JPWO2011105532A1 - Photocrosslinkable polyrotaxane, composition having the photocrosslinkable polyrotaxane, crosslinked product derived from the composition, and methods for producing the same - Google Patents

Abstract

The present invention provides a photocrosslinkable polyrotaxane having scratch resistance, low hysteresis loss and the like, a composition having the photocrosslinkable polyrotaxane, a crosslinked product from these compositions, and a method for producing them. The present invention relates to a polyrotaxane cyclic molecule in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of the pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule. MY (M is represented by the following formula II, X represents a linear alkylene group having 1 to 8 carbon atoms, n is an average value of 1 to 10, and Y has a photopolymerizable group. A photocrosslinkable polyrotaxane having a group represented by formula (1), a composition having the photocrosslinkable polyrotaxane, a crosslinked product derived from the composition, and a method for producing them. [Chemical 1]

Description

  The present invention relates to a photocrosslinkable polyrotaxane in which the cyclic molecule constituting the polyrotaxane has a photocrosslinkable group, a composition consisting essentially of the photocrosslinkable polyrotaxane, a composition having the photocrosslinkable polyrotaxane, and compositions thereof The present invention relates to a crosslinked product derived from a product, and a method for producing them.

The polyrotaxane is considered to have various applications depending on the viscoelastic properties of the polyrotaxane and various materials have been developed.
Patent Document 1 discloses a material in which a polyrotaxane and a polymer other than the polyrotaxane, that is, at least a part of another polymer are bonded via a cyclic molecule. Specifically, Patent Document 1 discloses an example in which a polyrotaxane and another polymer are bonded by adding a cross-linking agent; and a photopolymerizable group is imparted to the polyrotaxane and other polymer and both are bonded by ultraviolet irradiation. An example is disclosed.

  Patent Document 2 discloses a material in which polyrotaxane molecules or polyrotaxane molecules and another polymer are bonded by a photocrosslinking reaction. Specifically, in Patent Document 2, polyrotaxane is made hydrophilic or water-soluble (hydroxypropylated polyrotaxane, methylated polyrotaxane, etc.), and a photocrosslinking group (photopolymerizable group) is further introduced into an aqueous solution of these polyrotaxanes. Disclosed are highly transparent gels and cross-linked products by irradiation with ultraviolet rays.

  Patent Document 3 discloses a hydrophobic polyrotaxane obtained by modifying the hydroxyl group of cyclodextrin of a polyrotaxane with a hydrophobic group. In particular, it is disclosed that cyclodextrin is modified with ε-caprolactone to improve the solubility of polyrotaxane in solvents such as toluene, ethyl acetate, and acetone. However, the hydrophobic polyrotaxane in the examples has a low degree of modification with ε-caprolactone, and only about 0.02 is disclosed.

WO2005-095493. WO 2006-088200. WO2007-026578.

However, Patent Documents 1 and 2 disclose that polyrotaxane and other polymers are crosslinked by photocrosslinking, but the properties of the obtained crosslinked product are merely to improve the viscoelasticity and optical properties of the hydrogel. No other characteristics are disclosed.
Patent Document 3 discloses a hydrophobic polyrotaxane obtained by modifying the hydroxyl group of cyclodextrin with a hydrophobic group, and discloses that the solubility in a solvent is improved. However, there is no disclosure or suggestion about photocrosslinking. Not.
Furthermore, in general materials such as polyacrylic resin, polyurethane resin, rubber, etc., especially when used in an environment where deformation is continuously repeated (for example, printing plates, paints, roll parts of electric equipment, cushioning materials, etc.) By suppressing the loss of part of mechanical energy due to heat (hysteresis loss), improvements such as small residual strain after stretching, repeated resistance, and suppression of deterioration are required, but it is still insufficient.

