfate ester, polyoxyethylene alkyl phenyl ether sulfate ester Part of salt, polyoxyethylene styryl phenyl ether sulfate ester, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl phenyl ether phosphate ester salt, styrene-maleic anhydride copolymer And olefin-maleic anhydride copolymer partial saponification product, naphthalene sulfonate formalin condensate, alkyl polyoxyalkylene sulfoalkyl ether salt, alkenyl polyoxyalkylene sulfoalkyl ether salt, and the like.

The cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts (for example, hexadecyltrimethylammonium chloride), polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like.

The amphoteric surfactant is not particularly limited, and a conventionally known amphoteric surfactant can be used. Examples thereof include carboxybetaine, aminocarboxylic acid, sulfobetaine, aminosulfuric acid ester, imidazoline and the like.

The concentration of the emulsifier is preferably more than 0% by mass and 20% by mass or less, more preferably from 0.005% by mass to 10% by mass, with respect to the total mass of the emulsion that is a mixture of the oil phase and the aqueous phase. The content is more preferably from 01% by mass to 10% by mass, and particularly preferably from 1% by mass to 5% by mass.

The aqueous phase may contain other components such as an ultraviolet absorber, an antioxidant, and a preservative as necessary. Such other components are, for example, more than 0% by mass and 20% by mass or less, preferably more than 0.1% by mass and 15% by mass or less, more preferably more than 1% by mass and 10% by mass with respect to the total mass of the aqueous phase. The following may be contained.

(dispersion)
Dispersion refers to dispersing (emulsifying) the oil phase of the present disclosure as oil droplets in the water phase of the present disclosure. The dispersion can be carried out by means usually used for dispersion of an oil phase and an aqueous phase, for example, a homogenizer, a Manton Gory, an ultrasonic disperser, a dissolver, a teddy mill, or other known dispersion devices.

The mixing ratio of the oil phase to the water phase (oil phase mass / water phase mass) is preferably 0.1 to 1.5, more preferably 0.2 to 1.2, and still more preferably 0.4 to 1.0. . When the mixing ratio is in the range of 0.1 to 1.5, an appropriate viscosity can be maintained, the production suitability is excellent, and the stability of the emulsion is excellent.

[Encapsulation process]
The method for producing a microcapsule of the present disclosure includes an interfacial polymerization method in which a shell material is polymerized at an interface between an oil phase and an aqueous phase to form a shell, and an oil phase and an aqueous phase are emulsified and then a shell material is added and polymerized. A step of forming a microcapsule enclosing a fragrance is included by using a selvage method. Thereby, the microcapsule in which the fragrance | flavor of this indication was included in the shell is formed.

(polymerization)
Polymerization is a step of polymerizing the shell material contained in the emulsion, whereby a shell is formed. The polymerization is preferably performed under heating. The reaction temperature in the polymerization is usually preferably 40 ° C to 100 ° C, more preferably 50 ° C to 80 ° C. The polymerization reaction time is usually preferably about 0.5 to 10 hours, more preferably about 1 to 5 hours. The higher the polymerization temperature, the shorter the polymerization time, but when using inclusions or shell materials that may decompose at high temperatures, select a polymerization initiator that works at low temperatures and polymerize at relatively low temperatures. Is desirable.

In order to prevent the microcapsules from aggregating during the polymerization step, it is preferable to further add an aqueous solution (for example, water, an aqueous acetic acid solution, etc.) to reduce the collision probability between the microcapsules, and perform sufficient stirring. Is also preferable. A dispersing agent for preventing aggregation may be added again during the polymerization process. Furthermore, a charge control agent such as nigrosine, or any other auxiliary agent can be added as necessary. These adjuvants can be added at the time of shell formation or at any point.

<Use of microcapsule-containing composition>
The microcapsule-containing composition of the present disclosure can be used for various applications.
Examples of the microcapsule-containing composition may include uses such as washing, hair care, and day care.

