JP2013040230A - Method for producing composition containing cyclodextrin inclusion compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a composition containing cyclodextrin inclusion compound which can prevent or reduce alteration or elimination of a guest compound even if the cyclodextrin inclusion compound is in contact with water.SOLUTION: The method for producing a composition containing cyclodextrin inclusion compound includes: a first step for contacting an inclusion compound obtained by making the guest compound to be included in cyclodextrin and an amphiphilic polymer compound in an aqueous phase to form a hydrous first composition; and a second step for dehydrating the first composition formed in the first step and obtaining solid containing the inclusion compound.

Description

  The present invention relates to a method for producing a cyclodextrin inclusion compound-containing composition, and more specifically, even when an inclusion compound (cyclodextrin inclusion compound) obtained by inclusion of a guest compound in cyclodextrin is contacted with water, The present invention relates to a production method capable of producing a cyclodextrin inclusion compound-containing composition that can be altered, such as dissolution and swelling, or can prevent or reduce the release of a guest compound.

Cyclodextrin (CD) is a kind of cyclic oligosaccharide in which a plurality of glucoses are combined to form a cyclic structure, and various compounds (guest compounds) in ring vacancies (hollow part of the cyclic structure) formed in the CD molecule. Is used in various fields (for example, refer to Patent Document 1).
Patent Document 1 states that “when an excrement comes into contact with the excrement disposal sheet, an improvement is added to the conventional excrement disposal sheet so that the odor of the excrement can be quickly masked by the aroma generated by the fragrance. Specifically, “Patent Document 1, Paragraph No. 0004 in Detailed Description of the Invention”, specifically, “Liquid-absorbent core material between liquid-permeable sheet and liquid-impermeable sheet” The excrement treatment sheet for pets includes a fragrance that generates a fragrance capable of masking the odor of the excrement when the excrement of the pet animal comes into contact with the excrement. A particulate inclusion compound that is included in dextrin, wherein the core is located on the liquid-permeable sheet side, and the lower surface is located on the liquid-impermeable sheet side. Having said inclusion And the upper surface of the compound is the core, wherein the processing sheet "(Patent Document 1, claim 1), characterized in that between the liquid-permeable sheet immediately above the top surface is disclosed. According to the excrement disposal sheet, “the excrement disposal sheet according to the present invention includes a perfume in water-soluble cyclodextrin, and the inclusion compound by the cyclodextrin has an upper surface of the absorbent core, Since the urine is excreted on the excrement disposal sheet, the inclusion compound quickly dissolves in the urine and the odor of the fragrance is liquid permeable. It can pass through the sheet and quickly diffuse into the atmosphere to mask the odor of urine ”(Patent Document 1, paragraph number 0014 in the detailed description of the invention).

Japanese Unexamined Patent Application Publication No. 2010-51261 (for example, abstracts, claims, paragraph numbers 0001 to 0014 in the detailed description of the invention, FIG. 2, etc.)

  In the particulate inclusion compound (cyclodextrin inclusion compound) in which the fragrance (guest compound) is included in the cyclodextrin contained in the excrement treatment sheet of Patent Document 1 described above, urine is placed on the excrement treatment sheet. When excreted, the inclusion compound (cyclodextrin inclusion compound) is quickly dissolved by the urine, and the odor of the fragrance as a guest compound quickly passes through the liquid-permeable sheet and diffuses into the atmosphere. Thus, when the cyclodextrin clathrate compound comes into contact with moisture, the cyclodextrin clathrate compound usually has a property of dissolving or swelling (deterioration), or the guest compound is detached from the cyclodextrin clathrate compound. In the excrement disposal sheet of Patent Document 1 described above, the cyclodextrin inclusion compound dissolves quickly in urine using such properties, and the odor of the fragrance as a guest compound passes through the liquid-permeable sheet and quickly enters the atmosphere. It is preferable that the cyclodextrin inclusion compound is altered (dissolved, swelled, etc.) or the guest compound is detached by contact with water (urine) because it can diffuse into the masking odor of urine. However, the cyclodextrin inclusion compound may not be used for applications where the cyclodextrin inclusion compound is altered (dissolved or swollen) by contact with water or the guest compound is not intended to be detached. It was.

  Therefore, in the present invention, even when the clathrate compound (cyclodextrin clathrate compound) in which the guest compound is clathrated with cyclodextrin is contacted with water, it is altered such as dissolution or swelling, or the guest compound is desorbed. It aims at providing the manufacturing method of the cyclodextrin inclusion compound containing composition which can prevent or reduce.

  As a result of intensive studies, the inventors of the present invention have found that an inclusion compound (cyclodextrin inclusion compound) in which a guest compound is included in a cyclodextrin (hereinafter also referred to as “CD”). The amphiphilic polymer compound is contacted in an aqueous phase to form a hydrous first composition, and then the first composition is dehydrated to contain the inclusion compound (cyclodextrin inclusion compound). It is found that a cyclodextrin clathrate compound-containing composition can be produced as the cyclodextrin clathrate compound-containing composition. The clathrate compound (cyclodextrin clathrate compound) is altered such as dissolution or swelling, and the guest compound is detached from the clathrate compound (cyclodextrin clathrate compound). And we have completed the present invention by finding that it is possible to prevent or reduce.

That is, the production method for producing the cyclodextrin clathrate compound-containing composition of the present invention (hereinafter referred to as “the present method”) includes an clathrate compound in which a guest compound is clathrated in cyclodextrin and an amphiphilic polymer. A first step of contacting the compound in an aqueous phase to form a hydrous first composition, and dehydrating the first composition formed by the first step to obtain a solid containing the inclusion compound And a method for producing a cyclodextrin inclusion compound-containing composition comprising two steps.
The method includes a first step and a second step.
In the first step, an inclusion compound in which a guest compound is included in cyclodextrin (CD) and an amphiphilic polymer compound are contacted in an aqueous phase to form a hydrous first composition. As described in detail later, the CD may be any one or a mixture of α type (polymerization degree 6), β type (polymerization degree 7) and γ type (polymerization degree 8). Alternatively, a chemically modified hydroxyl group may be used. The clathrate compound in which the guest compound is clathrated with the CD is conventionally known and widely used, but in the present invention, in order to prevent or reduce the quality change and the guest compound detachment when the clathrate compound comes into contact with water. Amphiphilic polymer compounds are used. As will be described later, the amphiphilic polymer compound is a polymer compound having both a hydrophilic group and a hydrophobic group in one molecule, and is formed by contacting an inclusion compound and an amphiphilic polymer compound in an aqueous phase. By dehydrating one composition in the second step, the amphiphilic polymer compound binds the inclusion compound as a binder component.
In the second step, the first composition obtained in the first step is dehydrated to obtain a solid (cyclodextrin inclusion compound-containing composition) containing the inclusion compound. In the cyclodextrin clathrate-containing composition thus obtained, the clathrate compound in which the guest compound is clathrated with the cyclodextrin is combined with an amphiphilic polymer compound as a binder component to form an aggregate. Even if the cyclodextrin clathrate-containing composition comes into contact with water, the clathrate compound contained therein is prevented from being altered or the guest compound is prevented from being detached from the clathrate compound.

In this method, the first step is to mix the clathrate compound water composition containing the clathrate compound and water and the amphiphilic polymer compound water composition containing the amphiphilic polymer compound. It may be performed by doing.
The first step of contacting the clathrate compound with the amphiphilic polymer compound in the aqueous phase to form a first composition containing water includes the clathrate compound water composition containing the clathrate compound and water, the parents If the amphiphilic polymer compound water composition containing the amphiphilic polymer compound and water is mixed, both the inclusion compound and the amphiphilic polymer compound are preliminarily mixed with water. And the mixture of the clathrate compound and water (the clathrate compound water composition) and the mixture of the amphiphilic polymer compound and water (the amphiphilic polymer compound water composition) The clathrate compound and the amphiphilic polymer compound can be mixed evenly. Thus, when the inclusion compound and the amphiphilic polymer compound are sufficiently mixed, the inclusion compound can be uniformly bonded by the amphiphilic polymer compound when dehydrated in the second step.

In this method, the ratio (w4 / m3) of the mass w4 of the amphiphilic polymer compound to the total mass m3 of the cyclodextrin and the guest compound may be 0.03 to 0.24.
If the ratio (w4 / m3) is too large, the detachment of the guest compound is promoted from the inclusion compound in the first step. Conversely, if the ratio (w4 / m3) is too small, the cyclodextrin inclusion compound-containing composition is Since the degradation of the clathrate compound and the detachment of the guest compound from the clathrate compound upon contact with water cannot be reduced or prevented well, the range may satisfy both of these conditions. It may be set to ~ 0.24.

