JP2009120759A - Polyrotaxane compound, composition containing the same, and manufacturing method of gelatinous material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel polyrotaxane compound which is easy to deal with and can be controllably gelatinized by an external stimulation such as light and heat, and a composition containing the same. <P>SOLUTION: The compound has a structure of a cyclic molecule (A) pierced with a straight chain molecule (B) having substituent groups at the both ends, characterized in that the cyclic molecule (A) has a polymerizable group. The composition includes the compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel polyrotaxane compound and a composition useful for preparing various gel materials using the same. The present invention also relates to a method for producing a gel material.

Various polyrotaxanes and their uses have been proposed.
For example, a compound having a so-called crosslinked polyrotaxane containing two polyrotaxanes and in which cyclic molecules contained in each of them are crosslinked is proposed (Patent Document 1). In the Example of patent document 1, it was confirmed that it gelatinized by progress of the crosslinking reaction.
Further, (A) a linear molecule penetrates through openings of at least two cyclic molecules, the cyclic molecule has a reactive group, and a blocking group is present at both ends of the linear molecule. There has been proposed a pressure-sensitive adhesive composition comprising a polyrotaxane, and (B) a pressure-sensitive adhesive polymer having two or more functional groups capable of reacting with the reactive group (Patent Document 2).
WO01 / 083566 JP 2007-224133 A

Since the polyrotaxane material disclosed in Patent Document 1 is a gel-like material that already has a cross-linked structure, it is difficult to dissolve in a desired solvent when used to produce various functional materials, and improvement in handling properties is desired.
Moreover, since the composition disclosed in Patent Document 2 has high reactivity, there is a problem that gelation proceeds during storage, and similarly, improvement in handleability is desired.

The present invention was made for the purpose of improving the convenience of handling polyrotaxane materials, is easy to handle, and can freely control gelation by polymerization by external stimuli such as light and heat. It is an object of the present invention to provide a novel polyrotaxane compound and a composition that can be used.
Moreover, this invention makes it a subject to provide the manufacturing method of a novel gel-like material.

（式中、Ｒ⁵¹¹、Ｒ⁵¹²、Ｒ⁵¹³、Ｒ⁵²¹、Ｒ⁵²²、Ｒ⁵²³、Ｒ⁵³¹、Ｒ⁵³²、Ｒ⁵³³、Ｒ⁵⁴¹、Ｒ⁵⁴²、Ｒ⁵⁴³、Ｒ⁵⁴⁴、及びＲ⁵⁴⁵はそれぞれ、水素原子又は置換もしくは無置換のアルキル基を表し；ｎは０又は１を表す。） Means for solving the above problems are as follows.
[1] A compound having a structure in which a linear molecule (B) having substituents at both ends penetrates a cyclic molecule (A), wherein the cyclic molecule (A) has a polymerizable group. A compound.
[2] The compound according to [1], wherein the polymerizable group is a polymerizable group that undergoes polymerization by donating heat or light.
[3] The compound according to [1] or [2], wherein the polymerizable group is a polymerizable group capable of an addition polymerization reaction or a condensation polymerization reaction.
[4] The compound according to any one of [1] to [3], wherein the polymerizable group is a polymerizable group represented by any one of the following general formulas P1 to P4.

Wherein R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ , and R ⁵⁴⁵ are each hydrogen Represents an atom or a substituted or unsubstituted alkyl group; n represents 0 or 1)

[5] The molecules of [1] to [4], wherein the cyclic molecule (A) is a molecule of a cyclodextrin derivative in which all or part of the hydrogen atoms of the hydroxyl group are substituted with the polymerizable group. Any compound.
[6] In the cyclic molecule (A), all or part of the hydrogen atoms of the hydroxyl group are substituted with the polymerizable group, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a silyloxy group. The compound according to any one of [1] to [4], wherein the compound is a molecule of a cyclodextrin derivative.
[7] The cyclic molecule (A) is a molecule of a cyclodextrin derivative in which all or part of the hydrogen atoms of the hydroxyl group are substituted with the polymerizable group and an acyl group having 1 to 20 carbon atoms. Any one of [1] to [4].
[8] The compound according to any one of [5] to [7], wherein a substitution degree of a hydrogen atom of a hydroxyl group in the cyclodextrin derivative is 5 to 95%.
[9] A composition comprising at least one of the compounds according to any one of [1] to [8].
[10] The composition of [9], comprising at least one solvent and capable of being applied.
[11] A method for producing a gel-like material, comprising a polymerization step in which light and / or heat is supplied to the compound of any one of [1] to [8] to polymerize.