(Laundry composition)
-Softener for clothing-
The microcapsule-containing composition of the present disclosure can be made into a softener for clothing by including, for example, a core material (for example, a fragrance). Thereby, the microcapsule-containing composition of the present disclosure can be applied to a laundry composition.
The microcapsule-containing composition, which is a softener for clothing of the present disclosure, is obtained by immersing the clothing in the microcapsule-containing composition, dehydrating and drying, so that the microcapsules contained in the microcapsule-containing composition are adsorbed on the fibers of the clothing Or enter into the fine gaps between the fibers and held by the clothing. For this reason, softening, an antistatic property, etc. are provided with respect to clothing, Furthermore, a core material can be discharge | released at a desired time by including the microcapsule containing a core material.

When wearing clothing treated with the softener for clothing of the present disclosure, the core material is stably contained in the microcapsule in addition to the soft comfort, so even after lapse of time, stress is applied by rubbing the clothing, etc. The core material can be released by disintegrating the microcapsules. Moreover, even if it does not give stress in particular, by wearing clothes and acting, the microcapsules are gradually collapsed, and the core material can be gradually released.

The softening agent for clothing preferably contains 0.3 to 3% by mass of the core encapsulated in the microcapsule with respect to the microcapsule-containing composition in the total amount of the microcapsule-containing composition.
In addition, it can further contain a known component contained in the softener for clothing, such as an antifoaming agent, a coloring material, and a fragrance. The dispersion medium used for the softener for clothing is preferably water such as ion exchange water.

(Hair Care Composition)
The microcapsule-containing composition containing the microcapsules and the microcapsule dispersion medium in the present disclosure can be applied to the hair care composition as it is.
The use of the hair care composition can be arbitrarily applied to hair cosmetics such as rinses, conditioners, hair styling agents, and the like.
When applied to hair, the microcapsule-containing composition of the present disclosure, which is a hair cosmetic, adheres to the hair, and when the hair is rubbed or combed, the microcapsule disintegrates due to stress, and the core material Can be released.

In the case of liquid hair cosmetics, it is preferable that the microcapsules can be stably stored for a longer time by filling the spray container.
When the hair cosmetic is applied to the hair by spraying, the dispersion medium and the microcapsules adhere to the hair. Thereafter, by performing massage or the like on the scalp, the microcapsules are collapsed by applying stress to the microcapsules, and the core material can be attached to the hair.
The microcapsule-containing composition of the present disclosure that is a hair cosmetic can optionally contain known components that can be included in the hair cosmetic.
Known components that can be included in hair cosmetics include aqueous media such as alcohol, oil agents, surfactants as cleaning or dispersing components, active ingredients that penetrate the skin, colorants, and fragrances.

(Day care composition)
The microcapsule-containing composition of the present disclosure is applied to, for example, a day care composition such as a cosmetic sheet or a diaper including a support and the microcapsule-containing composition of the present disclosure described above impregnated in the support. Can do.
The support is not particularly limited as long as the liquid component can be retained. The support is preferably a non-woven fabric, a woven fabric or the like, a fiber assembly having a void for retaining moisture therein, a porous material such as a sponge sheet, and the like.
By impregnating the support with the microcapsule-containing composition of the present disclosure, the support is pressed against the skin and rubbed, so that the microcapsules are disintegrated and the core material can be released at an arbitrary time. Moreover, it can be set as the sheet | seat for skin wiping because a microcapsule containing composition contains cleaning components, such as surfactant.
Cosmetic sheets, diapers and the like are preferably packaged with a water-impermeable packaging material in order to stably hold the microcapsule-containing composition, from the viewpoint of sustaining effects.

As described above, since the microcapsule-containing composition of the present disclosure can release the core material at an arbitrary timing at a necessary timing, it can be applied to various uses. The use described above is an example thereof, and the use of the microcapsule-containing composition of the present disclosure is not limited to the above description.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.