In this method, the amphiphilic polymer compound may be an ethylene / acrylic acid copolymer and / or an ethylene vinyl acetate copolymer.
The ethylene / acrylic acid copolymer and the ethylene vinyl acetate copolymer can be made into a polymer compound having both a hydrophilic group and a hydrophobic group in a balanced manner in one molecule, and ethylene / acrylic acid is used as an amphiphilic polymer compound. By using a copolymer and / or an ethylene vinyl acetate copolymer, it can function well as a binder component for binding an inclusion compound.

In this method, the 2nd step may dehydrate by spray-drying the 1st composition.
In the second step of dehydrating the first composition, if the first composition is dehydrated (dried) by a spray drying method, the cyclodextrin inclusion compound-containing composition has a substantially spherical shape. If the cyclodextrin inclusion compound-containing composition (CD inclusion in Examples etc.) has a spherical shape with a small specific surface area (surface area per unit volume), the cyclodextrin inclusion compound-containing composition (CD inclusion) Since the specific surface area in contact with water is small even if the product is in contact with water, the quality of the clathrate compound contained in the cyclodextrin clathrate compound-containing composition (CD clathrate) due to contact with water and The elimination of the guest compound can be successfully reduced or prevented.

In this method, the first composition may be homogenized prior to the second step.
In the first composition in which the inclusion compound and the amphiphilic polymer compound are brought into contact with each other in the aqueous phase and mixed, the inclusion of the inclusion compound and the amphiphilic polymer compound is the second step. The cyclodextrin inclusion compound-containing composition formed by dehydrating the first composition is preferable because it has a nearly uniform structure. Therefore, the clathrate compound and the amphiphilic polymer compound may be sufficiently mixed by homogenizing the first composition prior to the second step.

The present invention also provides a cyclodextrin inclusion compound-containing composition (hereinafter referred to as “the present composition”) comprising an inclusion compound in which a guest compound is included in cyclodextrin.
That is, the present composition is a cyclodextrin inclusion compound-containing composition that can be produced by the present method. As described above, the present composition forms an aggregate formed by the inclusion of an inclusion compound obtained by inclusion of a guest compound in cyclodextrin by an amphiphilic polymer compound as a binder component. Even when the composition comes into contact with water, the inclusion compound contained in the composition is prevented from being deteriorated or the guest compound is prevented from being detached from the inclusion compound.

Even when the composition is in contact with water, the inclusion compound contained in the composition can be prevented from being denatured or the guest compound can be prevented from being detached from the inclusion compound. The composition can also be used in applications where the contact is made.
For example, by adding the present composition to a pulp suspension in which a large amount of water is present in the paper making process, it is possible to produce a paper to which the present composition is attached. That is, by carrying out a papermaking process using a pulp suspension to which the present composition is added, paper to which the present composition is attached can be produced. Since the present composition attached to such paper has the inclusion compound altered even when it comes into contact with water in the papermaking process and the detachment of the guest compound from the inclusion compound is greatly suppressed, the original inclusion compound It is possible to give the paper properties according to the above.

4 is a flowchart illustrating an embodiment of the method. It is a scanning electron micrograph after carrying out water dispersion of CD inclusion. It is a conceptual diagram which shows the sustained-release rate measuring apparatus used for discharge | release experiment of the guest compound from CD inclusion body (cyclodextrin inclusion compound containing composition). It is a conceptual diagram which shows the sustained-release rate measuring apparatus used for discharge | release experiment of the guest compound from CD clathrate carrying | support paper. It is a graph which shows the change of F (sustained release rate per unit mass and unit area) with respect to an amphiphilic polymer compound and its addition amount. It is a graph which shows the change of F (unit mass and the sustained release rate per unit area) at the time of changing the temperature of an air thermostat. 2 is a graph showing the results of a guest compound release experiment from the CD inclusion of Example 1. FIG. It is a graph which shows the result of discharge | release experiment of the guest compound from CD clathrate carrying | support paper.

An embodiment of the present invention will be described with reference to FIG.
In the present invention, an inclusion compound obtained by inclusion of a guest compound in cyclodextrin and an amphiphilic polymer compound are contacted in an aqueous phase to form a first composition containing water, and then the first composition And a solid (cyclodextrin clathrate-containing composition) containing the clathrate compound is obtained. Here, as shown in FIG. A clathrate compound water composition containing a compound and water) and an amphiphilic polymer compound liquid 19 (amphiphilic polymer compound water composition containing an amphiphilic polymer compound and water) 20 (Contact between the clathrate compound and the amphiphilic polymer compound in the aqueous phase), and after performing homogenization 23, drying 27 is performed to obtain CD clathrate 29 (cyclodextrin clathrate compound-containing composition). To manufacture.

Here, the CD clathrate water mixture 17 is prepared by mixing the CD water mixture 11 and the guest compound 13 in the aqueous phase.
(CD water mixture 11)
The cyclodextrin (CD) water mixture 11 is prepared by mixing cyclodextrin (CD) with water.
Cyclodextrins exist in α-type (degree of polymerization 6), β-type (degree of polymerization 7) and γ-type (degree of polymerization 8) with glucose polymerization degrees 6, 7 and 8, respectively. Here, α-type, Any one of β-type and γ-type or a mixture of two or more types can be suitably used. In addition, one glucose unit of CD has three hydroxyl groups (for example, one molecule of β-type (polymerization degree 7) CD has 21 modifiable hydroxyl groups), and these hydroxyl groups are chemically modified. CD can also be used. The proportion (100 × nc / nt) of chemically modified hydroxyl groups (nc) among hydroxyl groups (nt) in one molecule of CD is 0% (no modification) or more and 100% (all hydroxyl groups are modified) The following is acceptable. Examples of the chemical modification of these hydroxyl groups include methylation and hydroxypropylation, but are not limited thereto, and any modification can be used as long as the desired guest compound 13 (described later) can be included in a desired degree. . In addition, CD may be water-soluble, sparingly water-soluble, or insoluble, and when not dissolved in water, CD water mixture 11 in a slurry state may be used (that is, CD water mixture 11 includes CD aqueous solution, Any of CD slurry liquid and a mixture of both may be used.)

When the CD water mixture 11 used is too high in the concentration of CD, the CD itself is not uniformly dispersed in water, and the guest compound 13 to be added later is not well dispersed. Not uniformly included (non-uniform inclusion). Conversely, if the CD concentration in the CD water mixture 11 is too low, the amount of the emulsion 25 described later increases, and the desorption (volatilization) of the guest compound 13 from the CD in the final drying step 27 increases. Since the yield of the CD clathrate 29 decreases, it may be within a range satisfying both of these conditions, and is usually 30 to 70% (the CD mass w6 in the CD water mixture 11 with respect to the total mass w5 of the CD water mixture 11). The concentration range may be a ratio (100 × w6 / w5).
The CD water mixture 11 may be prepared, for example, by gradually adding CD while stirring water (for example, distilled water) injected into a container at room temperature.

(Guest compound 13)
As the guest compound 13 to be used, a compound (a volatile compound is particularly preferable) that can be included in the ring vacancies (hollow portion of the ring structure) of the CD contained in the CD water mixture 11 can be used without particular limitation.
An example of the guest compound 13 is as follows. For example, ingredients contained in essential oils used in perfumes and antibacterial agents can be mentioned. Specifically, natural trees, branches and leaves, rhizomes, bark, fruits and the like are used as raw materials, and the raw materials are steam distilled, compressed, various Natural essential oil components (for example, hiba oil, mint essential oil, lemongrass essential oil, etc.) that can be used in the extraction method may be used. Such a natural essential oil component is a natural product contained in a plant, and thus is highly safe for the human body. However, the guest compound 13 is not limited to a natural product, and a synthetic product synthesized artificially is used. It may be used.
Examples of natural essential oil components include substances such as terpenes (terpene hydrocarbons such as limonene, terpene alcohols, terpene aldehydes, terpene ketones, terpene oxides) and allyl isothiocyanate (known as the pungent component of mustard and horseradish). Can be mentioned. These essential oil components may be used alone or in combination of two or more. In addition, two or more kinds of substances can be mixed and used as long as they can be included in the ring vacancies of the CD (a case where two or more kinds of substances are included in one ring vacancy and each ring This includes both cases where one substance is included in the vacancies, but the substance included in each ring vacancy is different.