According to the present invention, a novel polyrotaxane material can be handled with ease of handling, easy to handle, and gelation by polymerization can be freely controlled by external stimuli such as light and heat. Polyrotaxane compounds and compositions can be provided.
Moreover, according to this invention, the method which can manufacture the various gel-like material which shows the physical property different from the conventional bridge | crosslinking polyrotaxane can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The present invention relates to a compound having a structure in which a linear molecule (B) having substituents at both ends penetrates the cyclic molecule (A), wherein the cyclic molecule (A) has a polymerizable group. Relates to the characterized compound. The compound of the present invention is a so-called “polyrotaxane” compound having a molecular skeleton composed of a cyclic molecule (A) and a linear molecule (B) penetrating the cavity. The compound of the present invention is characterized in that the cyclic molecule (A) has a polymerizable group. When the polymerization reaction of the polymerizable group proceeds, a crosslinked structure is formed between the cyclic molecules (A) and / or within the cyclic molecules (A), and the compound becomes a gel. Since the compound of the present invention does not contain a crosslinked structure before polymerization, it is soluble in various solvents and has excellent handleability. Further, since the polymerization reaction of the compound of the present invention proceeds only by an external stimulus such as light and heat, there is no problem of unexpected gelation during storage and use, and in that respect, it is excellent in handling property. ing.

・ Cyclic molecule (A)
In the compound of the present invention, the cyclic molecule (A) can include the linear molecule (B) and penetrates the linear molecule (B). If it can move above, it will not be limited in particular. In the present specification, “cyclic” of “cyclic molecule” means substantially “cyclic”. In other words, the cyclic molecule may not be completely closed as long as it can move on the linear molecule, and may have a helical structure, for example.

  The cyclic molecule (A) may be a molecule of any kind of compound as long as the above conditions are satisfied. Examples include cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyetheramines, cyclic polyamines; cyclodextrins such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin; The cyclic molecule (A) may be a mixture of two or more kinds of compounds.

  In the present invention, the cyclic molecule (A) has a polymerizable group. The polymerizable group may be directly bonded to the atoms constituting the ring skeleton of the cyclic molecule, or may be bonded to the atoms constituting the ring skeleton via one or more atoms. . Among the above-exemplified cyclic compounds, cyclodextrins have a plurality of hydroxyl groups in the molecule, so that hydrogen atoms in the hydroxyl groups can be easily substituted with polymerizable groups by various methods. Of course, after the hydrogen atom in the hydroxyl group is substituted with a substituent other than the polymerizable group, such as an acyl group or an alkyl group, the hydrogen atom in these substituents may be substituted with the polymerizable group. For example, the polymerizable group may be bonded to a substituent of an atom constituting the ring skeleton, such as an alkoxy group, an alkoxycarbonyl group, or an alkoxycarbonyloxy group. In this embodiment, a divalent linking group having 1 or more atoms exists between the atoms constituting the ring skeleton and the polymerizable group. Examples of the linking group include an alkyleneoxy group (for example, an alkyleneoxy group such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, and a substituted alkyleneoxy group containing an ether bond such as ethyleneoxyethoxy). Group), alkyleneoxycarbonyloxy group (eg, alkyleneoxycarbonyloxy group such as ethyleneoxycarbonyloxy, propyleneoxycarbonyloxy, butyleneoxycarbonyloxy, pentyleneoxycarbonyloxy, hexyleneoxycarbonyloxy, heptyleneoxycarbonyloxy, etc.) And substituted alkyleneoxycarbonyloxy groups containing an ether bond such as ethyleneoxyethoxycarbonyloxy), alkyleneoxycarbonyl groups For example, an ethyleneoxycarbonyl group, a propyleneoxycarbonyl group, a butyleneoxycarbonyl group, a pentyleneoxycarbonyl group, a hexyleneoxycarbonyl group, an alkyleneoxycarbonyl group such as a heptyleneoxycarbonyl group, or an ether such as an ethyleneoxyethoxycarbonyl group Substituted alkyleneoxycarbonyl group containing a bond) and the like. However, as described above, the polymerizable group may be directly bonded to the atoms constituting the ring skeleton.

