Composition containing siloxane bond-containing polymer compound having host group and / or guest group

Abstract

The present invention provides a composition which contains a host / guest siloxane polymer compound and in which the solubility of the host / guest siloxane polymer compound is improved. A composition according to the present invention contains: a liquefaction accelerator; and a combination of a host polymer compound including cyclodextrin as a host group and a guest polymer compound having a guest group, or a host-guest polymer compound including a guest group and cyclodextrin as a host group. The host-guest polymer compound, or at least one of the host polymer compound and the guest polymer compound includes a siloxane bond. The liquefaction accelerator is an alcohol having 3-5 carbon atoms, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, toluene, dichloromethane, chloroform, or a combination of the same.

Description

Composition containing a siloxane bond-containing polymer compound having a host group and / or a guest group

[0001] The present invention relates to a composition comprising a siloxane bond-containing polymer compound having a host group and / or a guest group.

[0002] Conventionally, it has been known that host polymer compounds having a host group and guest polymer compounds having a guest group, or host-guest polymer compounds having a host group and a guest group, can reversibly form bonds (host-guest interaction) depending on the combination of the host group and the guest group (International Publication No. 2012 / 036069).

[0003] Furthermore, resin materials and cosmetics containing polymer compounds having a host group and / or a guest group and containing a siloxane bond (hereinafter sometimes referred to as "host / guest siloxane polymer compounds") are known, and can form films via host-guest interactions (International Publication No. 2021 / 172463, International Publication No. 2021 / 172468).

[0004] International Publication No. 2012 / 036069, International Publication No. 2021 / 172463, Special Publication No. 2021 / 172468

[0005] Compositions containing host / guest siloxane polymer compounds tend to exhibit relatively high viscosity due to host-guest interactions. This can cause problems with handling and film formation.

[0006] It is possible to improve the film-forming properties of a composition by dissolving host / guest siloxane polymer compounds using solvents such as isododecane. However, heating is often required, and this method may not be suitable depending on the application.

[0007] The present invention aims to provide a composition containing a host / guest siloxane polymer compound in which the solubility of the host / guest siloxane polymer compound has been improved.

[0008] The present inventors have found that the above problems can be solved by the following means. <Aspect 1> A composition containing a combination of a host polymer compound having cyclodextrin as a host group and a guest polymer compound having a guest group, or a host-guest polymer compound having cyclodextrin as a host group and a guest group, and a liquefaction accelerator, wherein at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound contains a siloxane bond, and the liquefaction accelerator is an alcohol having 3 to 5 carbon atoms, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, toluene, dichloromethane, chloroform, or a combination thereof. <Aspect 2> The composition according to Aspect 1, wherein the mass ratio of the content of the liquefaction accelerator to the content of the combination of the host polymer compound and the guest polymer compound, or the mass ratio of the content of the liquefaction accelerator to the content of the host-guest polymer compound is 0.1 or more and 2.5 or less. <Aspect 3> The composition according to Aspect 1 or 2, wherein the liquefaction accelerator is 1-propanol, isopropanol, 1-butanol, acetone, tetrahydrofuran, toluene, chloroform, or a combination thereof. <Aspect 4> The composition according to any one of Aspects 1 to 3, further containing a solvent. <Aspect 5> The composition according to Aspect 4, wherein the solvent is dimethylpolysiloxane, isododecane, hexane, or a combination thereof. <Aspect 6> The composition according to Aspect 4 or 5, wherein the mass ratio of the content of the liquefaction accelerator to the content of the solvent is 0.1 or more and 1.0 or less. <Aspect 7> The composition according to any one of Aspects 1 to 6, wherein at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound contains a siloxane bond in the main chain. <Aspect 8> The composition according to any one of Aspects 1 to 7, wherein the guest group is an alkyl group having 5 to 16 carbon atoms. <Aspect 9> The composition according to any one of Aspects 1 to 8, wherein at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound is represented by the following formula 1: (In Formula 1, R ４ is independently a group selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and R ５ is independently an alkyl group having 5 to 16 carbon atoms, R ６ is independently a group having a cyclodextrin represented by the following Formula 2, and R ７ is independently a group selected from the groups described above with respect to R ４ or R ６ ; c is an integer of 100 to 600, d is an integer of 0 to 50, e is an integer of 0 to 50, and f is an integer of 0 to 20. However, at least one of d or e is 1 or more, c + d + e satisfies the range of 101 to 700, and the bonding order of the siloxane units enclosed by c, d, e, and f may be block or random.) (In Formula 2, L' is an alkylene group having 2 to 12 carbon atoms, and R １ is independently a group selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and R ２ is an alkylene group having 1 to 4 carbon atoms, and R ３ is independently a group selected from an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms; a is an integer of 0 to 8, b is an integer of 5 to 7, and x is 0 or 1. * is a free radical that binds to the silicon atom of the siloxane unit.) <Aspect 10> A composition according to any one of Aspects 1 to 9 for use as a cosmetic.

[0009] According to the present invention, a composition containing a host / guest siloxane polymer compound with improved solubility of the host / guest siloxane polymer compound can be provided.

[0010] Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be variously modified and implemented within the scope of the gist of the disclosure.

[0011] <<Composition>> The composition of the present invention contains a combination of a host polymer compound having cyclodextrin as a host group and a guest polymer compound having a guest group, or a host-guest polymer compound having cyclodextrin as a host group and a guest group, and a liquefaction accelerator. At least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, contains a siloxane bond. The liquefaction accelerator is an alcohol having 3 to 5 carbon atoms, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, toluene, dichloromethane, chloroform, or a combination thereof.