(Mixing 15)
In order to include the guest compound 13 in the CD in the CD water mixture 11, the guest compound 13 is mixed 15 with the CD water mixture 11. The guest compound 13 is added to the CD water mixture 11 at room temperature, and the CD water mixture 11 is mixed 15 with the guest compound 13 by stirring the mixture at room temperature for 1 day, and the CD clathrate water mixture 17 containing the clathrate compound is obtained. obtain.
The mixture 15 of the CD water mixture 11 and the guest compound 13 is included in the CD if the ratio (Mg / Mc) of the number of moles Mg of the guest compound 13 to the number Mc of CD contained in the CD water mixture 11 is too high. Since a large amount of the guest compound 13 that remains is lost, the guest compound 13 is wasted. On the other hand, if the guest compound 13 is too low, the guest compound 13 is not included in the CD well. It may be set to 1.0 to 1.5 (for example, the ratio (Mg / Mc) may be about 1.5).
Further, if the stirring time after adding the guest compound 13 to the CD water mixture 11 is too short, the guest compound 13 cannot be successfully included in the CD, and conversely, if the guest compound 13 is too long, the guest compound 13 is encased in the CD. Since the contact amount does not increase, it may be in a range where both of them are compatible, and may be usually 12 to 24 hours. If the temperature during stirring after adding the guest compound 13 to the CD water mixture 11 is too high, the loss due to volatilization of the guest compound 13 increases. Conversely, if the temperature is too low, the guest compound 13 is difficult to be included in the CD. Therefore, it may be set as the range which satisfies both these conditions, and may be normally 10-40 degreeC.
If the ratio of the total mass of CD and guest compound 13 in the CD inclusion body / amphiphilic polymer compound dispersion liquid 21 described later is too high, the CD inclusion body / amphiphilic polymer compound dispersion liquid When the viscosity of 21 is increased, the particle diameter of the resulting CD inclusion 29 may be too large, or the resulting CD inclusion 29 may have a distorted shape rather than a spherical shape. On the contrary, if the ratio is too low, the amount of the emulsified liquid 25 increases, and the desorption (volatilization) of the guest compound 13 from the clathrate compound in the final drying step 27 increases, and the CD clathrate 29 Therefore, it may be within the range satisfying both of these conditions, and the ratio (CD inclusion body / amphiphilic polymer compound dispersion 21 with respect to the total mass w7 of CD and guest compound contained therein) The ratio of the total mass w8 to 13 (100 × w8 / w7)) may usually be 25% to 40%.

(Amphiphilic polymer liquid 19)
As the amphiphilic polymer compound liquid 19, an amphiphilic polymer compound aqueous solution and an aqueous dispersion (suspension etc.) of the amphiphilic polymer compound can be used.
The amphiphilic polymer compound is a polymer compound having both a hydrophilic group and a hydrophobic group in one molecule, and the inclusion compound (the guest compound 13 is included in the CD) included in the CD inclusion body water mixture 17. ) Is formed as an aggregate, and the aggregate needs to be retained even in water. For that purpose, the balance between hydrophilicity and hydrophobicity of the amphiphilic polymer compound is important. That is, when the hydrophilicity of the amphiphilic polymer compound is too high, the clathrate collapses due to water absorption or the clathrate detachment occurs in water, and the retention rate of the clathrate compound decreases (the aggregate in water May interfere with the maintenance of And, when the hydrophobicity of the amphiphilic polymer compound is too high, it becomes difficult to disperse in water or floats (such as hindering the formation of CD inclusions as an aggregate). Can occur). The amphiphilic polymer compound is soluble in water or can be dispersed in water with particles of the amphiphilic polymer compound (the average particle size of the particles dispersed in water is 5 μm or less) The average particle size is measured three times using a laser diffraction particle size distribution measuring apparatus using distilled water as a dispersion medium, and the arithmetic average value of the three times is defined as the average particle size. ) May be used.

As the amphiphilic polymer compound, it is preferable to use a substance having both a hydrophilic group and a hydrophobic group in one molecule so that the hydrophilic property and the hydrophobic property are balanced. As the hydrophilic group, vinyl type CH ₂ —CHX (X = OH, COOH, CONH ₂ , COOCH ₃ , COOC ₂ H ₅ , COOC ₄ H ₉ , OCOCH ₃ , OCOC ₂ H ₅ ), vinylidene type CH ₂ —CXY (Where X = CH ₃ , Y = COOH, CN, COOCH ₃ , COOC ₂ H ₅ COOC ₄ H ₉ ) and the like. As the hydrophobic group, vinyl type CH ₂ —CHX (where X = H, CH ₃ , CN, Cl), vinylidene type CH ₂ —CXY (where X = Cl Y = Cl, X = CH ₃ Y = CH ₃ ), Examples include diene type CH ₂ —CHX—CH ₂ CH ₂ (where X = H, CH ₃ , Cl). In addition, a hydrophilic polymer such as a poorly water-soluble polyvinyl alcohol as an amphiphilic polymer compound is cross-linked with a water-soluble polymer that is hardly soluble in water after it is solidified. Polymers that are cross-linked using an agent and hardly soluble in water may also be used.
Examples of substances that have a good balance between hydrophilicity and hydrophobicity and can be used as an amphiphilic polymer compound include ethylene / acrylic acid copolymers and ethylene vinyl acetate copolymers. Specifically, both the ethylene / acrylic acid copolymer and the ethylene vinyl acetate copolymer are soluble in water, or particles in which the copolymer particles can be dispersed in water (particles dispersed in water). The average particle size is preferably 5 μm or less, and this average particle size is measured three times using a laser diffraction particle size distribution measuring device and distilled water as a dispersion medium, and the three arithmetic operations are performed. As long as the average value is the average particle diameter, it can be used without particular limitation.

The amphiphilic polymer compound liquid 19 may be either an amphiphilic polymer compound aqueous solution or an aqueous dispersion (suspension etc.) of the amphiphilic polymer compound.
If the concentration of the amphiphilic polymer compound 19 in the amphiphilic polymer compound liquid 19 is too high, the CD inclusion body / amphiphilic polymer compound dispersion 21 cannot be formed well. 25, the amount of the solution 25 increases, and the desorption (volatilization) of the guest compound 13 from the CD in the final drying step 27 increases, leading to a large loss of the CD inclusion 29. In general, the concentration (ratio of the mass of the amphiphilic polymer compound contained in the total mass of the amphiphilic polymer compound liquid 19) may be 20% to 70%.

(Mixing 20)
The CD clathrate / amphiphilic polymer compound dispersion liquid 21 is prepared by mixing 20 the amphiphilic polymer compound liquid 19 with the CD clathrate water mixture 17 and stirring the mixture.
In the mixing 20, the amount of the amphiphilic polymer compound liquid 19 added to the CD clathrate water mixture 17 can be defined as the amount of the amphiphilic polymer compound contained in the amphiphilic polymer compound liquid 19. . That is, the total mass (m3 (g) = m1 + m2) of the CD (m1 (g)) containing the CD water mixture 11 used to prepare the CD clathrate water mixture 17 and the guest compound 13 (m2 (g)). ) And the mass (w4 / m3) of the mass w4 (g) of the amphiphilic polymer compound contained in the amphiphilic polymer compound liquid 19 is too large. The elimination of the guest compound 13 from the compound is promoted, which is not preferable. Conversely, when the ratio (w4 / m3) is too small, the CD inclusion 29 is dispersed in water when the CD inclusion 29 is dispersed in water. Since the dissolution of the guest compound 13 from the clathrate compound is promoted and a sufficient effect by the amphiphilic polymer compound cannot be obtained, it may be within a range satisfying both of these conditions. It may be set to ~ 0.24. For example, when an ethylene / acrylic acid copolymer (ethylene unit: acrylic acid = 8: 2) is used as the amphiphilic polymer compound, the ratio (w4 / m3) is set to 0.03 to 0.24. After the CD inclusions 29 are dispersed in water with respect to the amount (m5) of the guest compound 13 included in the CD inclusions 29 before the CD inclusions 29 described later are dispersed in water. The ratio (m6 / m5) of the amount (m6) of the guest compound 13 included in the CD inclusion product 29 was 0.327 when the ratio (w4 / m3) = 0.03 ( When a conventionally known CD inclusion of limonene was used, the ratio (m6 / m5) = 0.12) and the ratio (w4 / m3) = 0.36 were 0.347.

  If the temperature at which the amphiphilic polymer compound liquid 19 is mixed 20 with the CD clathrate water mixture 17 is too high, the CD clathrate (cladding compound) contained in the CD clathrate water mixture 17 will be the guest compound. 13 desorption (volatilization) increases, leading to loss of the CD inclusion 29, and conversely, if it is too low, the amphiphilic polymer liquid 19 is unstable (for example, in the amphiphilic polymer liquid 19 When the amphiphilic polymer compound 19 forms an emulsion, the amphiphilic polymer compound liquid 19 is melted by bonding the emulsion particles when the amphiphilic polymer compound liquid 19 is frozen. However, the emulsion state may not be formed, etc.). Therefore, it may be in a range satisfying both of these conditions, and may be usually 5 ° C. to 40 ° C. If the stirring time of the mixing 20 is too long, the effect does not increase. Conversely, if the mixing time is too short, the CD inclusion body (inclusion compound) does not disperse well in the amphiphilic polymer compound. It may be set as the range to satisfy | fill, and may be normally made into 5 to 30 minutes.