The polymerizable group is preferably a group capable of an addition polymerization reaction or a condensation polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.
Preferable examples of the polymerizable group include polymerizable groups represented by the following P1, P2, P3, and P4.

In the formula, R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ , and R ⁵⁴⁵ are each a hydrogen atom Or a substituted or unsubstituted alkyl group; n represents 0 or 1;

R ⁵¹¹ and R ⁵¹³ in the polymerizable group P1 each represents a hydrogen atom or a substituted or unsubstituted alkyl group. The substituents R ⁵¹¹ and R ⁵¹³ are each independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl). Preferably a hydrogen atom or a lower alkyl group such as methyl and ethyl; more preferably a hydrogen atom or methyl. Among them, it is preferable that R ⁵¹¹ is a methyl group and R ⁵¹³ is a hydrogen atom, or both R ⁵¹¹ and R ⁵¹³ are hydrogen atoms.

R ⁵¹² in the polymerizable group P1 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl). , Nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxyethyl); preferably a hydrogen atom or a lower alkyl group such as substituted or unsubstituted methyl and ethyl; a hydrogen atom or substituted or unsubstituted methyl Is more preferable. Among these, a hydrogen atom or an unsubstituted lower alkyl group is preferable, and a hydrogen atom is most preferable.

  That is, the polymerizable group P1 is preferably a vinyl group (n = 0) or a vinyloxy group having a high polymerization activity.

The polymerizable group P2 is a substituted or unsubstituted oxirane group.
The substituents R ⁵²¹ and R ⁵²² in the polymerizable group P2 are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Pentyl, hexyl, heptyl, octyl, nonyl) are preferred; a hydrogen atom or a lower alkyl group such as substituted or unsubstituted methyl and ethyl is more preferred; a hydrogen atom or substituted or unsubstituted methyl is more preferred. Most preferably, both R ⁵²¹ and R ⁵²² are hydrogen atoms.

The substituent R ⁵²³ in the polymerizable group P2 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, Heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxyethyl) are preferred; a hydrogen atom or a substituted or unsubstituted lower alkyl group such as methyl, ethyl, n-propyl is more preferred; a hydrogen atom, Or, a substituted or unsubstituted lower alkyl group such as methyl, ethyl or n-propyl is more preferred; a hydrogen atom or a lower alkyl group such as unsubstituted methyl, ethyl or n-propyl is more preferred.

The polymerizable group P3 is a substituted or unsubstituted acryloyloxy group.
The substituents R ⁵³¹ and R ⁵³³ in the polymerizable group P3 are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Pentyl, hexyl, heptyl, octyl, nonyl) are preferred; a hydrogen atom or a lower alkyl group such as substituted or unsubstituted methyl and ethyl is more preferred; a hydrogen atom or substituted or unsubstituted methyl is more preferred. Among them, it is preferable that R ⁵³¹ is a methyl group and R ⁵³³ is a hydrogen atom, or both R ⁵³¹ and R ⁵³³ are hydrogen atoms.

The substituent R ⁵³² is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2- Chloroethyl, 3-methoxyethyl, methoxyethoxyethyl) are preferable; a hydrogen atom or a lower alkyl group such as substituted or unsubstituted methyl and ethyl is more preferable; a hydrogen atom or substituted or unsubstituted methyl is more preferable. Among these, a hydrogen atom or an unsubstituted lower alkyl group is preferable, and a hydrogen atom is most preferable.

  That is, the polymerizable group P3 is preferably an unsubstituted acryloxy group, methacryloxy group, or crotonyloxy group having high polymerization activity.

The polymerizable group P4 is a substituted or unsubstituted oxetane group.
In the polymerizable group P4, each of the substituents R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, Isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl); preferably a hydrogen atom, or a lower alkyl group such as substituted or unsubstituted methyl and ethyl; a hydrogen atom, or substituted or unsubstituted methyl Is more preferable. Among them, it is preferable that R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ are all hydrogen atoms.

In the polymerizable group P4, the substituent ^R541 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl). Octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxyethyl); preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group such as methyl, ethyl, n-propyl; a hydrogen atom, or A substituted or unsubstituted lower alkyl group such as methyl, ethyl or n-propyl is more preferred; a hydrogen atom or a lower alkyl group such as unsubstituted methyl, ethyl or n-propyl is still more preferred.