[0012] The inventors of this case believe that one of the reasons why it is difficult to dissolve host / guest siloxane polymer compounds in compositions containing them is due to host-guest interactions between the host / guest siloxane polymer compounds themselves. In other words, although this is not intended to be bound by any theory, when attempting to dissolve host / guest siloxane polymer compounds in a solvent, host-guest interactions cause crosslinking between the host / guest siloxane polymer compounds, resulting in low solubility.

[0013] In contrast, the inventors of this invention unexpectedly discovered that host / guest siloxane polymer compounds dissolve in certain liquefaction accelerators. While not intended to be bound by any theory, the reason for this is presumed to be as follows: The specific liquefaction accelerator acts on cyclodextrin as the host group, thereby inhibiting the host-guest interaction. For example, the liquefaction accelerator according to the present invention is thought to bind to cyclodextrin, the host group, in competition with the guest group, thereby weakening the host-guest interaction between the host and guest groups. The resulting composition is, in particular, liquid at room temperature.

[0014] According to the present invention, by selecting the type and / or amount of liquefaction accelerator to be added, and by further optionally adding a solvent, the viscosity of the host / guest siloxane polymer compound composition can be freely adjusted over a relatively wide range. Furthermore, for example, a composition having a relatively low viscosity due to the liquefaction accelerator can be spread relatively easily as a coating film, and a film can be formed by removing this liquefaction accelerator.

[0015] <Host / Guest Polymer Compounds> The compositions of the present invention contain a combination of a host polymer compound having cyclodextrin as a host group and a guest polymer compound having a guest group, or a host-guest polymer compound having cyclodextrin as a host group and a guest group (hereinafter sometimes referred to as "host / guest polymer compounds").

[0016] A "polymer compound" refers to a polymer composed of one or more monomer units, and more specifically, one that has a molecular weight distribution and a number-average molecular weight of 1 × 10⁻¹⁶ in terms of polystyrene. ３ (For example, 1 x 10) ３ ~1 x 10 ８ The polymer is a block copolymer, random copolymer, alternating copolymer, graft copolymer, or any other form.

[0017] The host / guest polymer compound may be a polymer consisting of a single monomer unit, or it may be a copolymer, block copolymer, or graft copolymer.

[0018] The content of the host / guest polymer compound in the composition is not particularly limited and can be appropriately set depending on the type and amount of the liquefaction accelerator described later.

[0019] The content of the host / guest polymer compound may vary depending on whether or not the composition further contains the solvent described later.

[0020] That is, for example, if the composition does not contain the solvent described later, the content of the host / guest polymer compound may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, with respect to the total mass of the composition, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0021] For example, if the composition contains a solvent as described later, the content of the host / guest polymer compound may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 8% by mass or more, or 10% by mass or more, relative to the total mass of the composition, and may be 50% by mass or less, 40% by mass or less, 30% by mass or less, or 25% by mass or less. In this case, the above content may be 5% to 40% by mass, 8% to 30% by mass, or 10% to 25% by mass.

[0022] <Host Group and Guest Group> "Host-guest interaction" refers to the bond formed between a host group and a guest group. A host group bonds to a guest group by encapsulating it. A host-guest interaction occurs when the size of the guest group is suitable for being incorporated into the internal space of the host group, and when the host group and the guest group have an interaction involving at least one of the following: hydrophobic interaction, hydrogen bonding, electrostatic interaction, and coordination bonding.

[0023] (Host group) The host group is a cyclodextrin (CD), specifically α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. When these groups are used as the host group, a stable host-guest interaction can be formed.

[0024] (Guest Group) The guest group is not particularly limited as long as it is a group that can be a guest group with respect to the corresponding host group. Examples of guest groups include alkyl groups and aryl groups. Also, examples of guest groups include trialkylsilyl groups (e.g., trimethylsilyl group, triethylsilyl group, and tripropylsilyl group, especially trimethylsilyl group). These guest groups may have substituents.

[0025] Examples of guest groups include C1-C18 alkyl groups, which are linear, branched, or cyclic. Preferably, the alkyl group has 3-C18 atoms, more preferably 5-C16 atoms, and these are preferably linear. Specifically, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl, heptyl, octyl, dodecyl, octadecyl, and adamantyl alkyl groups. These alkyl groups may have 1-3 substituents, such as halogen atoms (e.g., fluorine, chlorine, bromine), carboxyl groups, ester groups, amide groups, or protected hydroxyl groups. Alkyl groups may also have ferrocene, an organometallic complex, attached as a substituent.

[0026] Among the guest groups, examples of aryl groups include monocyclic or bicyclic or multicyclic aryl groups, preferably aryl groups having 6 to 18 carbon atoms, more preferably aryl groups having 6 to 12 carbon atoms, specifically including phenyl, toluyl, xylyl, naphthyl, anthuryl, phenanthuryl, etc. This aryl group may have 1 to 3 substituents such as alkyl groups (e.g., C1-18 alkyl groups), halogen atoms (e.g., fluorine, chlorine, bromine, etc.), carboxyl groups, ester groups, amide groups, azo groups having an aryl group, or protected hydroxyl groups.