(Homogenize 23)
The CD clathrate / amphiphilic polymer compound dispersion 21 obtained by mixing 20 is homogenized 23 (for example, 8000 rpm) using a homogenizer (for example, trade name “POLYTRON PT6100” manufactured by Kinematica). 3 minutes) to prepare emulsion 25. The purpose of homogenizing 23 of the CD clathrate / amphiphilic polymer compound dispersion 21 is to sufficiently mix the CD clathrate and the amphiphilic polymer compound.

(Dry 27)
The emulsified liquid 25 is dried 27 to form a powdered CD inclusion 29.
The drying 27 of the emulsion 25 can be performed by a known CD microcapsule preparation method such as a spray drying method or a kneading method.
The CD inclusion 29 formed by the spray drying method has a spherical shape. If the CD inclusion 29 has a spherical shape with a small specific surface area (surface area per unit volume), even if the CD inclusion 29 comes into contact with water, the specific surface area that comes into contact with water is small. It is possible to prevent or reduce deterioration of the CD inclusion (inclusion compound) (for example, disintegration due to water absorption, detachment of the guest compound 13). In this respect, the drying 27 is preferably a spray drying method.
The CD inclusion 29 thus obtained has a cluster-like or spherical shape under a microscope, and has a moisture content as will be described later, compared to the conventionally known CD inclusion (inclusion compound). It is possible to prevent or reduce deterioration due to contact with water (for example, disintegration due to water absorption, detachment of the guest compound 13).

(Characteristics of CD inclusion 29)
The CD inclusion 29 obtained as described above has the following properties.
(1) Contact with moisture Compared to a conventional clathrate compound, the CD clathrate 29 has less dissolution of the clathrate compound in water and detachment of the guest compound due to contact with water.
(2) Form The CD inclusion 29 has a cluster shape or a spherical shape under a microscope.
(3) Release of guest compound In the CD inclusion 29, the release amount of the guest compound increases as the humidity in the surrounding atmosphere increases (the release amount increases remarkably when the relative humidity exceeds about 70%). To do.)
The humidity dependency of the release amount of the guest compound shows the same tendency for the paper carrying the CD inclusion 29.
(4) Antibacterial property of paper carrying CD inclusion 29 If guest compound 13 is selected to have antibacterial properties (for example, hiba oil), the paper exhibits antibacterial properties.

(Paper manufacturing process)
The paper carrying (attaching) the CD inclusion 29 can be manufactured as follows.
By making a paper suspension using a pulp suspension to which the CD inclusion 29 is added, the CD inclusion 29 can be contained in the paper.
The suspension of the pulp used here can be the same as that conventionally used for the desired paper, and the CD inclusion 29 is added to the suspension so that the paper making process similar to the conventional one is performed. By doing so, a paper containing the CD inclusion 29 can be manufactured. That is, by adding the CD inclusion 29 to the pulp suspension, which is a conventional papermaking raw material, paper containing the CD inclusion 29 can be manufactured according to the same paper manufacturing process as before.
When the amount of the CD inclusion 29 added to the pulp suspension is too small, the CD inclusion 29 is not sufficiently contained in the paper. Conversely, when the amount is too large, the CD inclusion 29 that is not carried on the paper is made. This may be a cause of trouble in the production process (for example, the CD inclusion 29 adheres to the paper mesh and closes the mesh, etc.), and may be within a range satisfying both of these conditions, and is usually 30% to 70% ( (CD inclusion 29 mass) / (pulp suspension mass)).

Hereinafter, the present invention will be described in more detail with reference to examples. Also in the examples, the experimental operation will be described with reference to FIG.
(Preparation of CD water mixture 11)
Table 1 summarizes the experimental conditions of Examples 1 to 22 and Comparative Example 1. The experimental operation will be described with reference to Table 1 as well.
In each of Examples 1 to 22 and Comparative Example 1, while adding distilled water w9 (g) to a beaker and stirring (at room temperature), β-cyclodextrin (β-CD, manufactured by Cyclochem) m1 (g) was added. Slowly added, a CD water mixture 11 was prepared.

(Preparation of CD inclusion body water mixture 17)
In any of Examples 1 to 22 and Comparative Example 1, m2 (g) guest compound corresponding to the number of moles of Rm times the number of moles of CD contained in the CD water mixture 11 prepared as described above. 13 was mixed with the CD water mixture 11 and then stirred at room temperature for 1 day (24 hours) to prepare a CD inclusion body water mixture 17 (here, a CD inclusion body / amphiphilic polymer described later). The ratio of the total mass ((m1 + m2) (g)) of CD (m1 (g)) and guest compound 13 (m2 (g)) to the entire compound dispersion 21 is “CD in the total weight” in Table 1. As shown in the column “Concentration of total weight of guest compound”, Example 5 and Example 6 were 25% and 20%, respectively, while other Examples and Comparative Examples were both 40%.) . Here, as the guest compound 13, a trade name “d-limonene” (model number 20503-55) manufactured by Nacalai Tesque Co., Ltd. and a trade name “Aomori Hiba Essential Oil” (Aomori Hiba Oil) manufactured by Kiseitec Co., Ltd. were used.

(Preparation of amphiphilic polymer compound liquid 19)
In any of Examples 1 to 22, as the amphiphilic polymer compound liquid 19, the amphiphilic polymer compound w4 (g) was gradually added while adding distilled water w3 (g) to a beaker and stirring (at room temperature). In addition, an amphiphilic polymer liquid 19 was prepared. In Comparative Example 1, the amphiphilic polymer compound liquid 19 was not used.
Here, as an amphiphilic polymer compound, trade name “Bettersol” (component: ethylene / acrylic acid copolymer (ethylene unit ratio 80%), manufactured by Seishin Enterprise Co., Ltd., solid content: 20%. "Ethylene acrylic acid (ethylene about 80%)"), trade name "Sumikaflex 752" manufactured by Sumitomo Chemical Co., Ltd. (component: ethylene vinyl acetate copolymer (ethylene unit ratio 10%), solid content: 50%, indicated as “ethylene vinyl acetate (ethylene about 10%)” in Table 1.), trade name “Sumikaflex 755” manufactured by Sumitomo Chemical Co., Ltd. (component: ethylene vinyl acetate copolymer (ethylene unit ratio) 25%), solid content: 50%, indicated as “ethylene vinyl acetate (ethylene about 25%)” in Table 1.), trade name “Sumika Frette” manufactured by Sumitomo Chemical Co., Ltd. 408 "(component: ethylene vinyl acetate copolymer (ethylene unit ratio 40%), solid content: 50%. In Table 1, it is shown as" ethylene vinyl acetate (ethylene about 40%) ". The display of the amphiphilic polymer compound of Example 22 is shown as “ethylene acrylic acid”, which is the same as the above “ethylene acrylic acid (ethylene about 80%)”.

(Preparation of CD inclusion body / amphiphilic polymer compound dispersion 21)
In any of Examples 1 to 22, the amphiphilic polymer liquid 19 ((w3 + w4) (g)) was added to the CD clathrate water mixture 17 ((w9 + m1 + m2) (g)), and the mixture was stirred at room temperature for 30 minutes. (Mixing 20), CD inclusion body / amphiphilic polymer compound dispersion 21 was prepared. The amount w4 (g) of the amphiphilic polymer compound is a ratio of the mass m1 (g) of CD and the mass m2 (g) of guest compound 13 to the total mass (m3 (g) = m1 + m2) (g) (100 Xw4 / m3) is shown as “added amount” (%) in Table 1.
For Comparative Example 1, the CD clathrate / amphiphilic polymer was stirred for 30 minutes at room temperature without adding the amphiphilic polymer liquid 19 to the CD clathrate water mixture 17 (mixing 20). A liquid in place of the compound dispersion 21 was prepared.

(Preparation of emulsion 25)
In each of Examples 1 to 22 and Comparative Example 1, the CD inclusion body / amphiphilic polymer compound dispersion liquid 21 (Examples 1 to 22) or the CD inclusion body / amphiphilic polymer compound dispersion liquid 21 was used. The alternative liquid (Comparative Example 1) was subjected to a homogenizer (trade name “POLYTRON PT6100” manufactured by Kinematica Co., Ltd.) and homogenized for 3 minutes at 8000 revolutions / minute of the homogenizer to obtain an emulsion 25.

(Preparation of CD inclusion 29)
In each of Examples 1 to 22 and Comparative Example 1, each emulsion 25 was spray-dried (drying 27) using a spray dryer (model number L-8 type) manufactured by Okawara Chemical Industries Co., Ltd. Article 29 was prepared. The operating conditions of the spray dryer were an inlet temperature of 200 ° C., an outlet temperature of 150 ° C., an atomizer speed of 10,000 revolutions / minute, a raw material charging speed (emulsion feed speed) of 30 ml / minute, and an air flow rate of 110 kg / hour.