The cyclic molecule (A) may have a non-polymerizable substituent. Examples of the substituent include the following substituents.
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert- Butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl) Group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. , Bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), alke Group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it is a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed, for example, a 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group (substituted or substituted). An unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), alkynyl group ( Preferably, it is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as an ethynyl group or a propargyl group, an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as a phenyl group, p-tolyl group, naphthyl group), a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group), a cyano group. , A nitro group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an n-octyl group). Tiloxy group, 2-methoxyethoxy group), aryloxy group (preferably substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group) , 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocyclic oxy Group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, carbon A substituted or unsubstituted alkylcarbonyloxy group of 2 to 30 carbon atoms 6-30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octyl An aminocarbonyloxy group, an Nn-octylcarbamoyloxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, ter -Butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy group, p-methoxy Phenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms) A substituted or unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Aminocal Bonylamino groups such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Substituted alkoxycarbonylamino groups such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably Is a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxypheno. Cicarbonylamino group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms) For example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably, carbon number) 1-30 substituted or unsubstituted alkylthio Group such as methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group) Group), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group ( Preferably, the substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N- Acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′phenylcarbamoyl) Sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl group, Ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms) Sulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, carbon number 7-30 substituted or unsubstituted a A reelcarbonyl group such as an acetyl group or a pivaloylbenzoyl group, an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as a phenoxycarbonyl group, o-chlorophenoxy Carbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group , Tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as carbamoyl group, N-methylcarbamoyl group, N, N- Dimethyl Rubamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, carbon number 3 to 30 substituted or unsubstituted heterocyclic azo groups such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N -Succinimide group, N-phthalimide group), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl A group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group; Dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy group) , Dioctyloxyphosphinyloxy group), phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino group, dimethylaminophosphinyl group) An amino group) and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as a trimethylsilyl group, a tert-butyldimethylsilyl group, or a phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  Non-polymerizable substituents that the cyclic molecule (A) has are alkyl group, alkenyl group, alkynyl group, silyloxy group, acyloxy group, acylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkyl and arylsulfonyl Group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group and silyl group are preferred; alkyl group, alkenyl group, silyloxy group, acyloxy group, alkyl and arylsulfonyl group, acyl group, alkoxycarbonyl group, And more preferably selected from alkyl groups, alkenyl groups, silyloxy groups, acyloxy groups, acyl groups, and alkoxycarbonyl groups.

  The cyclic molecule (A) may have a plurality of types of substituents, and at least one of them may be a polymerizable group. Examples of combinations of plural kinds of substituents that the cyclic molecule (A) has include acyl groups / polymerizable groups having 1 to 20 carbon atoms, alkyl groups / polymerizable groups having 1 to 20 carbon atoms, and silyloxy groups / polymerization. Combinations such as sex groups can be mentioned. The two substituents may be present on the same cyclic molecule, or may be present on the same polyrotaxane molecule, but may be present on non-identical cyclic molecules.

The number of substituents contained in one molecule of the cyclic molecule (A) varies depending on how many sites into which substituents can be introduced in one molecule. For example, when the cyclic molecule (A) is an α-cyclodextrin derivative, the α-cyclodextrin has 18 hydroxyl groups in one molecule into which a substituent can be introduced. When an average of 9 substituents is introduced in one molecule, the degree of substitution is 50%. In the cyclic molecule (A), the degree of substitution of the polymerizable group (and the total when there are other substituents) is preferably 5 to 95%, and more preferably 5 to 90%. More preferred. The degree of substitution can be calculated from ¹ H-NMR measurement data.

  The degree of substitution and the kind of the polymerizable group and the non-polymerizable substituent introduced as required are selected in consideration of the handleability of the compound or composition of the present invention. For example, in applications that require solubility in a solvent, the type of substituent and the degree of substitution are determined within a range that does not impair the solubility of the compound in the solvent.

・ Linear molecule (B)
The linear molecule (B) is a molecule or substance that is included in the cyclic molecule (A) and can be integrated by a mechanical bond rather than a chemical bond such as a covalent bond. If it is, it will not be specifically limited. In the present specification, “linear” of “linear molecule” means substantially “linear”. That is, as long as the cyclic molecule (A) can move on the linear molecule (B), the linear molecule (B) may have a branched chain or may have a substituent. . Examples of the substituent that may be included are the same as those of the substituent that the cyclic molecule (A) has.