[0027] (Combination of host group and guest group) In the present invention, with respect to the host group and guest group in the composition, the host group is α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin, and / or the guest group is (1) a linear alkyl group having 4 to 18 carbon atoms, (2) a linear alkyl group having hydroxyl group, (3) a linear alkyl group having 4 to 18 carbon atoms having carboxyl group, (4) a linear alkyl group having amino group, (5) a cyclic alkyl group, (6) a phenyl group, (7) an azobenzene group, (8) a cinnamic acid group, (1') a t-butyl group, (2') an adamantyl group, (3') an aryl group, (4') an aryl group having hydroxyl group, (5') an aryl group having carboxyl group, (6') an aryl group having amino group, (7') a ferrocele It may be at least one selected from the group consisting of a nyl group, an (8′) azobenzene group, and a (9′) dansyl group, (1′′) an alkyl group having up to 18 carbon atoms, (2′′) an alkyl group having up to 18 carbon atoms having a hydroxyl group, (3′′) an alkyl group having up to 18 carbon atoms having a carboxyl group, (4′′) an alkyl group having up to 18 carbon atoms having an amino group, (5′′) an adamantyl group, (6′′) a group having clusters composed of carbon atoms, (7′′) a dansyl group having an aryl group, (8′′) a ferrocenyl group, and (9′′) anthracenyl group.

[0028] The guest group is preferably an alkyl group having 5 to 16 carbon atoms, more preferably an alkyl group having 6 to 14 carbon atoms, and particularly preferably an alkyl group having 7 to 12 carbon atoms. These are preferably linear in shape.

[0029] (Host group / guest group content) The ratio of host groups to guest groups in the composition is not particularly limited. Preferably, the number of host groups in the composition is N. Ｈ and the number of guest groups N Ｇ Ratio (N Ｈ / N Ｇ ) may be 0.1 to 10, and may be 0.2 to 5, 0.3 to 3, or 0.4 to 2.5.

[0030] (Position of host group and guest group) In the present invention, the host polymer compound may have a host group in its side chain, and the guest polymer compound may have a guest group in its side chain.

[0031] In this invention, the host polymer compound may have a host group in its side chain, and the guest polymer compound may have a guest group at its terminal end.

[0032] In this invention, the host polymer compound may have a host group at its terminal end, and the guest polymer compound may have a guest group in its side chain.

[0033] <Siloxane bond> In the composition according to the present invention, at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, contains a siloxane bond.

[0034] In the siloxane bond according to the present invention, the silicon atom (Si) constituting the siloxane bond is preferably a hydrogen atom or R Ｓ It has a group represented by R. Ｓ R is an alkyl group, cycloalkyl group, alkenyl group, alkoxy group, cycloalkoxy group, hydroxy group, carboxy group, aldehyde group, aryl group, aryloxy group, or monovalent heterocyclic group, and these groups may have substituents. Ｓ If there are multiple instances, they may be identical or different. Ｓ This may be an alkyl group having 1 to 12 carbon atoms, or an aryl group which may have substituents. Ｓ The group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0035] At least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, may contain a siloxane bond in its main chain. The main chain may be, for example, a polyorganosiloxane main chain. When the polymer compound contained in the composition according to the present invention contains a polyorganosiloxane main chain, the chemical stability of the composition may be further improved, and it is also preferable because it exhibits better solubility in hydrocarbon oils and silicone oils, etc.

[0036] The polymer compound according to the present invention may have polyorganosiloxane units in its main chain or side chains. When the polymer compound according to the present invention contains polyorganosiloxane units, the proportion of polyorganosiloxane units may be 20% by mass or more, 30% by mass or more, or 40% by mass or more, and / or 100% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less, based on the total amount of the polymer compound. When the proportion of polyorganosiloxane units is within this range, the chemical stability and solubility of the polymer compound are further improved.

[0037] When the composition according to the present invention contains a host polymer compound and a guest polymer compound, preferably, both of these polymer compounds may contain siloxane bonds in their main chains, and in particular, both may have polyorganosiloxane main chains.

[0038] Examples of polymer compounds that form the host / guest polymer compound according to the present invention include polyorganosiloxanes. Other examples include block copolymers of polyorganosiloxane with vinyl resin, acrylic resin, urethane resin, epoxy resin, polyimide resin, polyester resin, or polycarbonate resin; and graft copolymers in which polyorganosiloxane is grafted onto vinyl resin, acrylic resin, urethane resin, epoxy resin, polyimide resin, polyester resin, or polycarbonate resin. Examples also include acrylic silicone resin, acrylic-silicone graft copolymer, copolymer of polynorbornene and silicone, copolymer of pullulan and silicone, etc. These resins and / or polyorganosiloxanes may have substituents other than the host group and / or guest group.

[0039] Examples of polyorganosiloxanes include methylpolysiloxane, phenylpolysiloxane, and methylphenylpolysiloxane. These polysiloxanes may have substituents other than the host group and / or guest group. The polymeric compound according to the present invention particularly preferably has a methylpolysiloxane skeleton.

[0040] <Host / Guest Siloxane Polymer Compounds> In the present invention, the host polymer compound or host-guest polymer compound is not particularly limited, but may be a cyclodextrin-modified organopolysiloxane which is an addition reaction product of the following components A and B: (A) an organohydrogenpolysiloxane having one or more hydrosilyl groups in one molecule (B) a cyclodextrin derivative having an unsaturated group represented by the following general formula 3 (In formula 3, L is an alkenyl group having 2 to 12 carbon atoms, R １ R is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. ２ R is an alkylene group having 1 to 4 carbon atoms. ３ (The group is independently selected from an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms, where a = an integer from 0 to 8, b = an integer from 5 to 7, and x is 0 or 1.)