In this example, the volume-based median diameter, standard deviation, and volume average particle diameter were measured by Microtrac MT3300EXII (manufactured by Nikkiso Co., Ltd.). The wall thickness was measured by observing the cross section of the microcapsule with a scanning electron microscope JSM-7800F (manufactured by JEOL Ltd.).

(Measurement of breaking strength of microcapsules)
In this example, the breaking strength of the microcapsules was obtained by diluting the microcapsule aqueous dispersion 1000 times with water, and dropping and drying on a slide glass. The breaking strength of microcapsules having a diameter of about 20 μm on the slad glass was measured using a microhardness meter DUH-W201 (manufactured by Shimadzu Corporation). Measurement was performed on 6 microcapsules per sample, and the average value was taken as the measured value.

(Example 1)
18.2 parts by mass of Saracos (registered trademark) HG-8 (manufactured by Nisshin Oillio Group Co., Ltd.) as a solvent, 54.7 parts by mass of D-limonene (manufactured by Yashara Chemical Co., Ltd., fragrance), and trifunctional as a shell material 13.5 parts by mass of Takenate (registered trademark) D-160N (made by Mitsui Chemicals, Inc., hexamethylene diisocyanate trimethylolpropane adduct), 4,4′-diphenylmethane diisocyanate (MDI, Wako Pure Chemical) Kogyo Co., Ltd .; specific diisocyanate compound) 4.5 parts by mass was stirred and mixed to obtain an oil phase solution. The content ratio of the structure derived from the bifunctional aromatic isocyanate compound to the total mass of the shell material is 25% by mass.
Further, an oil phase solution was added to and dispersed in 157 parts of a 5.8% aqueous solution of Kuraray Poval (registered trademark) PVA-217E (manufactured by Kuraray Co., Ltd., PVA), which is polyvinyl alcohol, and the resulting emulsion was heated to 70 ° C. Warmed up. After stirring for 6 hours, 3.8 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added to obtain an aqueous microcapsule dispersion.
The volume-based median diameter (D50) of the obtained microcapsules was 18 μm. The CV value [= (standard deviation / volume average particle size) × 100] of the particle size distribution was 36%. The breaking strength of the microcapsule was 20.5 MPa.

<Creation of evaluation sample>
A microcapsule-containing composition was prepared by mixing with a fragrance-free softener (ULTRA Downy, manufactured by Procter & Gamble Japan Co., Ltd.) so that the fragrance conversion of the microcapsule produced above was 1.0 mass%. Put about 1.5 kg of cotton towel (36 cm x 36 cm) into automatic washing machine AW-422S (H) (manufactured by Toshiba Corporation), add 30 L of water, and add 10 parts by weight of the microcapsule-containing composition as a washing base softener. It was put into the injection port and a washing process (washing 10 minutes, rinsing 25 minutes, dehydration 10 minutes) was performed. Thereafter, the sample was dried for 24 hours to obtain a sample for sustained release evaluation.

(Example 2)
A microcapsule aqueous dispersion was obtained in the same manner as in Example 1 except that the polyvinyl alcohol used in Example 1 was used as described in Table 1.
The volume-based median diameter, standard deviation, volume average particle diameter, wall thickness, and microcapsule breaking strength of the obtained microcapsules were measured in the same manner as in Example 1.

(Example 3 to Example 17)
A microcapsule aqueous dispersion was obtained in the same manner as in Example 1 except that the polyvinyl alcohol used in Example 1 was changed and the type and mixing ratio of the isocyanate compound were changed as shown in Table 1. It was.
The volume-based median diameter, standard deviation, volume average particle diameter, wall thickness, and microcapsule breaking strength of the obtained microcapsules were measured in the same manner as in Example 1.

(Comparative Examples 1 to 5)
A microcapsule aqueous dispersion was obtained in the same manner as in Example 1 except that the type and mixing ratio of the isocyanate compound used were changed as shown in Table 1 in Example 1.
The volume-based median diameter, standard deviation, volume average particle diameter, wall thickness, and microcapsule breaking strength of the obtained microcapsules were measured in the same manner as in Example 1.