  Examples of the linear molecule (B) include polyethers (eg, polyethylene glycol, polypropylene glycol, polytetrahydrofuran), polyolefins (eg, polyethylene, polypropylene, etc.), celluloses (eg, carboxymethyl cellulose, hydroxypropyl cellulose, etc.) And so on. Two or more kinds of these linear molecules (B) may be mixed. Polyethers are preferred.

  The preferred molecular weight of the linear molecule (B) is a number average molecular weight of 1,000 to 1,000,000, and more preferably 5,000 to 100,000.

  The linear molecule (B) has substituents at both ends. The substituents at both terminals are terminal capping groups introduced for the purpose of preventing inclusion of the cyclic molecule (A) from the linear molecule (B). If it is a substituent which achieves this object, the type, shape and the like are not particularly limited. Preferably, the substituent is bulky and / or ionic. The bulky substituent prevents the cyclic molecule (A) from detaching due to its bulkiness, and is selected according to the size of the opening of the cyclic molecule (A). The ionic substituent is selected according to the electronic state of the opening of the cyclic molecule (A), preventing the cyclic molecule (A) from leaving by electrostatic action.

Preferable examples of the end-capping substituent include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, anthracenes and the like. In addition, a polymer main chain or side chain having a number average molecular weight of 1,000 to 1,000,000 can also be used for end-capping. Examples of the polymer having a number average molecular weight of 1,000 to 1,000,000 include polyamide, polyimide, polyurethane, polydimethylsiloxane, and polyacrylic acid ester.
These sealing substituents may be a mixture of two different types in one molecule of the linear molecule (B), or may be different between the molecules of the linear molecule (B). Good.
Moreover, a cyclic molecule (A) can also be utilized as the substituent for the end capping. The cyclic molecule used for end-capping may be a cyclic molecule that includes the linear molecule or a cyclic molecule that includes another linear molecule.

  Various methods can be used for the method of substituting both ends of the linear molecule (B) with a substituent. For example, the method described in WO01 / 83566 can be used.

In the compound of the present invention, the number of cyclic molecules (A) penetrating through one molecule of the linear molecule (B) is not particularly limited. It is preferable that two or more cyclic molecules (A) are penetrated by one molecule of the linear molecule (B). Since there is a limit to the cyclic molecule (A) through which one molecule of the linear molecule (B) can penetrate, the number of cyclic molecules (A) that inevitably penetrate one molecule of the linear molecule (B) is The maximum number will be below. In the compound of the present invention, the number of cyclic molecules (A) penetrating through one molecule of the linear molecule (B) may be any of 1 to the maximum number. It is preferable to adjust the number to a desired range depending on the application. The number of cyclic molecules (A) penetrated by one molecule of the linear molecule (B) depends on the mixing ratio of the cyclic molecule (A) and the linear molecule (B), and / or the mixing conditions (time, temperature, Pressure etc.).
The number of cyclic molecules (A) penetrating through one molecule of the linear molecule (B) can be calculated from ¹ H-NMR measurement data.

Synthesis examples of the compounds of the present invention are described below.
For the compound of the present invention, with reference to synthesis examples of polyrotaxanes described in various documents, and introduction of substituents such as polymerizable groups into the cyclic molecule (A), reaction examples of various organic compounds It can be synthesized with reference. A general synthesis scheme is shown below.

  When a linear compound and a cyclic compound are mixed (1) and kept at a constant temperature (or heated or cooled as required), one or more cyclic molecules are in a state of inclusion of the linear molecule (2). In this state, a bulky substituent or the like is introduced into the end of the linear molecule, so that the cyclic molecule does not leave the linear molecule (3). Next, the reactive site of the cyclic molecule is reacted with a reagent to introduce a substituent (4). If this substituent is a polymerizable group, the compound of the present invention can be obtained up to this step. When synthesizing a compound in which the cyclic molecule (A) has two or more kinds of substituents, the remaining reactive active site in the cyclic molecule is reacted with a reagent to introduce another substituent (5 ) To obtain a compound of the invention. The polymerizable group may be introduced in any of the steps (4) and (5). However, in order to avoid unexpected polymerization, a non-polymerizable substituent was introduced in (4). Thereafter, it is preferable to introduce a polymerizable group in the step (5).