[0041] Regarding the organohydrogenpolysiloxane as component A above, the kinematic viscosity at 25°C is 50 mm. ２ The viscosity may be greater than or equal to / s, and / or the number average molecular weight may be 8,000 or greater. The kinematic viscosity at 25°C can be measured according to Method 1 of the Viscosity Measurement Method for Quasi-Drug Raw Materials.

[0042] While there is no intention to limit the theory, it is thought that when the molecular weight of organohydrogenpolysiloxane is relatively large, the proportion of multiple host / guest polymer compounds in a single molecule increases, making it easier to form the composition into a film.

[0043] (Addition Reaction) The mode of the addition reaction of components A and B is not particularly limited and can be carried out by known methods. Specifically, for example, a cyclodextrin-modified organopolysiloxane can be produced by mixing components A and B, a catalyst, and an optional solvent, and reacting them by heating and / or stirring as optional. For example, platinum can be used as a catalyst for the addition reaction. In the addition reaction, the reaction proceeds via the hydrosilyl group of component A and the unsaturated group (e.g., vinyl group) of component B.

[0044] (Component A) Component A used in the formation of the above addition reaction product is an organohydrogenpolysiloxane having one or more hydrosilyl groups in one molecule. Specifically, examples include polyorganohydrogenmethylsiloxane.

[0045] (Component B) With respect to component B used in the formation of the above addition reaction product, in formula 3 above, L is an alkenyl group having 2 to 12 carbon atoms. Preferably, in formula 3 above, L is an alkenyl group having 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms, and more preferably CH ３ =CH ２ -CH ２ - or CH ３ =CH ２ - Most preferably CH ３ =CH ２ - is the case.

[0046] In formula 3, R １R is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. １ Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

[0047] In formula 3, R ２ R is an alkylene group having 1 to 4 carbon atoms. ２ Preferably, -(CH ２ ) ２ - or - (CH ２ ) ３ - and especially preferably - (CH ２ ) ３ - is the case.

[0048] In formula 3, R ３ R is a group selected from alkyl groups having 1 to 4 carbon atoms, or acyl groups having 1 to 4 carbon atoms. ３ Preferably, it is an acetyl group (Ac group).

[0049] In formula 3, a is an integer between 0 and 8. a is preferably 0 or 1, and particularly preferably 0.

[0050] In equation 3, b is an integer between 5 and 7. Preferably, b is 6.

[0051] In equation 3, x is either 0 or 1.

[0052] The cyclodextrin-modified organopolysiloxane may be an addition product of component A, component B, and (component C) an α-olefin having 2 to 16 carbon atoms.

[0053] An example of an α-olefin with 2 to 16 carbon atoms is 1-octene.

[0054] At least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, may be represented by the following formula 1: (In formula 1, R ４ R is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. ５R is an alkyl group having 5 to 16 carbon atoms, independently. ６ R is an independent group having a cyclodextrin represented by the following formula 2, ７ R is independent of R ４ or R ６ The group is selected from the aforementioned groups, where c = an integer from 100 to 600, d = an integer from 0 to 50, e = an integer from 0 to 50, and f = an integer from 0 to 20. However, at least one of d or e is 1 or greater, and c + d + e = 101 to 700. The bonding order of the siloxane units enclosed by c, d, e, and f may be in blocks or random. (In formula 2, L' is an alkylene group having 2 to 12 carbon atoms, R １ R is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. ２ R is an alkylene group having 1 to 4 carbon atoms. ３ * is independently selected from alkyl groups having 1 to 4 carbon atoms, or acyl groups having 1 to 4 carbon atoms, where a = an integer from 0 to 8, b = an integer from 5 to 7, and x is 0 or 1. * is a free radical that bonds to the silicon atom of the siloxane unit.

[0055] When d = 1 to 50 and e = 0, the compound represented by formula 1 is a guest polymer compound.

[0056] Such guest polymer compounds can be produced, for example, by adding a compound such as an alkene to an organopolysiloxane having a Si-H group. Alkenes having 5 to 16 carbon atoms are preferred. For example, a platinum catalyst can be used as the catalyst for the addition reaction.

[0057] When d = 0 and e = 1 to 50, the compound represented by formula 1 is a cyclodextrin-modified organopolysiloxane and a host polymer compound.

[0058] When d = 1 to 50 and e = 1 to 50, the compound represented by formula 1 is a cyclodextrin-modified organopolysiloxane and a host-guest polymer compound.

[0059] The specific method for producing such a host polymer compound or host-guest polymer compound is not particularly limited, but for example, a cyclodextrin-modified organopolysiloxane, which is an addition reaction product of components A and B, can be produced by the method described above.

[0060] In formula 1, R ４ The group is preferably selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. ４ The more preferably is an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

[0061] In formula 1, R ５ R is an alkyl group having 5 to 16 carbon atoms. ５ The alkyl group is preferably an alkyl group having 6 to 12 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms, and particularly preferably an alkyl group having 7 to 9 carbon atoms.

[0062] In formula 1, R ７ R ４ or R ６ R is a group selected from the groups mentioned above. ７ The group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0063] In formula 1, c is an integer between 100 and 600. Preferably, c is between 200 and 580, more preferably between 300 and 550, and particularly preferably between 400 and 500.