Accordingly, an object of the present invention is to provide a photocrosslinkable polyrotaxane having the properties that cannot be expected from the prior art, particularly Patent Documents 1 and 2 and Patent Document 3, such as scratch resistance and low hysteresis loss, and the photocrosslinkable polyrotaxane. It is in providing the composition which consists essentially only of this, the composition which has this photocrosslinkable polyrotaxane, and the crosslinked body from these compositions.
The object of the present invention is to provide a method for producing a photocrosslinkable polyrotaxane having the above-mentioned characteristics in addition to or in addition to the above object, and a method for producing a composition consisting essentially of the photocrosslinkable polyrotaxane. Another object of the present invention is to provide a method for producing a composition having the photocrosslinkable polyrotaxane and a method for producing a crosslinked product from the composition.

The inventors have found the following invention.
In addition, by using the photocrosslinkable polyrotaxane described later, the present inventors are excellent not only in the viscoelasticity inherently possessed by the polyrotaxane and the flexibility and / or stretchability that can be generated thereby, but also in scratch resistance, low hysteresis loss, etc. It was found that a crosslinked product exhibiting the above properties and a composition for the crosslinked product can be provided.

<1> A photocrosslinking composition consisting essentially of (A) a photocrosslinkable polyrotaxane;
In the photocrosslinkable polyrotaxane, the cyclic molecule of the polyrotaxane has a group represented by the following formula I:
The above-mentioned composition, wherein the polyrotaxane is formed by arranging blocking groups so that the cyclic molecules are not detached at both ends of the pseudo-polyrotaxane in which the openings of the cyclic molecules are clasped by the linear molecules.
In the formula I, M is represented by the following formula II,
X represents a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; a branched alkylene group or alkenylene group having 3 to 20 carbon atoms; a part of the alkylene group or alkenylene group is an —O— bond or —NH -An alkylene group or alkenylene group substituted with a bond; or a part of hydrogen of the alkylene group is substituted with at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom. N is an average value of 1 to 10, preferably 2.0 to 9.0, more preferably 3.0 to 6.0,
Y is a group having a photopolymerizable group.

<2> (A) a photocrosslinkable polyrotaxane;
In the photocrosslinkable polyrotaxane, the cyclic molecule of the polyrotaxane has a group represented by the above formula I (M and Y in the formula I have the same definition as above),
The above-mentioned composition, wherein the polyrotaxane is formed by arranging blocking groups so that the cyclic molecules are not detached at both ends of the pseudopolyrotaxane in which the openings of the cyclic molecules are clasped by the linear molecules.
<3> In the above item <2>, the composition may further include (B) a photocrosslinkable compound;
The photocrosslinkable compound (B) is represented by the following formulas III′-1 to III′-4 (wherein R ₃₃ and R ₃₄ are each independently H or CH ₃ , m2 is 0 or 1, * Represents at least one group selected from the group Y ′ consisting of the compound directly bonded to the polymer of the compound or bonded to the polymer via a second spacer group). It is preferable that the polymer has at least two molecules in the molecule.

<4> In any one of the above items <1> to <3>, M may be a polymer derived from a lactone monomer and / or a cyclic carbonate monomer.
<5> In any one of the above items <1> to <4>, Y is represented by the following formulas III-1 to III-4 (wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m1 Is 0 or 1, and * may have at least one group selected from the group consisting of (directly bonded to M of formula I or bonded to M via the first spacer group) .

<6> In any one of the above items <1> to <5>, M may be a ring-opening polymer from a lactone, and Y may be a group having the formula III-1.
<7> In the above <6>, the lactone of M is ε-caprolactone, and Y may have an acryloyl group and / or a methacryloyl group. For example, Y is an acryloyloxyethylcarbamoyl group and / or a methacryloyloxyethylcarbamoyl group. It is good to be.