  As the linear compound used in the step (1), a compound in which both ends are modified with reactive groups in advance is used in order to introduce a terminal-capping substituent at both ends in the step (3). preferable. For example, when the linear compound is selected from polyethers, it is preferable to use bisaminopolyethylene glycol having both ends modified with amino groups. In addition, the mixing in the step (1) is generally performed in a dissolved state. For example, both the linear compound and the cyclic compound are dissolved and mixed in water. Heating may be performed for dissolution, or cooling may be performed for precipitation after the state (2) has been reached.

  The introduction of substituents in the steps (3) to (5) can be carried out with reference to reaction examples of various organic compounds as described above. For example, when dextrins are used as the cyclic compound, since dextrins have a plurality of hydroxyl groups in one molecule, it is preferable to introduce substituents using these as reaction sites. For example, in the step (4), after substituting a part of the hydrogen atom of the hydroxyl group in the dextrin molecule with an acetyl group by a conventional method, in the step (5), using a reagent such as acrylic acid chloride, Examples include a method of substituting a hydrogen atom of the remaining hydroxyl group of the dextrin molecule (in this case, a part of the acetyl group introduced in the step (4) may be substituted) with a (meth) acryloyl group. It is done.

  The compound of the present invention can be used alone for the production of various gel materials. When an external stimulus such as light or heat is applied to the compound of the present invention, polymerization of the polymerizable group proceeds, and a cross-link is formed within the cyclic molecule (A) and / or between the cyclic molecules (A). This causes the compound to gel. A gel-like material having desired physical properties can be obtained by adjusting the degree of gelation by varying the energy of the external stimulus to be provided. In addition, the gel having the desired physical properties can be obtained by adjusting the substitution degree and distribution of the polymerizable group, that is, adjusting the density and distribution of the cross-linking points, instead of or in addition to variously changing the energy of the external stimulus to be provided. A shaped material is obtained.

External stimuli for proceeding the polymerization of the polymerizable group of the cyclic molecule (A) include light irradiation and / or donation of heat. Light irradiation is easy to control. For light irradiation, ultraviolet rays are preferably used. There is no particular restriction on the irradiation energy, in general, is preferably from 10mJ~50J / cm ^2, further preferably 50mJ~800mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. In addition, since the oxygen concentration in the atmosphere at the time of the polymerization is related to the degree of polymerization, if the polymerization does not proceed in the air or does not reach the desired degree of polymerization, the oxygen concentration is reduced by a method such as nitrogen substitution. It is preferable to reduce. A preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and still more preferably 3% or less.

The invention also relates to compositions containing the compounds of the invention. The composition of the present invention may contain additives for promoting polymerization such as a polymerization initiator and a sensitizer, and other polymerization components such as a polymerizable monomer.
-Polymerization initiator The composition of this invention may contain the polymerization initiator. The polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator may be preferable depending on the application. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).
The addition amount of the polymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the composition.

-Polymerizable monomer A polymerizable monomer may be added to the composition of the present invention. The polymerizable monomer to be used is not particularly limited. For example, a compound having a polymerization active ethylenically unsaturated group such as a vinyl group, a vinyloxy group, an acryloyl group and a methacryloyl group is preferably used. Moreover, a polyfunctional polymerizable monomer having two or more polymerizable groups can also be used.
The addition amount of the polymerizable monomer is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content of the composition.

  In addition, when a photofunctional compound, for example, a compound exhibiting ultraviolet, visible light absorption characteristics, high refractive index, and fluorescence / phosphorescence characteristics, is used as the polymerizable monomer, the light possessed by the photofunctional compound Functional sites can be incorporated into the crosslinked structure. Moreover, a liquid crystalline compound can also be used as a polymerizable monomer. By incorporating the residue of such a compound into the cross-linked portion of polyrotaxane, it is expected that these compounds exhibit physical properties that were not exhibited in a single molecule state.