[0064] In Equation 1, d is an integer between 0 and 50. Preferably, d is between 1 and 50, more preferably between 1 and 20, and particularly preferably between 2 and 10.

[0065] In Equation 1, e is an integer between 0 and 50. Preferably, e is between 1 and 50, more preferably between 1 and 20, and particularly preferably between 2 and 10.

[0066] In Equation 1, f is an integer between 0 and 20. Preferably, f is between 0 and 10, more preferably between 0 and 5, and particularly preferably f = 0.

[0067] In formula 1, R６ This is independently a group having a cyclodextrin represented by formula 2 above.

[0068] In formula 2, L' is an alkylene group having 2 to 12 carbon atoms. Preferably, L' is an alkylene group having 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms, and most preferably -(CH ２ ) ３ - is the case.

[0069] In formula 2, R １ , R ２ , R ３ For the values ​​of a, b, and x and their preferred ranges, refer to the description of Formula 1 above.

[0070] In the above formula 2, R １ is a methyl group, R ３ R may be an acetyl group, and / or, in formula 2 above, ４ and R ７ All of these may be methyl groups.

[0071] With respect to the above-mentioned cyclodextrin-modified organopolysiloxane, the glass transition temperature (Tg) measured by dynamic viscoelasticity measurement may be 30 to 130°C or 40 to 100°C.

[0072] The composition may contain a host polymer compound and a guest polymer compound, and the host polymer compound may be the cyclodextrin-modified organopolysiloxane described above.

[0073] The composition may contain a host-guest polymer compound, which may be the cyclodextrin-modified organopolysiloxane described above.

[0074] <Polymers without siloxane bonds> In the present invention, either the host polymer compound or the guest polymer compound contained in the composition may not contain siloxane bonds. Examples of polymers without siloxane bonds (hereinafter also referred to as "non-siloxane polymer compounds") include polymers and copolymers of at least one monomer selected from vinyl compounds, acrylic compounds, olefins, styrene, acrylic acid esters, and methacrylic acid esters, as well as block copolymers containing these polymers and copolymers. Examples include vinyl resins, acrylic resins, urethane resins, epoxy resins, polyimide resins, polyester resins, or polycarbonate resins. These resins may have substituents other than host groups and / or guest groups. For polymer compounds that have guest groups and / or host groups and do not contain siloxane bonds, refer to the description in Patent Document 1.

[0075] Host polymer compounds that do not contain siloxane bonds (non-siloxane polymer compounds having a host group) can be produced by known methods, for example, by the method described in Patent Document 1.

[0076] Guest polymer compounds that do not contain siloxane bonds (non-siloxane polymer compounds having guest groups) can be produced by known methods, for example, by the method described in Patent Document 1.

[0077] <Combinations of polymer compounds contained in the composition> For example, the composition according to the present invention may have at least one of the following (i) to (iv): (i) a siloxane bond-free polymer compound having a host group and a siloxane bond-containing polymer compound having a guest group; (ii) a siloxane bond-containing polymer compound having a host group and a siloxane bond-free polymer compound having a guest group; (iii) a siloxane bond-containing polymer compound having a host group and a siloxane bond-containing polymer compound having a guest group; (iv) a siloxane bond-containing polymer compound having a host group and a guest group.

[0078] <Crosslinking> In this invention, at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, is crosslinked. The crosslinking may be by means other than host-guest interactions, for example, by covalent bonding (e.g., siloxane crosslinking).

[0079] Common reactions used for crosslinking main-chain silicones can be used. For example, hydrosilylation reactions, which involve the catalytic addition of hydrosilyl and vinyl groups, can be used. In addition, crosslinked products can also be synthesized using condensation reactions and other methods.

[0080] <Liquefaction Accelerator> The composition of the present invention contains a liquefaction accelerator. The liquefaction accelerator may be, for example, a compound that can suppress host-guest interactions by binding to a host group (cyclodextrin) in competition with a guest group.

[0081] Specifically, the liquefaction accelerator is an alcohol having 3 to 5 carbon atoms, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, toluene, dichloromethane, chloroform, or a combination thereof. In particular, the liquefaction accelerator may be 1-propanol, isopropanol, 1-butanol, acetone, tetrahydrofuran, toluene, chloroform, or a combination thereof.

[0082] The amount of liquefaction accelerator in the composition is not particularly limited and can be set appropriately depending on the type and amount of polymer compound, etc.

[0083] The mass ratio of the liquefaction accelerator content to the content of the host polymer compound and guest polymer compound combination, or the mass ratio of the liquefaction accelerator content to the content of the host-guest polymer compound, may be 0.1 or more and 2.5 or less. This mass ratio may be 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more, and may be 2.0 or less, 1.5 or less, or 1.0 or less.

[0084] The amount of liquefaction accelerator may vary depending on whether or not the composition further contains the solvent described later.

[0085] That is, for example, if the composition does not contain the solvent described later, the content of the liquefaction accelerator may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, and may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the total mass of the composition.

[0086] For example, if the composition contains a solvent as described later, the content of the liquefaction accelerator may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and may be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, based on the total mass of the composition. In this case, the above content may be 1 to 25% by mass, 3 to 20% by mass, or 5 to 15% by mass.

[0087] The SP value of the liquefaction accelerator is not particularly limited, but may be, for example, 8.0 or more and 12.0 or less.

[0088] The molecular weight of the liquefaction accelerator is not particularly limited, but may be, for example, 50 to 120.