(Evaluation experiment of influence of moisture contact of CD inclusion 29)
Effects (specifically, on the water) when the CD inclusion 29 is used in a process including contact of the CD inclusion 29 with moisture (for example, wet papermaking process, fiber processing, etc.) Solubility and retention of guest compound 13) were evaluated. Using a wet papermaking process as a process involving moisture contact, the CD inclusion 29 was dispersed in water, and the weight change before and after the water dispersion and the retention of the guest compound were calculated. Here, the CD inclusions 29 of Examples 1 to 6 in Table 1 were used as the CD inclusions 29.

1.8 g of CD inclusion 29 was added to 300 ml of water, stirred at room temperature for 1 hour and dispersed in water to obtain a dispersion, and the weight change before and after that and the amount of guest compound retained were calculated. Further, assuming that the ratio of the CD inclusion 29 to the water was reduced, 1.8 g of the CD inclusion 29 was added to 1.5 L of water, and the mixture was dispersed in water by stirring at room temperature for 0.5 hour and 1 hour. The weight change before and after that and the retained amount of the guest compound were also calculated.
Specifically, the weight change before and after the water dispersion was obtained by filtering the dispersion by filtration under reduced pressure (filter paper was Kiriyama funnel filter paper No. 5C (φ60 mm)) and collecting the CD inclusions. The CD inclusion product was dried at 105 ° C. for 30 minutes, and the mass of the CD inclusion product obtained after drying was measured.

  The amount of the guest compound retained before and after the water dispersion is contained in both the 1.8 g CD inclusion sample 29 before the water dispersion and the CD inclusion sample collected after the water dispersion. The amount of limonene (guest compound 13) produced was evaluated by the following method. That is, 40 mL of distilled water and 10 mL of chloroform for extraction (including 1 μL / mL cyclohexanone) are added to 1 g of CD inclusion (for example, in the case of 1.8 g of CD inclusion, distilled water is added). 72 mL and 18 mL of extraction chloroform (containing 1 μL / mL cyclohexanone) were added.), And an extraction mixture was prepared. This extraction composition poured into the flask was subjected to hot water extraction in a constant temperature water bath at 80 ° C. for 30 minutes (however, it was stirred for about 10 seconds with a vortex mixer every 10 minutes). After extraction, the mixture was cooled at room temperature and then centrifuged at 3000 rpm for 10 minutes. From the extracted composition in which the oil layer and the aqueous layer were separated by centrifugation, 1 μL of the oil layer was separated using a 10 μL microsyringe, and injected into a gas chromatography (GC-14B, SHIMADZU) for measurement. Measurement was performed twice per sample, and the average was taken as the measured value. The amount of limonene was determined from the ratio of the peak area to the amount of limonene in the injected standard solution. The amount of limonene contained in the sample of filter residue (total amount) relative to the amount of limonene contained in 1.8 g of the CD inclusion 29 sample (mass: amount of limonene before water dispersion (g)) (mass: amount of limonene in water dispersion 30 minutes) The ratio (%) of (g), water-dispersed 60-minute limonene amount (g)) was defined as “limonene residual ratio” (%) ”.

In the wet papermaking process, when the CD inclusion 29 is made by paper and mixed, a stage of attaching the CD inclusion 29 to the pulp (hereinafter referred to as “previous stage”), and then the CD inclusion 29 There are two stages of paper making the attached pulp (hereinafter, “post-stage”), and in both stages, the CD inclusion 29 comes into contact with a large amount of water.
In the previous stage, the pulp is usually dispersed in water so that the pulp weight becomes 1%, and the CD inclusion 29 is expected to be added by 60% by weight with respect to the pulp weight. In the later stage, the pulp on which the CD inclusions 29 are fixed is made while being further diluted with water in the paper making stage. For this reason, the experiment in which 1.8 g of CD inclusion 29 was added to 300 ml of water approximated the state of the previous stage (hereinafter referred to as “previous stage approximation experiment”), and 1.8 g of CD inclusion 29 was added to 1.5 L of water. This experiment is considered to approximate the state of the later stage (hereinafter referred to as “the latter stage approximation experiment”).

(Results of an experiment for evaluating the influence of moisture contact on the CD inclusion 29)
(Preliminary approximation experiment)
Between the CD inclusion of Comparative Example 1 considered to be a conventional CD inclusion and the CD inclusion 29 of Examples 1 to 6, the previous stage approximation experiment showed great weight change and guest compound retention. No difference was observed. This is considered that the solubility (g / 100 ml) of various CD inclusion bodies in water at room temperature is about 0.1 g / 100 ml. The amount of water used in this preliminary approximate experiment is 300 ml, and if the solubility is about 0.1 g / 100 ml, the amount of dissolution is about 0.3 g / 300 ml. Since the addition amount of the CD clathrate is equal to or higher than the solubility, it is considered that no large difference was generated in this model.

(Post-stage approximation experiment)
Table 2 shows the experimental results (post-stage approximation experiment) regarding the weight change before and after water dispersion, and Table 3 shows the experimental results (post-stage approximation experiment) regarding the retention of the guest compound.

  According to Table 2, Comparative Example 1 has a weight retention of CD inclusions of 6.7% after water dispersion (water dispersion 60 minutes), while Examples 1 to 6 have a water retention ( The weight retention rate of the cyclodextrin clathrate with water dispersion (60 minutes) was 28 to 42%, and the retention rate was 4 to 6 times. From this, it was clarified that the CD inclusion 29 has decreased dissolution in water.

  According to Table 3, Comparative Example 1 has a limonene residual rate of about 12% after water dispersion (water dispersion 60 minutes), while Examples 1 to 6 have a water dispersion (water dispersion 60 minutes). The limonene residual rate was about 30 to 49%, which was about 2.5 to 4 times the retention rate. From this, it was clarified that in the CD inclusion product 29, the elimination of the guest compound in water is reduced. Further, even when ethylene acrylic acid is added in an amount of 12% or more, the limonene residual rate is almost constant, so that further addition of ethylene acrylic acid does not cause a further increase in the limonene residual rate.

(Form observation of CD inclusion 29)
The morphology of the CD inclusion 29 was observed with a scanning electron microscope. As a result, the form of the CD inclusion 29 was clustered in Examples 1, 7 to 9, 12, 13, and 17, and Examples 2 to 6, 10, 11, 14 to 16, and 18 to 21 were used. Sometimes it was spherical.
The CD inclusion 29 after being dispersed in water was also observed for morphology by a scanning electron microscope. The CD clathrate 29 after dispersion in water is obtained by adding 1.8 g of the CD clathrate 29 to 300 ml of water, stirring it at room temperature for 1 hour to disperse it in water, and then filtering the dispersion under reduced pressure (filter paper is The resulting product was filtered through Kiriyama funnel filter paper No. 5C (φ60 mm), and the CD inclusions were collected. The collected CD inclusions were dried at 105 ° C. for 30 minutes to obtain CD inclusions 29 after water dispersion for morphology observation. A scanning electron micrograph of the CD inclusion 29 after water dispersion is shown in FIG. The example numbers in FIG. 2 correspond to the example numbers in Table 1. In FIG. 2, the horizontal direction represents the type of amphiphilic polymer compound, and the vertical direction represents the amount of addition of the amphiphilic polymer compound (w4 / m3).

The form of the CD clathrate 29 after water dispersion is such that the higher the hydrophobicity of the amphiphilic polymer compound used (from the lower hydrophobicity, ethylene vinyl acetate (ethylene about 10%), ethylene vinyl acetate (ethylene about 25%), ethylene vinyl acetate (ethylene about 40%), ethylene acrylic acid (ethylene about 80%) in this order), and the shape before water dispersion is maintained.
As described above, whether the form of the original CD inclusion 29 is clustered or spherical is determined by the type of amphiphilic polymer compound used and the amount added (w4 / m3). For example, in the case of an ethylene acrylic acid copolymer (ethylene unit: acrylic acid = 8: 2), a spherical structure is formed by adding 3%, and the spherical shape can be maintained even after water dispersion by adding 6% or more. On the other hand, in the case of ethylene vinyl acetate copolymer, the lower the proportion of ethylene units, the higher the hydrophilicity and the higher the film-forming property, so that a spherical structure is formed even at a low concentration. However, after water dispersion, the one with a low ratio of ethylene units has high hydrophilicity and cannot maintain a spherical shape at a low concentration. In order to maintain the spherical shape after water dispersion, addition of 12% or more is necessary.