(Example 18)
75 parts by mass of Isoban (registered trademark) 10 (manufactured by Kuraray Co., Ltd., 10% isobutylene-maleic anhydride copolymer aqueous solution) and 80 parts by mass of water were mixed, and the pH of this mixture was adjusted with a 10% aqueous sodium hydroxide solution. The aqueous phase solution was adjusted to 4.5. 18.3 parts by mass of Saracos (registered trademark) HG-8 (manufactured by Nisshin Oillio) as a solvent, 54.7 parts by mass of D-limonene (manufactured by Yashara Chemical Co., Ltd., fragrance) as a fragrance, and 4,4′- as a shell material 4.5 parts by mass of diphenylmethane diisocyanate (MDI, manufactured by Wako Pure Chemical Industries, Ltd .; specific diisocyanate compound) is mixed to form an oil phase solution, and the total amount of the oil phase solution adjusted to 140 parts by mass of the aqueous phase solution is added and dispersed to emulsify. A liquid was obtained. 10.1 parts by mass of melamine-formaldehyde prepolymer Nical Resin S-260 (manufactured by Nippon Carbide Industries Co., Ltd.) as a shell material was added to the emulsified liquid, heated to 65 ° C., and then formed into a capsule film for 24 hours The reaction was continued and allowed to react. In order to reduce the residual formaldehyde, after cooling to 30 ° C., 29% aqueous ammonia was added until the pH reached 7.5 to obtain a microcapsule aqueous dispersion.
The volume-based median diameter (D50) of the obtained microcapsules was 18 μm. The CV value [= (standard deviation / volume average particle size) × 100] of the particle size distribution was 36%. The breaking strength of the microcapsule was 24.3 MPa.

(Example 19 to Example 33)
A microcapsule aqueous dispersion was obtained in the same manner as in Example 18 except that the type and mixing ratio of the melamine formaldehyde prepolymer and isocyanate compound used were changed as shown in Table 2.
The volume-based median diameter, standard deviation, volume average particle diameter, wall thickness, and microcapsule breaking strength of the obtained microcapsules were measured in the same manner as in Example 18.

(Comparative Examples 6 to 10)
In Example 18, a microcapsule aqueous dispersion was obtained in the same manner as in Example 18, except that the type and mixing ratio of the isocyanate compound used were changed as shown in Table 2.
The volume-based median diameter, standard deviation, volume average particle diameter, wall thickness, and microcapsule breaking strength of the obtained microcapsules were measured in the same manner as in Example 18.

-Evaluation-
(Sensory evaluation of sustained release)
The evaluation sample (cotton towel) obtained above was aged at 25 ° C., and the scent intensity was evaluated by 10 panelists every 24 hours. The score was given according to the following criteria, and an average value of 5 times (rounded to the nearest whole number) was obtained as an index for evaluating sustained release.
<Evaluation criteria>
0 point: There is no scent immediately after drying.
1 point: Scented immediately after drying, but not scented after 24 hours.
2 points: scented after 24 hours, but not scented after 48 hours.
3 points: scented after 48 hours, but not scented after 72 hours.
4 points: Scented after 72 hours.

(Evaluation of sustained release by reducing fragrance)
The evaluation sample (cotton towel) obtained above was cut into a square of 1/6 area, and the cut towel was immersed in 100 g of dimethyl sulfoxide and allowed to stand for 24 hours to extract the fragrance inside the microcapsule. The extracted amount (mg) of the fragrance was quantified in the obtained dimethyl sulfoxide solution with a gas chromatograph analyzer (QP2010Ultra, manufactured by Shimadzu Corporation). About this fragrance | flavor extraction amount, the fragrance | flavor reduction amount was computed using the following formula from the fragrance | flavor extraction amount immediately after preparation of an evaluation sample and 48 hours after a time lapse.
(formula)
Fragrance reduction amount (% by mass) = (fragrance extraction amount immediately after preparation (mg) −fragrance extraction amount after aging at 25 ° C. for 48 hours (mg)) / fragrance extraction amount immediately after preparation (mg) × 100

In addition, PVA in Table 1 represents an emulsifier.