[0089] The number of carbon atoms in the liquefaction accelerator is not particularly limited, but may be, for example, 3 to 7.

[0090] The polarity of the liquefaction accelerator is not particularly limited, but it can be relatively low, for example, lower than that of ethanol.

[0091] The liquefaction accelerator may be a volatile compound. With this configuration, a good film can be formed relatively easily. Specifically, a composition with relatively low viscosity can be uniformly and easily applied as a coating film to a substrate using the liquefaction accelerator, and the film can then be formed relatively easily by removing the volatile liquefaction accelerator by evaporation or other means.

[0092] <Solvent> The composition of the present invention may further contain a solvent. By further containing a solvent, it is possible to provide a composition that has particularly excellent coatability on a substrate.

[0093] The solvent is not particularly limited, but examples include water, alcohols, silicones, hydrocarbon compounds, ester compounds, ethers, and waxes.

[0094] Examples of alcohols include glycerin, butylene glycol (BG), propylene glycol (PG), dipropylene glycol (DPG), polyethylene glycol (PEG), ethanol, and oleyl alcohol.

[0095] Examples of silicones include dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylpolysiloxane, caprylyl methicone, methylpolysiloxane, methylphenylpolysiloxane, cyclopentasiloxane, aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer, aminopropyl dimethicone, methyl trimethicone, tris(trimethylsilyl)methylsilane, tetrakis(trimethylsilyl)silane, amodimethicone, and cyclomethicone. Among these, one or more selected from decamethylcyclopentasiloxane and dimethylpolysiloxane are more preferred, and dimethylpolysiloxane with a degree of polymerization of 10 or less is even more preferred.

[0096] Examples of hydrocarbon compounds include hydrogenated polyisobutene, petrolatum, mineral oil, squalane, paraffin, isoparaffin, alkyl benzoate, polyisobutene, isododecane, isotridecane, and isohexadecane light isoparaffin, with isododecane being preferred.

[0097] Examples of ester compounds include isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate, and octyldodecyl myristate.

[0098] Ethyl perfluorobutyl ether is an example of an ether.

[0099] The solvent is particularly preferably volatile. When the composition according to the present invention contains a volatile solvent, the solvent evaporates when the composition is applied to a substrate, causing the composition to form a film, thus making it relatively easy to form a resin sheet.

[0100] In addition to the alcohols mentioned above, volatile solvents include silicones such as dimethylpolysiloxane, methyl trimethicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tris(trimethylsilyl)methylsilane, and tetrakis(trimethylsilyl)silane; hydrocarbon compounds such as isododecane, isotridecane, isohexadecane, light isoparaffin, and hydrogenated polyisobutene; and ethers such as ethyl perfluorobutyl ether.

[0101] The solvent may be dimethylpolysiloxane, isododecane, hexane, or a combination thereof.

[0102] Conventionally, when using the solvents described above, it was necessary to treat the host / guest siloxane polymer compound at a high temperature (e.g., 90°C). In contrast, according to the present invention, since the composition contains a liquefaction accelerator, even when using the solvents described above, it is possible to obtain a composition that dissolves at a relatively low temperature (especially room temperature) and exhibits a liquid state.

[0103] The solvent content in the composition is not particularly limited and can be appropriately set depending on the type and amount of polymer compound and liquefaction accelerator.

[0104] The mass ratio of the liquefaction accelerator content to the solvent content may be 0.1 or more and 1.0 or less. This mass ratio may be 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, or 0.25 or less.

[0105] The solvent content may be 40% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, and may be 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on the total mass of the composition. The above content may be 50 to 90% by mass, 55 to 85% by mass, or 60 to 80% by mass.

[0106] <Other Additives> The composition according to the present invention, in particular, the composition for use as a cosmetic, may contain various components other than those described above, to the extent that it does not impair the effects of the present invention. For example, lower alcohols, higher alcohols, spherical powders, film-forming agents, cooling agents, oily components, surfactants, aqueous components, water-soluble polymers, ultraviolet absorbers, moisturizers, browning inhibitors, antioxidants, defoaming agents, cosmetic ingredients, preservatives, metal ion encapsulants, blood circulation promoters, various extracts, inorganic pigments, organic pigments, minerals, organic dyes and other colorants, pigments, thickeners, pH adjusters, cooling agents, antiperspirants, bactericides, skin activators, fragrances, etc., may be appropriately included to impart various effects. The content of these other additives (i.e., other components other than host / guest siloxane polymer compounds, liquefaction accelerators, and solvents) in the composition may be 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total mass of the composition.

[0107] Lower alcohols are widely used in cosmetics as texture modifiers and preservatives. Ethanol is an example of a lower alcohol.

[0108] Examples of spherical powders include spherical inorganic powders such as anhydrous silicic acid, spherical polymethyl methacrylate, spherical cellulose, spherical nylon, spherical polyethylene, and spherical silicone powder.

[0109] If a film-forming agent is additionally included, oil-based film-forming agents are examples. The oil-based film-forming agent is preferably soluble and dispersible in a non-polar volatile solvent; for example, silicone-based film-forming agents such as trimethylsiloxysilicate are examples.

[0110] Examples of cooling agents include menthol derivatives, camphor derivatives, and essential oils.

[0111] <Applications> The composition of the present invention may be used as a cosmetic. The composition of the present invention can be suitably used as a UV protection cosmetic, such as sunscreen lotion and sunscreen cream; and as a makeup cosmetic, such as a makeup base, foundation, concealer, blush, eyeshadow, mascara, eyeliner, eyebrow pencil, overcoat, and lipstick. The cosmetic may be the composition of the present invention itself, or it may contain the composition of the present invention.