(Paper making experiment)
3 g of pulp (weight in terms of absolute dry weight) was added to 300 ml of water and stirred thoroughly.
Next, 50% (1.5 g) of the CD inclusion product 29 was added to the weight of the pulp and sufficiently stirred.
Then, cationic polyacrylamide (trade name “FIREX” (model number RC104) manufactured by Meisei Chemical Co., Ltd.) and anionic polyacrylamide (product name “FIREX” manufactured by Meisei Chemical Industry Co., Ltd.) (model number M) as fixing agents. )) Was added to each 1% (vs. pulp weight, that is, 0.03 g of each) and stirred sufficiently (this caused CD inclusions 29 to adhere to the pulp).
And after adding 0.03g (1% with respect to pulp weight) of polyethylene oxide papermaking adhesive (trade name “Alcox” (model number K2) manufactured by Meisei Chemical Industry Co., Ltd.), a square sheet machine (paper area) 25 × 25 cm), pressed with a press pressure of 0.5 MPa, and then dried with a rotary dryer at a dryer temperature of 105 ° C. for 2 minutes to obtain a CD inclusion-carrying paper.

(Experiment of guest compound release from CD inclusions)
An experiment was conducted on how the guest compound 13 is released from the CD inclusion 29.
In the release experiment, a sustained release rate measuring apparatus 101 whose conceptual diagram is shown in FIG. 3 was used. First, the sustained release rate measuring apparatus 101 will be described with reference to FIG. The sustained release rate measuring apparatus 101 generally includes a humidity control gas production unit 111 and a sustained release rate measurement unit 131.

  The humidity control gas production unit 111 includes a bypass unit 113 and a humidity application unit 118. The bypass part 113 includes a bypass pipe part 115 that circulates nitrogen gas (carrier gas) from a pressurized nitrogen gas source (not shown) (specifically, a pressurized nitrogen gas cylinder), and a nitrogen gas that circulates the bypass pipe part 115. And a bypass flow rate adjusting valve 117 for adjusting the flow rate of the nitrogen gas from the pressurized nitrogen gas source, the flow rate of which is adjusted by the bypass flow rate adjusting valve 117, introduced into the junction 127 described later at the same humidity. To do. The humidity applying unit 118 includes a humidity applying unit pipe 119 that allows the nitrogen gas from the pressurized nitrogen gas source to flow, and a humidity applying unit flow rate adjustment valve 121 that adjusts the flow rate of the nitrogen gas flowing through the humidity applying unit pipe 119. And bubbling bottle 123 for imparting moisture (saturated humidity at the water temperature in bubbling bottle 123) to nitrogen gas by bubbling nitrogen gas flowing through humidity applying section pipe portion 119 in water and bringing nitrogen gas and water into contact with each other , A constant temperature water tank 125 that holds the bubbling bottle 123 at a predetermined temperature (specifically, the constant temperature water tank 125 includes a water tank body 125a into which the water 125d for infiltrating the bubbling bottle 123 is injected, and water 125d in the water tank body 125a). The heater 125b that infiltrates and heats the water 125d and the heater 125b to the water 125d so that the temperature of the water 125d is maintained at a predetermined temperature. And bubbling to the nitrogen gas from the pressurized nitrogen gas source whose flow rate is adjusted by the humidity applying unit flow rate adjustment valve 121. The bottle 123 is humidified and introduced into a junction 127 described later. The nitrogen gas (dry) whose flow rate is adjusted by the bypass flow rate adjustment valve 117 of the bypass unit 113 and the nitrogen gas (humidification. Humidification. The bubbling bottle 123 in the bubbling bottle 123 is adjusted by the humidity application unit flow rate adjustment valve 121 of the humidity application unit 118. Saturated humidity at the water temperature) is mixed at the junction 127 of the bypass pipe 115 and the humidity applying pipe 119, and the mixed and conditioned nitrogen gas flows into the sustained release rate measuring section 131. Note that the humidity of the nitrogen gas flowing into the sustained release rate measuring unit 131 is adjusted by adjusting the bypass flow rate adjusting valve 117 and the humidity applying unit flow rate adjusting valve 121 (the larger the opening degree of the humidity applying unit flow rate adjusting valve 121 is, The humidity of the nitrogen gas flowing into the speed measuring unit 131 increases), and the temperature adjustment of the water 125d that the bubbling bottle 123 infiltrates (as the set temperature of the water 125d of the program temperature controller 125c increases, the sustained release rate measuring unit And the humidity of the nitrogen gas flowing into 131 increases).

  The sustained release rate measuring unit 131 is a steel tube coil for sufficiently warming the nitrogen gas containing humidity sent from the humidity control gas production unit 111 to the set temperature of the controlled release rate measuring unit 131 (set temperature of the air thermostat 143). 132 (a spiral internal flow path is formed, and nitrogen gas from the junction 127 flows through the internal flow path), and a discharge vessel 133 (specifically, nitrogen gas flowing out from the steel tube coil 132 flows in). In the gas sampled by the gas sampler 135, the gas sampler 135 for separating the gas flowing out from the discharge container 133), And a gas chromatograph analyzer 13 for measuring the concentration of limonene (guest compound 13) in the gas fractionated by the gas sampler 135 A sampler control device 141 for controlling the gas sampler 135 (specifically, an electromagnetic valve 141a for intermittently supplying compressed air, a timer 141b for intermittently connecting the electromagnetic valve 141a at a predetermined interval, and compressed air is supplied by the electromagnetic valve 141a. And an air actuator 141c for operating the gas sampler 135.), an air thermostat 143 (FIG. 5) for housing the steel tube coil 132, the discharge container 133, the gas sampler 135, and the hygrometer 137 at a constant temperature. 3, indicated by a dotted line).

In the release container 133, a sample 148 (CD inclusion 29) used for a release experiment is loaded at the bottom. Therefore, the conditioned nitrogen gas flows into the discharge container 133 where the sample 148 exists in the internal space, and flows out of the discharge container 133 with the components released from the sample 148 in the internal space. Nitrogen gas flowing out from the discharge container 133 is introduced into the gas chromatograph analyzer 139 by the gas sampler 135 at a predetermined interval while measuring the humidity by being usually introduced into the hygrometer 137 by the gas sampler 135. The concentration of limonene (guest compound 13) contained therein was measured.
Sample 148 was filled into a bottomed and uncovered aluminum container with an inner diameter of 9 mm and a depth of 1 mm (internal space in the shape of a right circular cylinder) while being vibrated, then ground with a spatula and the bottom of the discharge container 133 after weighing. Set. Therefore, the surface area A in the internal space of the discharge container 133 of the sample 148 is an apparent surface area of the upper surface of the sample when the sample (sample) is loaded into a hollow, straight cylindrical aluminum container with no bottom and a lid. Is 4.5 mm × 4.5 mm × 3.14.

Calculation of “sustained release rate F per unit mass and unit area” of guest compound 13 (limonene) from sample 148 was calculated by the following equation.
(Formula 1) N = v × Cg
(Formula 2) F = N / (A · m)
However, each character of Formula 1 and Formula 2 represents the following.
N: Slow release rate [g / s]
A: Surface area [cm ² ]
v: Nitrogen gas flow [mL / s]
m: Mass of CD inclusion [g]
Cg: Limonene concentration [g / mL]
F: Unit mass and sustained release rate per unit area [g / s? Cm ² ? G]
Among these, v is the total flow rate of the bypass flow rate adjusting valve 117 and the humidity applying unit flow rate adjusting valve 121, Cg is the limonene concentration analysis value in the gas chromatograph analyzer 139, and A is the apparent surface area of the sample. Specifically, it was 4.5 mm × 4.5 mm × 3.14, and m was the mass of the sample 148 set at the bottom of the discharge container 133.

In any experiment, the atmospheric humidity was changed while using both the adjustment of the bypass flow rate adjustment valve 117 and the humidity applying unit flow rate adjustment valve 121 and the temperature adjustment of the water 125d.
Here, as the CD inclusion 29, the experimental results using Examples 1 to 5, 7 to 21 and Comparative Example 1 in Table 1 are shown in FIGS.

FIG. 5 shows evaluation of changes in F (unit mass and sustained release rate per unit area) of the guest compound (here, limonene) with respect to the amphiphilic polymer compound used and the amount added (w4 / m3). . Examples of the amphiphilic polymer compound used include ethylene vinyl acetate (ethylene about 10%), ethylene vinyl acetate (ethylene about 25%), ethylene vinyl acetate (ethylene about 40%), and ethylene acrylic acid (ethylene about 80%). When four types are used and the addition amount of the amphiphilic polymer compound is 3% (Examples 1, 7, 12, and 17) in each amphiphilic polymer compound (plotted with ● in FIG. 5) When the addition amount of the amphiphilic polymer compound is 6% (Examples 2, 8, 13, and 18) (plotted by □ in FIG. 5), the addition amount of the amphiphilic polymer compound Is 9% (Examples 3, 9, 14, 19) (plotted with ♦ in FIG. 5), the addition amount of the amphiphilic polymer compound is 2% (Examples 4, 10, 15, 20) (plotted as Δ in FIG. 5) And it shows a case where the addition amount of the amphiphilic polymer compound 24% (Example 5,11,16,24) (in FIG. 5, and plotted in ○).
In FIG. 5, for each amphiphilic polymer compound, the horizontal axis represents the relative humidity (also referred to as relative humidity), the vertical axis represents F (unit mass and sustained release rate per unit area), and “Ramp "rate" indicates the rate of increase in relative humidity per minute, and here it is 0.375% per minute.