  The composition of the present invention may be prepared as a coating solution in which the compound of the present invention and optionally added additives are dissolved in a solvent. When prepared as a coating solution, it can be applied to the surface with various thicknesses to form a coating film, and then gelled by an external stimulus. Any solvent can be used for the preparation as long as the compound of the present invention is soluble. For example, ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents (eg, ethyl acetate, butyl acetate, etc.), amide solvents (N, N-dimethylacetamide, N-methylpyrrolidone, etc.), dimethyl sulfate, etc. A foxide, an alcohol solvent (such as methyl alcohol or ethyl alcohol), a halogen-based solvent (such as dichloromethane or chloroform), or a mixed solvent thereof can be used.

  The compounds and compositions of the present invention are useful for the production of various gel materials. Gel-like materials have various uses because of their high water absorption, high elasticity, high viscoelasticity, high viscosity and the like. For example, there are various uses such as medical materials such as contact lenses, adhesives, buffers, water-absorbing materials and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example]
(Synthesis Example 1)
<Preparation of end-capped polyrotaxane>
4.5 g of polyethylene glycol bisamine having a number average molecular weight of 20,000 and 18.0 g of α-cyclodextrin were added to 150 mL of water and dissolved by heating to 80 ° C. The solution was cooled and allowed to stand at 5 ° C. for 16 hours. The produced white paste-like precipitate was collected and dried.
The mixture was added to a mixed solution of 12.0 g of 2,4-dinitrofluorobenzene and 50 g of dimethylformamide and stirred at room temperature for 5 hours. The reaction mixture was dissolved by adding 200 mL of dimethyl sulfoxide (DMSO), and then poured into 3750 mL of water to separate a precipitate. The precipitate was redissolved in 250 mL of DMSO and then poured again into 3500 mL of 0.1% saline to separate the precipitate. The precipitate was washed with water and methanol three times each, and then vacuum-dried at 50 ° C. for 12 hours, whereby polyethylene glycol bisamine was included in α-cyclodextrin in a skewered manner, and both terminal amino groups had 2 Thus, 2.0 g of an inclusion compound to which a 4-dinitrophenyl group was bonded was obtained.

The obtained blocked polyrotaxane was subjected to ultraviolet light absorption measurement and ¹ H-NMR measurement, and the inclusion amount of α-cyclodextrin was calculated. As a result, the inclusion amount per molecule of polyethylene glycol bisamine was 72. .

<Acetyl modification of α-cyclodextrin>
1 g of the end-capped polyrotaxane synthesized above was dissolved in 50 g of a lithium chloride / N, N-dimethylacetamide 8% solution. Thereto were added 6.7 g of acetic anhydride, 5.2 g of pyridine, and 100 mg of N, N-dimethylaminopyridine, and the mixture was stirred overnight at room temperature. The reaction solution was poured into methanol, and the precipitated solid was separated by centrifugation. The separated solid was dried and then dissolved in acetone. The solution was poured into water, and the precipitated solid was separated by centrifugation and dried to obtain 1.2 g of an acetyl-modified polyrotaxane.
The obtained acetyl-modified polyrotaxane was subjected to ¹ H-NMR measurement, and the amount of acetyl introduced was calculated. The amount introduced (substitution degree) was 75%.

<Introduction of polymerizable group>
1 g of the acetyl-modified polyrotaxane synthesized above was dissolved in 50 g of an 8% solution of lithium chloride / N, N-dimethylacetamide. Thereto were added 5.9 g of acrylic acid chloride, 5.2 g of pyridine, and 100 mg of N, N-dimethylaminopyridine, and the mixture was stirred at room temperature overnight. The reaction solution was poured into methanol, and the precipitated solid was separated by centrifugation. The separated solid was dried and then dissolved in acetone. The solution was poured into water, and the precipitated solid was separated by centrifugation and dried to obtain 0.8 g of acryloyl and acetyl-modified polyrotaxane.
The obtained acryloyl and acetyl-modified polyrotaxane were subjected to 1H-NMR measurement to calculate the introduction amount of acryloyl and acetyl. The introduction amount (substitution degree) was 87%.

(Synthesis Example 2)
<Acetyl modification of α-cyclodextrin>
1 g of the end-capped polyrotaxane synthesized in Example 1 was dissolved in 50 g of a lithium chloride / N, N-dimethylacetamide 8% solution. Thereto were added 6.7 g of acetic anhydride, 5.2 g of pyridine, and 100 mg of N, N-dimethylaminopyridine, and the mixture was stirred at room temperature for 3 nights. The reaction solution was poured into methanol, and the precipitated solid was separated by centrifugation. The separated solid was dried and then dissolved in acetone. The solution was poured into water, and the precipitated solid was separated by centrifugation and dried to obtain 1.1 g of acetyl-modified polyrotaxane.