<8> In any one of the above items <3> to <7>, the polymer of the (B) photocrosslinkable compound has an average weight molecular weight of 300 to 10,000, preferably 350 to 8000, more preferably 400 to 5 000.
<9> In any one of the above items <3> to <8>, the (B) photocrosslinkable compound may be one selected from the group consisting of the following formulas IV-1 to IV-4.
In formulas IV-1 to IV-4,
R ₄₁ is H or CH ₃ ;
R ₄₂ represents a linear alkyl group or alkenyl group having 1 to 8 carbon atoms, a branched alkyl group or alkenyl group having 3 to 20 carbon atoms, a part of the alkyl group or alkenyl group being —O— bond or — An alkyl group or an alkenyl group substituted with an NH-bond, or at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom, in which a part of hydrogen of the alkyl group or alkenyl group is An alkyl group or an alkenyl group substituted with
R ₄₃ is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms, a branched alkylene group or alkenylene group having 3 to 20 carbon atoms, or a —Si (CH ₃ ) ₂ — group.
R ₄₄ is a group having trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, dipentaerythritol, isocyanuric acid, diisocyanuric acid, triazine, benzene, or a derivative thereof;
M ′ is a group having a polymer part,
Y ′ represents at least one group selected from the Y ′ group described above,
m2 ′ is 0 or 1,
Each Z independently represents a simple bond or a divalent second spacer group;
r ′ represents an integer of 3 to 6, preferably 3 to 4, more preferably 3.
Moreover, the symbol () in parentheses indicates a repeating unit.

<10> In any one of the above items <1> to <9>, the cyclic molecule may be selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.
<11> In any one of the above items <1> to <10>, the linear molecule is polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, a cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) , Polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and / or copolymers thereof, polyethylene, polypropylene, and other olefins Polyolefin resins such as copolymer resins with monomers, polyester resins, polyvinyl chloride resins, polystyrene and acrylonitrile-styrene copolymer trees Polystyrene resins such as fat, acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl Butyral resin, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polydienes such as polyimides, polyisoprene, and polybutadiene , Polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenyle , Polyhaloolefins, and derivatives thereof, such as polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and It is preferably selected from the group consisting of polyvinyl methyl ether, and more specifically, selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, particularly polyethylene glycol. It is good.

<12> In any one of the above items <1> to <11>, the linear molecule has a molecular weight of 3,000 or more, preferably 5,000 to 100,000, more preferably 10,000 to 50,000. It is good to be.
<13> In any one of the above items <1> to <12>, the blocking group is dinitrophenyl group, cyclodextrin, adamantane group, trityl group, fluorescein, silsesquioxane, pyrene, substitution Benzenes (Substituents include, but are not limited to, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more substituents may be present. ), Optionally substituted polynuclear aromatics (substituents include, but are not limited to, the same as those described above. One or more substituents may be present), and steroids Preferably selected from the group consisting of It is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, more preferably adamantane groups or trityl groups. It should be similar.

<14> In any one of the above items <1> to <13>, the cyclic molecule may be derived from α-cyclodextrin, and the linear molecule may be polyethylene glycol.
<15> In any one of the above items <1> to <14>, when the cyclic molecule is clasped with a linear molecule in a skewered manner, the amount by which the cyclic molecule is maximally included is 1, Cyclic molecules should be skewered into linear molecules in an amount of 0.001-0.6, preferably 0.01-0.5, more preferably 0.05-0.4.

<16> A crosslinked product derived from the composition described in any one of <1> and <10> to <15>.
<17> A crosslinked product derived from the composition described in any one of <2> and <10> to <15>.
<18> A crosslinked product derived from the composition described in any one of <2> to <15>.
<19> A crosslinked product derived from the composition described in any one of <3> to <15>.

<20> In any one of the above items <16> to <19>, the crosslinked body may be crosslinked through Y of (A) a crosslinkable polyrotaxane by light irradiation.
<21> In the above item <19>, the crosslinked body may be such that (A) Y of the crosslinkable polyrotaxane and (B) Y ′ of the crosslinkable compound are cross-linked by light irradiation.
<22> In any one of the above items <16> to <21>, the crosslinked product may have a hysteresis loss of 25% or less, preferably 20% or less, more preferably 15% or less.