  FIG. 6 shows the temperature of the air thermostat 143 (that is, the temperature of the sample 148 in the internal space of the discharge vessel 133 and the nitrogen gas in contact therewith) for each of Comparative Example 1, Example 1, Example 2 and Example 18. It was changed and F (the sustained release rate per unit mass and unit area) was evaluated. Comparative Example 1 does not use an amphiphilic polymer compound, and Example 1 is an amphiphilic polymer compound in which ethylene acrylic acid (ethylene about 80%) is added (w4 / m3) = 3%. In Example 2, ethylene acrylic acid (ethylene about 80%) was added as an amphiphilic polymer compound (w4 / m3) = 6%, and Example 18 was an amphiphilic polymer compound. The amount of ethylene vinyl acetate (ethylene about 10%) added (w4 / m3) = 6%. And in Comparative Example 1, Example 1, Example 2 and Example 18, the temperature when the temperature of the air thermostat 143 is set to 60 ° C. is plotted with ●, and the value when the temperature is set to 50 ° C. is indicated as □. And plotted at ▲ for 40 ° C. In FIG. 6, for each of Comparative Example 1, Example 1, Example 2, and Example 18, the horizontal axis represents the relative humidity (also referred to as relative humidity), and the vertical axis represents F (gradient per unit mass and unit area). The above-mentioned “Ramp rate” was again 0.375% per minute.

From FIG. 5 and FIG. 6, the change of F (unit mass and sustained release rate per unit area) of the guest compound (here limonene) with respect to the amphiphilic polymer compound to be used and its added amount (w4 / m3) was evaluated. . When F (unit mass and sustained release rate per unit area) of a guest compound (here, limonene) from a CD clathrate using ethylene / acrylic acid and ethylene vinyl acetate with different amounts of ethylene groups was measured, There was a difference in quantity. In FIG. 6, when Example 18 and Comparative Example 1 are compared, F (sustained release rate per unit mass and unit area) of the CD inclusion product (Example 18) using ethylene vinyl acetate as the amphiphilic polymer compound. ) Was comparable to the conventional CD clathrate (Comparative Example 1), but when comparing Example 1 and Example 2 with Comparative Example 1, ethylene acrylic acid was used as the amphiphilic polymer compound. F (the sustained release rate per unit mass and unit area) of the CD inclusion (Example 1, Example 2) was 50% or less of the conventional CD inclusion (Comparative Example 1) ( F (compared value of F (sustained release rate per unit mass and unit area) at 90% relative humidity where F (unit mass and sustained release rate per unit area) increases rapidly).
Further, regarding FIG. 5, F (unit mass and sustained release rate per unit area) of CD inclusions using ethylene acrylic acid (ethylene about 80%) having high hydrophobicity is ethylene vinyl acetate having high hydrophilicity. F (unit mass and unit area) at a relative humidity of 90% in which the value of F is about 50% or less (for example, F (unit mass and sustained release rate per unit area) increases rapidly). Compare the value of the sustained release rate). And it became clear that the sustained release rates of the CD inclusions using the three types of ethylene vinyl acetate were almost the same, and the amount of ethylene in the ethylene vinyl acetate did not greatly affect.
Then, the CD inclusion 29 was obtained by using ethylene / acrylic acid or ethylene vinyl acetate as the amphiphilic polymer liquid 19 as in the conventional CD inclusion (Comparative Example 1) (FIGS. 5 and 6). The middle example) was found to release the guest compound (here limonene) at a relative humidity of 70-90%.

(Experiment on the effect of guest compound release due to humidity change from CD inclusion and CD inclusion-supporting paper)
Next, an experiment was conducted to determine how the release of the guest compound from the CD inclusion and the CD inclusion-carrying paper carrying the CD inclusion changes with changes in atmospheric humidity.
Example 1 in Table 1 was used as the CD inclusion 29 used and the CD inclusion 29 used for the production of the CD inclusion-supporting paper. Further, using the CD inclusion 29 of Example 1, a CD inclusion carrying paper was formed as in the paper making experiment described above.
In addition, the release test of the guest compound from the CD inclusion 29 of Example 1 used for the paper making of the CD inclusion-supporting paper is the same as the guest compound from the CD inclusion using the above-described sustained release rate measuring apparatus 101. The same release experiment was conducted.

  The release experiment of the guest compound from the CD clathrate-carrying paper was performed using a sustained release rate measuring apparatus 201 whose conceptual diagram is shown in FIG. With reference to FIG. 4, the sustained release rate measuring apparatus 201 will be described. The sustained release rate measuring apparatus 201 roughly includes a humidity control gas production unit 111 and a sustained release rate measurement unit 231. Since the humidity control gas production unit 111 of the sustained release rate measuring device 201 is the same as the humidity control gas production unit 111 of the sustained release rate measurement device 101, the description thereof is omitted here (the sustained release rate measurement device 101 is necessary if necessary). (Refer to the description of the humidity control gas production unit 111). The sustained release rate measuring unit 231 includes a steel tube coil 132 and a discharge container 233 into which nitrogen gas flowing out of the steel tube coil 132 flows (specifically, an airtight inner space having an inner diameter of 20 mm in inner diameter and 85 mm in height). Glass bottle), a gas sampler 135 for separating the gas flowing out from the discharge container 233, a hygrometer 137 for measuring the humidity in the gas separated by the gas sampler 135, and in the gas separated by the gas sampler 135 The gas chromatograph analyzer 139 for measuring the concentration of limonene (guest compound 13), the sampler controller 141 for controlling the gas sampler 135 (specifically, the electromagnetic valve 141a for intermittently compressing compressed air, and the electromagnetic valve 141a at predetermined intervals) Gas sampler when compressed air is supplied by the intermittent timer 141b and solenoid valve 141a An air actuator 141c for operating 135.), an air thermostat 143 (in FIG. 4) for accommodating the steel tube coil 132, the discharge container 233, the gas sampler 135, and the hygrometer 137 at a constant temperature. (Indicated by a dotted line). Since these steel pipe coil 132, gas sampler 135, hygrometer 137, gas chromatograph analyzer 139, sampler control device 141 and air thermostat 143 are the same as those of the sustained release rate measuring device 101, description thereof is omitted here. (Refer to the explanation of the sustained release rate measuring apparatus 101 as necessary. Note that the column temperature is different in the analysis conditions of the gas chromatograph analyzer 139).

  As described above, the discharge container 233 is formed of an airtight glass bottle. As shown in FIG. 4B, the inside of the discharge container 233 is configured to support a CD inclusion carrying paper. Specifically, as shown in FIG. 4B (A), a bottom member formed of a disk-shaped wire mesh, and a plurality of metal supports whose lower ends are fixed to the bottom member so as to rise upward. And a support including the rod (the whole is shown in (b) of FIG. 4B). Inner strip paper 2.5 cm wide × 16 cm long formed by CD inclusion-carrying paper, and outer strip paper 2.5 cm wide × 22 cm long formed by CD inclusion-carrying paper; These two strips were rolled and locked to the support rod of this support as shown in (b) of FIG. 4 (b) (supported by being rolled inside (b) of FIG. 4 (b)). It is the strip for the inside, and the strip for the outside is rounded to the outside.) A support supporting the two strips formed as shown in (b) of FIG. 4B was placed inside the discharge container 233 as shown in FIG. 4B.