The obtained acetyl-modified polyrotaxane was subjected to ¹ H-NMR measurement, and the amount of acetyl introduced was calculated. The amount introduced was 88%.

<Introduction of polymerizable group>
1 g of the acetyl-modified polyrotaxane synthesized above was dissolved in 50 g of an 8% solution of lithium chloride / N, N-dimethylacetamide. Thereto were added 5.9 g of acrylic acid chloride, 5.2 g of pyridine, and 100 mg of N, N-dimethylaminopyridine, and the mixture was stirred at room temperature overnight. The reaction solution was poured into methanol, and the precipitated solid was separated by centrifugation. The separated solid was dried and then dissolved in acetone. The solution was poured into water, and the precipitated solid was separated by centrifugation and dried to obtain 0.6 g of acryloyl and acetyl-modified polyrotaxane.

  The obtained acryloyl and acetyl-modified polyrotaxane were subjected to 1H-NMR measurement, and the amount of acryloyl and acetyl introduced was calculated. The amount introduced (substitution degree) was 90%.

(Gelification example 1)
A solution prepared by dissolving the compound synthesized in Synthesis Example 1 and Irgacure 907 (3 parts by weight) in N-methylpyrrolidone was spread on a glass substrate with a pipette. When the liquid surface was irradiated with ultraviolet rays of 600 mJ, it changed from a liquid state to a gel state.

(Gelification example 2)
A solution prepared by dissolving the compound synthesized in Synthesis Example 1 and Irgacure 907 (3 parts by weight) in N-methylpyrrolidone was spread on a glass substrate with a pipette. When a mask was applied to the liquid surface and irradiated with 600 mJ of ultraviolet light from the upper part of the mask, the part that was not masked irradiated with ultraviolet light changed to a gel, and the part that was masked and not irradiated with ultraviolet light remained liquid. It did not change.

(Gelification example 3)
A solution prepared by dissolving the compound synthesized in Synthesis Example 1, the following discotic compound (X), and Irgacure 907 (3 parts by weight) in N-methylpyrrolidone was poured onto a glass substrate with a pipette and spread. When the liquid surface was irradiated with ultraviolet rays of 600 mJ, it changed from a liquid state to a gel state.

Claims (11)

A compound having a structure in which a linear molecule (B) having substituents at both ends penetrates a cyclic molecule (A), wherein the cyclic molecule (A) has a polymerizable group . The compound according to claim 1, wherein the polymerizable group is a polymerizable group that undergoes polymerization by heat or light donation. The compound according to claim 1 or 2, wherein the polymerizable group is a polymerizable group capable of an addition polymerization reaction or a condensation polymerization reaction. The compound according to any one of claims 1 to 3, wherein the polymerizable group is a polymerizable group represented by any one of the following general formulas P1 to P4.

Wherein R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ , and R ⁵⁴⁵ are each hydrogen Represents an atom or a substituted or unsubstituted alkyl group; n represents 0 or 1) The cyclic molecule (A) is a molecule of a cyclodextrin derivative in which all or part of the hydrogen atoms of the hydroxyl group are substituted with the polymerizable group. The described compound. In the cyclic molecule (A), all or part of the hydrogen atoms of the hydroxyl group are substituted with the polymerizable group, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a silyloxy group. The compound according to any one of claims 1 to 4, which is a molecule of a cyclodextrin derivative. The cyclic molecule (A) is a molecule of a cyclodextrin derivative in which all or part of the hydrogen atoms of the hydroxyl group are substituted with the polymerizable group and an acyl group having 1 to 20 carbon atoms. The compound according to any one of claims 1 to 4. The compound according to any one of claims 5 to 7, wherein a substitution degree of a hydrogen atom of a hydroxyl group in the cyclodextrin derivative is 5 to 95%. A composition comprising at least one of the compounds according to claim 1. The composition according to claim 9, comprising at least one solvent and capable of being applied. The manufacturing method of the gel-like material characterized by including the superposition | polymerization process which supplies light and / or heat to the compound of any one of Claims 1-8, and polymerizes.