<23> (A) A method for producing a photocrosslinkable polyrotaxane,
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which the openings of the cyclic molecules are included in a skewered manner by linear molecules;
(2) The following formula II (wherein X is a linear alkylene group having 1 to 8 carbon atoms or alkenylene group; a branched alkylene group having 3 to 20 carbon atoms; or An alkenylene group; an alkylene group or an alkenylene group in which a part of the alkylene group or alkenylene group is substituted with an —O— bond or an —NH— bond; or a part of hydrogen of the alkylene group is a hydroxyl group, a carboxyl group, or an acyl An alkylene group substituted with at least one selected from the group consisting of a group, a phenyl group, and a halogen atom; and n is an average value of 1 to 10, preferably 2.0 to 9.0, more preferably 3. 0 to 6.0)
A step of introducing -M- represented by formula:
(3) A step of introducing a group Y having a photopolymerizable group into M to form -MY.
The above method.

<24> A method for producing a composition comprising (A) a photocrosslinkable polyrotaxane; and (B) a photocrosslinkable compound,
(I) (A) a step of preparing a photocrosslinkable polyrotaxane;
(Ii) (B) preparing a photocrosslinkable compound; and (iii) (A) mixing a photocrosslinkable polyrotaxane and (B) a photocrosslinkable compound to obtain a composition having them;
Have
Step i)
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which the openings of the cyclic molecules are included in a skewered manner by linear molecules;
(2) a step of introducing -M- represented by the above formula II into a part or all of the polyrotaxane cyclic molecule; and (3) -M-Y by introducing a group Y having a photopolymerizable group into M. Forming a step;
The above method.

<25> A method for producing a crosslinked product from a composition having (A) a photocrosslinkable polyrotaxane; and (B) a photocrosslinkable compound,
(I) (A) a step of preparing a photocrosslinkable polyrotaxane;
(Ii) (B) preparing a photocrosslinkable compound;
(Iii) mixing (A) a photocrosslinkable polyrotaxane and (B) a photocrosslinkable compound to obtain a composition having them;
(Iv) a step of adding a photopolymerization initiator to the composition; and (v) a step of irradiating the obtained composition with light to form a crosslinked product;
Have
Step i)
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which the openings of the cyclic molecules are included in a skewered manner by linear molecules;
(2) a step of introducing -M- represented by the above formula II into a part or all of the polyrotaxane cyclic molecule; and (3) -M-Y by introducing a group Y having a photopolymerizable group into M. Forming a step;
The above method.

  <26> In any one of the above <23> to <25> (2), the following formula II ′ (wherein X is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; 20 branched alkylene groups or alkenylene groups; an alkylene group or alkenylene group in which a part of the alkylene group or alkenylene group is substituted with an —O— bond or —NH— bond; or a part of hydrogen of the alkylene group Is a ring-opening polymerization of a monomer having a structure of at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom; It is good to introduce.

According to the present invention, a photocrosslinkable polyrotaxane, a composition consisting essentially only of the photocrosslinkable polyrotaxane, the photocrosslinkable property, each having properties that cannot be expected from the prior art, such as scratch resistance and low hysteresis loss, etc. Compositions having polyrotaxanes and crosslinked products from these compositions can be provided.
Further, according to the present invention, a method for producing a photocrosslinkable polyrotaxane having the above characteristics in addition to or in addition to the above effects, a method for producing a composition consisting essentially of the photocrosslinkable polyrotaxane, The manufacturing method of the composition which has photocrosslinkable polyrotaxane, and the manufacturing method of the crosslinked body from these compositions can be provided.

It is a figure explaining that a hysteresis loss value is obtained from the stress-strain curve of a tensile test. It is a figure which shows the log | history which performed tension | pulling and recovery | restoration of the tension test for measuring a hysteresis loss value 5 times. In FIG. 2, (a) shows the result of Comparative Example 1, and (e) shows the result of Example 9. Moreover, (b), (c) and (d) are the results of Example 11. The arrow in the figure indicates the first drawing curve.

Hereinafter, the present invention will be described in detail.
The present invention relates to a photocrosslinkable polyrotaxane in which the cyclic molecule constituting the polyrotaxane has a photocrosslinkable group, a composition consisting essentially of the photocrosslinkable polyrotaxane, a composition having the photocrosslinkable polyrotaxane, and compositions thereof Provided are cross-linked products derived from products, and methods for producing these. Hereinafter, description will be given in the above order.