For this reason, the conditioned nitrogen gas flows into the discharge container 233 in which the CD inclusion-carrying paper (inner strip paper, outer strip paper) exists in the internal space, like the sustained release rate measuring apparatus 101, It flows out of the discharge container 233 with the components released from the CD inclusion-carrying paper in the space. The nitrogen gas flowing out from the discharge container 233 is introduced into the gas chromatograph analyzer 139 by the gas sampler 135 at a predetermined interval while the humidity is measured by being usually introduced into the hygrometer 137 by the gas sampler 135. Then, the concentration of limonene (guest compound 13) contained therein was measured.
The calculation of F (unit mass and sustained release rate per unit area) of the guest compound 13 (limonene) from the CD inclusion-carrying paper was calculated by the following equation.
(Formula 3) N = v × Cg
(Formula 4) F = N / (A · m)
However, each character of Formula 3 and Formula 4 represents the following.
N: Slow release rate [g / s]
A: Surface area [cm ² ]
v: Nitrogen gas flow [mL / s]
m: Mass of CD inclusion-carrying paper [g]
Cg: Limonene concentration [g / mL]
F: Unit mass and sustained release rate per unit area [g / s? Cm ² ? G]
Among these, v is the total flow rate of the bypass flow rate adjustment valve 117 and the humidity applying unit flow rate adjustment valve 121, Cg is the limonene concentration analysis value in the gas chromatograph analyzer 139, and A is 190 cm ² (inner strip paper 80 cm ² (2.5 cm × 16 cm × 2) + external strip paper 110 cm ² (2.5 cm × 22 cm × 2)), and m is the mass of the CD inclusion-carrying paper set in the discharge container 233.
It should be noted that in both experiments for the CD inclusion and the CD inclusion carrying paper, the atmospheric humidity was adjusted while using both the adjustment of the bypass flow rate adjustment valve 117 and the humidity applying unit flow rate adjustment valve 121 and the temperature adjustment of the water 125d. Changed.

The results of the guest compound release experiment from the CD inclusion 29 in Example 1 are shown in FIG. 7, and the guest compound release experiment from the CD inclusion support paper is shown in FIG.
In both FIG. 7 and FIG. 8, the horizontal axis represents time (minutes), and the vertical axis represents F (sustained release rate per unit mass and unit area) and the relative humidity (in the figure, the plot of ▲ is The relative humidity is shown, and the plot of ■ indicates F (unit mass and sustained release rate per unit area).
In both the CD inclusion 29 (FIG. 7) and the CD inclusion carrying paper (FIG. 8), the release amount of the guest compound (here, limonene) can be increased by increasing or decreasing the relative humidity in the atmosphere. Increased or decreased repeatedly. From this, it became clear that both the CD inclusion 29 and the CD inclusion carrying paper repeatedly increased and decreased the release amount of the guest compound (here limonene) according to the increase and decrease of the relative humidity in the atmosphere. .

(Antibacterial activity experiment of CD inclusion paper)
The antibacterial property of the CD inclusion-carrying paper was evaluated by the film adhesion method (JIS-Z-2801). Specifically, an antibacterial experiment was conducted at the Japan Spinning Inspection Association, and the test bacteria was Staphylococcus aureus. In the film adhesion method (JIS-Z-2801), the antibacterial activity value was calculated from the control bacterial count [A] and the sample bacterial count [B]. become. The antibacterial activity value is obtained from log [A / B].
Example 1 and Example 22 in Table 1 were used as the CD inclusion 29 used for the production of the CD inclusion carrying paper.

The results are shown in Table 4.

CD inclusion containing limonene as guest compound 13 (Example 1) The antibacterial activity value of the supporting paper was 0.5, which was low, but the CD inclusion containing Aomori Hiba oil as guest compound 13 (Example 22) ) The antibacterial activity value of the supported paper was 4.6, which was confirmed to be high.
Therefore, if a compound having volatile antibacterial properties is used as the guest compound 13, even if the CD inclusion 29 is brought into contact with moisture in the paper making process, the paper produced and produced exhibits sufficient antibacterial properties. It became clear.

  As described above, the examples show inclusion compounds (CD inclusion bodies) in which a guest compound (here, d-limonene, Aomori Hiba essential oil) is included in cyclodextrin (here, β-cyclodextrin of m1 (g)). Contained in the water mixture 17) and an amphiphilic polymer compound (here, ethylene acrylic acid (ethylene about 80%), ethylene vinyl acetate (ethylene about 10%), ethylene vinyl acetate (ethylene about 25%), ethylene acetate Vinyl (ethylene 40%)) in contact with the aqueous phase (20 mixing steps) to form the first hydrous composition (herein, CD inclusion body / amphiphilic polymer compound dispersion 21). The first composition (here, CD inclusion body / amphiphilic polymer compound dispersion liquid 21) formed by the first step (here, 20 mixing steps) and the first step (here, mixing 20) is dehydrated. A cyclodextrin clathrate-containing composition (here, CD clathrate), comprising a second step (here, drying step 27) to obtain a solid containing the clathrate compound (here, CD clathrate 29) 29) the production method.

Here, the first step (here, the mixture 20) contains the clathrate compound water composition containing the clathrate compound and water (here, the CD clathrate water mixture 17) and the amphiphilic polymer compound. This is carried out by mixing an amphiphilic polymer compound water composition (here, amphiphilic polymer compound solution 19).
Further, here, the ratio (w4 / m3) of the mass w4 of the amphiphilic polymer compound to the total mass m3 of the cyclodextrin and the guest compound is shown as “added amount” (%) in Table 1. In Examples 1 to 5 and 7 to 22, it is 0.03 to 0.24.
Further, in all of the examples, an ethylene / acrylic acid copolymer or an ethylene vinyl acetate copolymer is used as the amphiphilic polymer compound.

Furthermore, in any of the examples, the second step (27 drying steps) is to dehydrate the first composition (CD inclusion body / amphiphilic polymer compound dispersion 21) by spray drying.
In any of the examples, the first composition (CD inclusion body / amphiphilic polymer compound dispersion 21) is homogenized 23 prior to the second step (drying 27 step).
As described above, the CD inclusion product 29 produced according to the examples is a cyclodextrin inclusion compound-containing composition that can be produced by the present method. The cyclodextrin clathrate-containing composition that can be produced by this method comprises a cyclodextrin clathrate in which a clathrate compound in which a guest compound is clathrated with a cyclodextrin is bound by an amphiphilic polymer compound as a binder component. It is a compound-containing composition.
The CD inclusion inclusion-carrying paper is a paper to which a cyclodextrin inclusion compound-containing composition that can be produced by this method is attached (carrying). Such a CD clathrate-carrying paper is produced by a paper production method using a pulp suspension to which a cyclodextrin inclusion compound-containing composition that can be produced by this method is added.

11 CD water mixture 13 Guest compound 15 Mixing 17 CD inclusion body water mixture 19 Amphiphilic polymer compound liquid 20 Mixing 21 CD inclusion body / Amphiphilic polymer compound dispersion liquid 23 Homogenization 25 Emulsion liquid 27 Drying 29 CD packing Attachment 101 Sustained release rate measuring device 111 Humidity control gas preparation part 113 Bypass part 115 Bypass pipe part 117 Bypass flow rate adjusting valve 118 Humidity giving part 119 Humidity giving part pipe part 121 Humidity giving part flow rate regulating valve 123 Bubbling bottle 125 Constant temperature water tank 125a Water tank body 125b Heater 125c Program temperature controller 125d Water 127 Junction point 131 Sustained release rate measurement unit 132 Steel tube coil 133 Release container 135 Gas sampler 137 Hygrometer 139 Gas chromatograph analyzer 141 Sampler controller 141a Solenoid valve 141b Mer 141c air actuator 143 air thermostatic chamber 148 sample 201 slow release rate measuring device 231 sustained speed measurement unit 233 release the container

Claims (10)

A first step of contacting a clathrate compound comprising a cyclodextrin with a guest compound and an amphiphilic polymer compound in an aqueous phase to form a hydrous first composition;
A second step of dehydrating the first composition formed by the first step to obtain a solid containing the clathrate compound;
A process for producing a cyclodextrin clathrate-containing composition comprising:     The first step is performed by mixing the clathrate compound water composition containing the clathrate compound and water and the amphiphilic polymer compound water composition containing the amphiphilic polymer compound. The manufacturing method of Claim 1 which is a thing.     The manufacturing method of Claim 1 or 2 whose ratio (w4 / m3) of the mass w4 of an amphiphilic polymer compound with respect to the total mass m3 of a cyclodextrin and a guest compound is 0.03-0.24.     The production method according to any one of claims 1 to 3, wherein the amphiphilic polymer compound is an ethylene / acrylic acid copolymer and / or an ethylene vinyl acetate copolymer.     The manufacturing method according to any one of claims 1 to 4, wherein the second step is dehydration by spray-drying the first composition.     The manufacturing method according to any one of claims 1 to 5, wherein the first composition is homogenized prior to the second step.     The cyclodextrin inclusion compound containing composition which can be manufactured with the manufacturing method of any one of Claims 1 thru | or 6.     Paper with the cyclodextrin inclusion compound-containing composition according to claim 7 attached thereto.     The method for producing paper according to claim 8, wherein a pulp suspension to which the cyclodextrin inclusion compound-containing composition according to claim 7 is added is used.     A cyclodextrin inclusion compound-containing composition in which an inclusion compound in which a guest compound is included in cyclodextrin is bound by an amphiphilic polymer compound as a binder component.