In Tables 1 and 2, “-” indicates that no component is contained.

Details of the components in Tables 1 and 2 are as follows.
217E: Kuraray Poval PVA-217E (partially saponified polyvinyl alcohol), manufactured by Kuraray Co., Ltd. KM-618: Kuraray Poval KM-618 (anion modified polyvinyl alcohol), manufactured by Kuraray Co., Ltd. D-160N: Takenate D-160N (Hexamethylene diisocyanate trimethylolpropane adduct), manufactured by Mitsui Chemicals, Inc. MDI: 4,4′-diphenylmethane diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.)
・ HDI: Hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.)
DMDI: 4,4′-dicyclohexylmethane diisocyanate (Wako Pure Chemical Industries, Ltd.)
・ THDI: Trimethylhexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.)

・ Isoban 10: Concentrated 10% isobutylene-maleic anhydride copolymer aqueous solution, manufactured by Kuraray Co., Ltd. ・ Nikaresin S-260: Melamine-formaldehyde prepolymer, manufactured by Nippon Carbide Industries, Ltd.

As shown in Table 1, the shell material is a microcapsule containing polyurethane or polyurea, and i) at least one selected from a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound Examples 1 to 17 which are microcapsule compositions having a structure of 10% by mass to 70% by mass with respect to the total mass of the shell material and having a shell thickness of 0.3 to 2.0 μm are as follows: It was found that the sustained release properties were superior to those of Comparative Examples 1 to 5 that did not satisfy this requirement.
Further, from the microcapsules of Examples 6 to 11, it was found that there is a preferable range in the quantitative relationship between the trifunctional or higher functional aliphatic isocyanate compound and the specific diisocyanate compound in terms of sustained release.
Moreover, as shown in Table 2, the same results as described above were obtained when microcapsules containing a melamine formaldehyde resin as the shell material were used.

The microcapsule of the present disclosure can be suitably used as a core material, particularly in a mode in which a fragrance is included, and can exhibit various preferable functions such as fragrance protection and sustained release.

Claims

A microcapsule-containing composition comprising a microcapsule having a shell and a core containing a fragrance,
i) At least one structure selected from a structure derived from a bifunctional aliphatic isocyanate compound and a structure derived from a bifunctional aromatic isocyanate compound is 10% by mass with respect to the total mass of the shell material forming the shell. ~ 70% by mass,
ii) the thickness of the shell is 0.3 to 2.0 μm;
A composition containing microcapsules.
The microcapsule-containing composition according to claim 1, wherein the microcapsule has a breaking strength of 16 MPa or more.
The microcapsule-containing composition according to claim 1 or 2, wherein the shell material contains at least one of polyurethane and polyurea or a melamine formaldehyde resin.
The microcapsule-containing composition according to any one of claims 1 to 3, wherein the shell material includes at least one of polyurethane having a structure derived from a polyisocyanate compound and polyurea.
The shell material is at least one structure selected from a structure derived from a trifunctional or higher functional aliphatic isocyanate compound, a structure derived from a bifunctional aliphatic isocyanate compound, and a structure derived from a bifunctional aromatic isocyanate compound; The microcapsule-containing composition according to claim 4, comprising a polyurethane or polyurea having.
The microcapsule-containing composition according to any one of claims 1 to 3, wherein the shell material contains a melamine formaldehyde resin having a structure derived from a melamine formaldehyde prepolymer compound.
The shell material has at least one structure selected from a structure derived from a melamine formaldehyde prepolymer compound, a structure derived from a bifunctional aliphatic isocyanate compound, and a structure derived from a bifunctional aromatic isocyanate compound. The microcapsule-containing composition according to claim 6, comprising a melamine formaldehyde resin.
A laundry composition, day care composition or hair care composition comprising the microcapsule-containing composition according to any one of claims 1 to 7.