<Photocrosslinkable polyrotaxane in which the cyclic molecule constituting the polyrotaxane has a photocrosslinkable group>
In the photocrosslinkable polyrotaxane of the present invention, the cyclic molecule of the polyrotaxane has a group represented by the following formula I.
The polyrotaxane refers to a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of the pseudopolyrotaxane in which the openings of the cyclic molecules are skewered by linear molecules.
In formula I, M is represented by the following formula II, and Y represents a group having a photopolymerizable group.
In Formula II, X represents a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; a branched alkylene group or alkenylene group having 3 to 20 carbon atoms; a part of the alkylene group or alkenylene group is —O—. An alkylene group or an alkenylene group substituted with a bond or —NH— bond; or at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom in which part of hydrogen of the alkylene group is An alkylene group substituted with. Preferably, X is a linear alkylene group having 5 to 8 carbon atoms; a branched alkylene group having 5 to 8 carbon atoms; an alkylene group in which a part of the alkylene group is substituted with an —O— bond. More preferably, it is preferably a linear alkylene group having 5 to 8 carbon atoms; an alkylene group in which a part of the alkylene group is substituted with an —O— bond.
In the formula II, n has an average value of 1 to 10, preferably 2.0 to 9.0, more preferably 3.0 to 6.0. Note that n is an integer in terms of structure, but is not limited to an integer because it has dispersibility depending on the conditions for introducing M and the like.

As an example, n can be calculated as follows. That is, polyrotaxane (linear molecule: polyethylene glycol having an average molecular weight of 35,000, cyclic molecule: α-) produced by the method described in WO 2005-080469 (the contents of this document are all incorporated herein by reference) In cyclodextrin (α-CD), blocking group: polyrotaxane comprising an adamantaneamine group, 4-6 ppm (derived from H of the hydroxyl group of α-CD and H of C1) of the ¹ H-NMR (DMSO-d6) analysis chart; From the integration ratio with 3-4 ppm (H of PEG), it was found that the inclusion ratio of α-CD was 0.25. ¹ H-NMR analysis was performed with 400 MHz JEOL JNM-AL400 (manufactured by JEOL Ltd.). However, it is assumed that 2 units of PEG —CH ₂ —CH ₂ —O— repeating units are equivalent to the thickness of α-CD, and 1.0 is the case of being closely packed. Thereby, it is calculated that the theoretical hydroxyl value of the polyrotaxane is 13.6 mmol / g (average molecular weight: 35000+ (35000/88 * 0.25 * 972), hydroxyl number: (1 / average molecular weight) * (35000/88 * 0.25 * 18) mmol / g). Further, when a modifying group is added to a part of α-CD, for example, in the case of a hydroxypropyl group (—CH ₂ CH (CH ₃ ) OH), similarly, ¹ H-NMR (DMSO-d6) analysis (1 ppm signal) (Based on the integrated value of the methyl group of the hydroxypropyl group) can determine the modification rate of the hydroxypropyl group. For example, 50%. When the theoretical hydroxyl value is calculated by the same method, it is 9.7 mmol / g. Further, ring-opening polymerization is performed on the hydroxyl group using ε-caprolactone monomer. Consumption of the monomer used in the reaction is confirmed by gas chromatography (GC) (GC-2014, Shimadzu Corporation, column CBP1-W12-100 used). The consumption of monomer was almost the same as the supply amount (almost all reacted). Therefore, the value of [monomer] / [OH] in the polyrotaxane grafted with the target compound polycaprolactone can be calculated, and the value is defined as an average n. In the above example, if 1 g of hydroxypropyl modified polyrotaxane is used and 4.5 g of ε-caprolactone is used and all is consumed, n = (4.5 / 114.1 * 1000) / 9. 7 = 4.1.

  M may be a polymer derived from a lactone monomer and / or a cyclic carbonate monomer, and is preferably a ring-opening polymer from a lactone. More preferably, the lactone of M is ε-caprolactone, and M is a polymer derived from ε-caprolactone. In this case, the degree of polymerization (same as n in the above formula II) should be an average value of 1 to 10, preferably 2.0 to 9.0, more preferably 3.0 to 6.0.