[0112] When the composition according to the present invention is used as a cosmetic, it is believed that superior physical properties, such as improved makeup longevity, are obtained due to self-healing properties based on host-guest interactions. Although there is no intention to limit the theory, for example, when the composition according to the present invention is used for a cosmetic coating, it is believed that scratches (including microscopic scratches invisible to the naked eye) in the cosmetic coating are sealed by the reversible recombination of polymer compounds through host-guest interactions, resulting in further improvement of makeup longevity.

[0113] <<Method for Producing the Composition>> The composition according to the present invention can be produced by mixing a host / guest siloxane polymer compound, a liquefaction accelerator, and a solvent as desired.

[0114] In this invention, a liquid composition can be obtained at relatively low temperatures, particularly at room temperature, by dissolving a host / guest siloxane polymer compound in a liquefaction accelerator. Compositions that are liquid at room temperature are particularly preferred because they allow for relatively easy film formation.

[0115] Compositions that are liquid at room temperature can be easily obtained by using host / guest siloxane polymer compounds formed from polymer compounds that are liquid at room temperature. Examples of polymer compounds that are liquid at room temperature include polymer compounds having polyorganosiloxane as the main chain, particularly dimethylpolysiloxane.

[0116] The conditions for mixing the host / guest siloxane polymer compound, liquefaction accelerator, and optional solvent are not particularly limited. For example, the temperature, mixing time, and mixing method during mixing can be adjusted as appropriate.

[0117] <Resin Sheet> The composition can be molded into a film. The thickness of the composition when it is in film form is not particularly limited and can be set to an appropriate thickness depending on the application. For example, the composition can be adjusted from 1 nm to 1 cm, and can be adjusted from 1 μm to 100 μm in terms of good film-forming properties. When the composition is a cosmetic, it can be formed into a film and used as a cosmetic coating applied to the skin, etc.

[0118] The present invention also includes a method for manufacturing a resin sheet, which comprises applying a composition onto a substrate to form it into a sheet (forming step), and drying the composition formed into a sheet to form a resin sheet (forming step).

[0119] (Formation process) In the forming process, the composition is applied to a substrate and formed into a sheet (or film).

[0120] The substrate is not particularly limited. The substrate may be human skin.

[0121] The specific method for applying the composition onto a substrate to form a sheet is not particularly limited, and an appropriate method can be selected depending on the intended use of the composition. Specifically, for example, the composition can be dropped onto the substrate and spread with a coater or fingers to form a sheet.

[0122] The composition may be in the form of a paste or a liquid. By including a solvent, the composition may be made into a paste or a liquid, thereby improving its applicability.

[0123] (Formation Process) In the formation process, the composition formed into a sheet is dried to form a resin sheet. The drying method is not particularly limited and can be carried out by known methods.

[0124] (Decorative coating) Preferably, the resin sheet is a coating, particularly a decorative coating.

[0125] The method for forming a cosmetic composition into a cosmetic coating film is not particularly limited. For example, a cosmetic coating film can be formed by preparing a mixture of a polymer compound and a liquefaction accelerator and applying this mixture.

[0126] A method for forming a cosmetic coating film may include, for example, the following steps: applying the composition to an object (e.g., skin) with a finger and allowing it to dry to form a cosmetic coating film.

[0127] <<Examples and Comparative Examples>> <Example 1> (Synthesis of Cyclodextrin Derivatives) 50.0 g of mono-6-O-(p-toluenesulfonyl)-β-cyclodextrin (C6-Ts-β-CD) and 500.0 g of allylamine were charged into four flasks equipped with a stirrer, thermometer, reflux condenser, and dropping funnel. After purging the flasks with nitrogen, the mixture was stirred at 53°C for 7 hours, cooled to room temperature, and stirred overnight. The mixture was concentrated using an evaporator, and 1,000 mL of acetonitrile was added to the resulting solid. The precipitate was collected by filtration. 1,000 mL of distilled water was added to the obtained precipitate to dissolve it, and the solution was added dropwise to 1,000 mL of acetonitrile. The precipitate was collected by filtration. After washing the precipitate with acetone, it was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound A (white solid, 42.7 g).

[0128]

[0129] Four flasks, each equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, were charged with 30.0 g of vinyl-modified compound A, 110.0 g of acetic anhydride, and 170.0 g of pyridine. After purging the flasks with nitrogen, the mixture was stirred at 60°C for 7 hours, cooled to room temperature, and stirred overnight. 170 mL of toluene was added to the solution in the flasks, and the mixture was washed twice with 170 mL of 1 mM hydrochloric acid and once with 170 mL of saturated saline solution. The resulting solution was separated and concentrated using an evaporator. The recovered solid was then dissolved in 50 mL of acetone, and the solution was added dropwise to 500 mL of distilled water. The precipitate was collected by filtration. The precipitate was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound B (white solid, 31.8 g).