  As a lactone monomer, 4-membered ring lactone such as β-propiolactone, β-methylpropiolactone, L-serine-β-lactone derivative; γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ- Octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene- γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenylγ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α-bromo-γ-butyrolactone, γ-crotonolactone, α-me 5-membered ring lactones such as len-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone; δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone , Δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, etc. Examples thereof include, but are not limited to, ring lactones; 7-membered ring lactones such as ε-caprolactone; lactide and 1,5-dioxepan-2-one. The lactone monomer is preferably ε-caprolactone, γ-butyllactone, α-methyl-γ-butyllactone, δ-valerolactone, or lactide, and more preferably ε-caprolactone.

  Cyclic carbonates include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, glycerol 1,2-carbonate, 4- (methoxymethyl) -1,3-dioxolan-2-one, (chloromethyl) ethylene carbonate, vinylene carbonate 4,5-dimethyl-1,3-dioxol-2-one, 4-chloromethyl-5-methyl-1,3-dioxol-2-one, 4-vinyl-1,3-dioxolan-2-one, 5-membered ring carbonates such as 4,5-diphenyl-1,3-dioxolan-2-one and 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one; 1,3-dioxane-2- And 6-membered ring carbonates such as 5-methyl-5-propyl-1,3-dioxolan-2-one and 5,5-diethyl-1,3-dioxolan-2-one; It is not limited to these.

Y in Formula I represents a group having a photopolymerizable group.
In particular, Y preferably has at least one group selected from the group consisting of the following formulas III-1 to III-4. Here, R ₃₁ and R ₃₂ are each independently H or CH ₃ , m1 is 0 or 1, and * is directly bonded to M of formula I or via a first spacer group Indicates where to join.
The first spacer group is a divalent group, that is, a group bonded to Y and M. As the first spacer group, —CH ₂ —CH ₂ —, —C (═O) —NH—CH ₂ —CH ₂ —, —C (CH ₃ ) ₂ NH—C (═O) —, —CH ( _{OH) CH 2 -, - CH2} -CH2-O-CH2-CH2-NH-C (= O) -, - CH 2 -CH 2 -C (= O) -, - CH 2 -CH 2 -CH 2 - _{C (= O) -, -} CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -C (= O) -, - CH 2 -CH 2 -NH-C (= O) -O-CH 2 - Examples thereof include CH ₂ —, but are not limited thereto.

Specifically, Y can be introduce | transduced by making it react with the terminal hydroxyl group of M, for example using the following compounds.
(Meth) acryloyl chloride, (meth) acrylic anhydride, 2- (meth) acryloyloxyethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) Acrylate, mono (2- (meth) acryloyloxyethyl) succinate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, α-methacryloyloxy -Γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, p-vinylbenzoic acid, pt-butylstyrene, 3-isopropenyl-isocyanate-α, α-dimethylbenzyl, vinyl chloroacetate, 3-maleimidopropionic acid , 3-maleimidopropionic acid N-s Cuccinimidyl, 4-maleimidobutyric acid N-succinimidyl, 6-maleimidohexanoic acid N-succinimidyl, etc.

  In particular, Y is preferably a group having the formula III-1, more preferably an acryloyloxyethylcarbamoyl group and / or a methacryloyloxyethylcarbamoyl group.

Hereinafter, each element constituting the polyrotaxane will be described.
<< Cyclic molecule >>
The cyclic molecule is not particularly limited as long as it is a molecule in which a linear molecule is included in a skewered manner in the opening.
The cyclic molecule may be a cyclic molecule having a hydroxyl group, and may be selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, for example. When the cyclic molecule has a hydroxyl group, a part of the hydroxyl group may be substituted with another group. Examples of other groups include a hydrophilizing group that hydrophilizes the polyrotaxane of the present invention, a hydrophobizing group that hydrophobizes the polyrotaxane of the present invention, and a photoreactive group. Not.

<< Linear molecule >>
The linear molecule of the polyrotaxane of the present invention is not particularly limited as long as it can be clasped into the opening of the cyclic molecule.
For example, as linear molecules, polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulosic resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl Polyolefin resins such as acetal resins, polyvinyl methyl ether, polyamines, polyethyleneimine, casein, gelatin, starch, and / or copolymers thereof, polyethylene, polypropylene, and copolymers of other olefin monomers; Polyester resins, polyvinyl chloride resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, polymethyl Acrylic resins such as tacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc .; and their derivatives or Modified products, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane , Polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and the like Preferably selected from the group consisting of these derivatives. For example, it may be selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. More specifically, it may be selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, particularly polyethylene glycol.

The linear molecule may have a molecular weight of 3,000 or more, preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
In the polyrotaxane of the present invention, the cyclic molecule may be derived from α-cyclodextrin, and the linear molecule may be polyethylene glycol.

When the amount of cyclic molecules to be included at the maximum when the cyclic molecules are included in a skewered manner by linear molecules is 1, the cyclic molecules are 0.001 to 0.6, preferably 0.00. It is preferable to be included in a skewered manner in a linear molecule in an amount of 01 to 0.5, more preferably 0.05 to 0.4.
The maximum inclusion amount of the cyclic molecule can be determined by the length of the linear molecule and the thickness of the cyclic molecule. For example, when the linear molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount is experimentally determined (see Macromolecules 1993, 26, 5698-5703). The contents of this document are all incorporated herein.

<< Blocking group >>
The blocking group of the polyrotaxane of the present invention is not particularly limited as long as it is a group that is arranged at both ends of the pseudopolyrotaxane and acts so that the cyclic molecule is not eliminated.
For example, as a blocking group, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (substituents are alkyl, alkyloxy, hydroxy, Examples include, but are not limited to, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more substituents may be present), optionally substituted polynuclear aromatics (substituted) Examples of the group include, but are not limited to, the same as described above, and one or more substituents may be present.) And a group consisting of steroids. It is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, more preferably adamantane groups or trityl groups. It should be similar.

<Composition consisting essentially of photocrosslinkable polyrotaxane>
The present invention provides a composition consisting essentially of the photocrosslinkable polyrotaxane described above.
In the present application, “consisting essentially of only” means that, in the composition, the photocrosslinkable material is composed of only the photocrosslinkable polyrotaxane and does not include other photocrosslinkable materials, but various other additions. Products such as photopolymerization initiators; sensitizers; silane coupling agents; surfactants; plasticizers; thickeners; silica particles; alumina particles; pigments; Natural oils; solvents that dissolve photocrosslinkable polyrotaxanes; and the like.
In other words, when photocrosslinking is performed using the “composition consisting essentially of only the photocrosslinkable polyrotaxane” of the present invention, the resulting crosslinked product is derived only from the photocrosslinkable polyrotaxane. However, the above-mentioned additives may be included in the composition.
In addition, the solvent which melt | dissolves photocrosslinkable polyrotaxane is dependent on the above-mentioned kind of M, the above-mentioned kind of Y, the used linear molecule, the used cyclic molecule, the used blocking group, etc. Examples of this solvent include, but are not limited to, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methylene chloride, N, N′-dimethylformamide, dimethylacetamide and the like.

<Composition having photocrosslinkable polyrotaxane>
The present invention also provides a composition having the above-mentioned photocrosslinkable polyrotaxane.
In the present application, “having a photocrosslinkable polyrotaxane”, in particular, “having” means that the composition includes not only the photocrosslinkable polyrotaxane but also other photocrosslinkable ones. . Of course, the composition means that it may also contain various other additives such as those mentioned above; a solvent that dissolves the photocrosslinkable polyrotaxane;

<< (B) Photocrosslinking Compound >>
Examples of other photocrosslinkable compounds in the composition of the present invention include photocrosslinkable compounds. That is, the composition of the present invention preferably has (B) a photocrosslinkable compound in addition to (A) the photocrosslinkable polyrotaxane.
The photocrosslinkable compound may be a polymer having at least two groups selected from the group Y ′ consisting of the following formulas III′-1 to III′-4 in the molecule of the compound. . Where R ₃₃ and R ₃₄ are each independently H or CH ₃ , m2 is 0 or 1, and * is bonded directly to the polymer of the compound or via a second spacer group. The part couple | bonded with this polymer is shown. Note that the second spacer group has the same definition as the first spacer described above, and the same spacer can be used independently of the first spacer.