[0130]

[0131] (Synthesis of host-guest polymer compounds) Four flasks equipped with a stirrer, thermometer, reflux condenser, and dropping funnel were mixed with 100.0 g of polyorganohydrogensiloxane represented by the following formula (4) (hydrosilyl group content: 0.040 mol, kinematic viscosity at 25°C: 3,340 mmHg) ２ 24.9 g of the aforementioned vinyl-modified compound B (vinyl group amount: 0.012 mol), and 200.0 g of toluene were charged. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.3 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 4 hours. １ The progress of the reaction was confirmed by the disappearance of the vinyl group peak (5.6–6.1 ppm) by 1H-NMR. Subsequently, 6.4 g (0.057 mol) of 1-octene and 0.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature and toluene was removed under reduced pressure using an evaporator. 250 g of methanol was added to the resulting solid, and the process of washing the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain a host-guest polymer compound E (light brown solid, 119.7 g) in which the host group is cyclodextrin, the guest group is an octyl group, and the main chain contains a siloxane bond.

[0132]

[0133] A composition was prepared containing 50% by mass of the obtained polymer compound E and 50% by mass of isopropanol as a liquefaction accelerator. Specifically, the composition according to Example 1 was prepared by mixing at room temperature.

[0134] (Evaluation of Solubility) The solubility of the polymer compound in the liquefaction accelerator was evaluated based on the following criteria: A: All components dissolved B: Components partially dissolved C: Components did not dissolve at all.

[0135] The results are shown in Table 1 below.

[0136] <Examples 2-6 and Comparative Examples 1-7> Compositions were prepared and evaluated in the same manner as in Example 1, except that the type of liquefaction accelerator or the corresponding comparative compound was changed as shown in Table 1. The results are shown in Table 1. In the tables below, "polymer compound" refers to "host-guest polymer compound".

[0137]

[0138] As shown in Table 1, the compositions of the examples containing a host-guest polymer compound and a liquefaction accelerator exhibited good solubility of the host-guest polymer compound. In contrast, the compositions of the comparative examples containing a comparative compound of the liquefaction accelerator exhibited inferior solubility of the host-guest polymer compound compared to the examples.

[0139] <Examples 7 and 8> Compositions were prepared and evaluated in the same manner as in Example 1, except that the content of each component was changed as shown in Table 2. The results are shown in Table 2. For reference, the results of Example 6 are also included in Table 2.

[0140]

[0141] As shown in Table 2, even when the mass ratio of isopropanol content as a liquefaction accelerator to the host-guest polymer compound content was approximately 0.1, i.e., even when the composition contained an excess amount of the host-guest polymer compound, the solubility of the polymer compound was good.

[0142] <Examples 9 and 10, and Comparative Examples 8 and 9> Compositions were prepared and evaluated in the same manner as in Example 1, except that isododecane (manufactured by Maruzen Petrochemical Co., Ltd., product name: Marcazole R) was added as a solvent, and the content of each component was changed as shown in Table 3. The results are shown in Table 3.

[0143]

[0144] As shown in Table 3, the compositions of the examples exhibited good solubility of the host-guest polymer compound, even when containing a solvent.

Claims

1. A composition comprising a combination of a host polymer compound having cyclodextrin as a host group and a guest polymer compound having a guest group, or a host-guest polymer compound having cyclodextrin as a host group and a guest group, and a liquefaction accelerator, wherein at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, contains a siloxane bond, and the liquefaction accelerator is an alcohol having 3 to 5 carbon atoms, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, toluene, dichloromethane, chloroform, or a combination thereof.

2. The composition according to claim 1, wherein the mass ratio of the content of the liquefaction accelerator to the content of the combination of the host polymer compound and the guest polymer compound, or the mass ratio of the content of the liquefaction accelerator to the content of the host-guest polymer compound, is 0.1 or more and 2.5 or less.

3. The composition according to claim 1 or 2, wherein the liquefaction accelerator is 1-propanol, isopropanol, 1-butanol, acetone, tetrahydrofuran, toluene, chloroform, or a combination thereof.

4. The composition according to any one of claims 1 to 3, further comprising a solvent.

5. The composition according to claim 4, wherein the solvent is dimethylpolysiloxane, isododecane, hexane, or a combination thereof.

6. The composition according to claim 4 or 5, wherein the mass ratio of the content of the liquefaction accelerator to the content of the solvent is 0.1 or more and 1.0 or less.

7. The composition according to any one of claims 1 to 6, wherein at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, contains a siloxane bond in its main chain.

8. The composition according to any one of claims 1 to 7, wherein the guest group is an alkyl group having 5 to 16 carbon atoms.

9. The composition according to any one of claims 1 to 8, wherein at least one of the host polymer compound and the guest polymer compound, or the host-guest polymer compound, is represented by the following formula 1: (In formula 1, R ３ , １ , ２ , , ６ are independently groups selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and R ５ are independently an alkyl group having 5 to 16 carbon atoms, R ６ are independently groups having a cyclodextrin represented by the following formula 2, and R ７ are independently R ４ or R ６ are groups selected from the groups described above, c is an integer of 100 to 600, d is an integer of 0 to 50, e is an integer of 0 to 50, and f is an integer of 0 to 20. However, at least one of d or e is 1 or more, c + d + e satisfies the range of 101 to 700, and the bonding order of the siloxane units enclosed by c, d, e, and f may be block or random.) (In formula 2, L' is an alkylene group having 2 to 12 carbon atoms, and R １ are independently groups selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and R ２ is an alkylene group having 1 to 4 carbon atoms, and R ３ are independently groups selected from an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, a is an integer of 0 to 8, b is an integer of 5 to 7, and x is 0 or 1. * is a free radical bonded to the silicon atom of the siloxane unit.) 10. A composition according to any one of claims 1 to 9, for use as a cosmetic.

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