  The polymer of the photocrosslinkable compound of the present invention has an average weight molecular weight of 300 to 10,000, preferably 350 to 8,000, more preferably 400 to 5,000.

In particular, the photocrosslinkable compound may be one selected from the group consisting of the following formulas IV-1 to IV-4.
In formulas IV-1 to IV-4,
R ₄₁ is H or CH ₃ ;
R ₄₂ represents a linear alkyl group or alkenyl group having 1 to 8 carbon atoms, a branched alkyl group or alkenyl group having 3 to 20 carbon atoms, a part of the alkyl group or alkenyl group being —O— bond or — An alkyl group or an alkenyl group substituted with an NH-bond, or at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom, in which a part of hydrogen of the alkyl group or alkenyl group is An alkyl group or an alkenyl group substituted with
R ₄₃ is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms, a branched alkylene group or alkenylene group having 3 to 20 carbon atoms, or a —Si (CH ₃ ) ₂ — group.
R ₄₄ is a group having trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, dipentaerythritol, isocyanuric acid, diisocyanuric acid, triazine, benzene, or a derivative thereof;
M ′ is a group having a polymer part,
Y ′ represents at least one group selected from the Y ′ group described above,
m2 ′ is 0 or 1,
Each Z independently represents a simple bond or a divalent second spacer group;
r ′ represents an integer of 3 to 6, preferably 3 to 4, more preferably 3.
Further, in the formulas IV-1 to IV-4, the parenthesized symbol () indicates a repeating unit.
The second spacer group can be specifically the same as the first spacer group described above.

<Crosslinked product derived from the above composition>
The present invention provides a crosslinked product derived from the above composition.
That is, the present invention broadly categorizes two types: a) a crosslinked product derived from a composition consisting essentially of only a photocrosslinkable polyrotaxane; and a) a crosslinked product derived from a composition having a photocrosslinkable polyrotaxane. .
In addition, the cross-linked body derived from the composition consisting essentially of only the photocrosslinkable polyrotaxane is derived from only the photocrosslinkable polyrotaxane as described above. On the other hand, when the crosslinked product derived from the composition having a photocrosslinkable polyrotaxane is derived only from the photocrosslinkable polyrotaxane, the photocrosslinkable polyrotaxane and other photocrosslinkable ones, for example, the above-mentioned (B) photocrosslink It may be derived from a sex compound.

The cross-linked product of the above a) and / or a) is preferably cross-linked via Y of the above-mentioned (A) cross-linkable polyrotaxane by light irradiation.
In particular, the cross-linked product of a), that is, a cross-linked product derived from a composition consisting essentially only of a photo-crosslinkable polyrotaxane, should be cross-linked via at least two molecules of Y of the crosslinkable polyrotaxane (A).
The crosslinked product of (a), that is, the crosslinked product derived from the composition having a photocrosslinkable polyrotaxane, is a crosslinked product cross-linked through Y of at least two molecules of (A) the crosslinkable polyrotaxane; Y and other photocrosslinkable ones, for example, a cross-linked product that is cross-linked via the above-mentioned (B) Y ′ of the photocrosslinkable compound; In the crosslinked product of the present invention, at least (A) Y of the crosslinkable polyrotaxane and (B) Y ′ of the crosslinkable compound are preferably crosslinked at least.

The crosslinked product of the present invention has an initial elastic modulus in a stress-strain curve of 100 MPa or less, preferably 50 MPa or less, more preferably 25 MPa or less.
The crosslinked product of the present invention has a hysteresis loss of 25% or less, preferably 20% or less, more preferably 15% or less.

Here, the hysteresis loss refers to a material in which a strain due to a tensile test of a material is used in place of deformation of the material in a mechanical energy loss rate (hysteresis loss) in one cycle of deformation and recovery in accordance with JIS K6400.
Specifically, a sample having a length of 30 mm, a width of 4 mm, and a thickness of 0.20 mm is subjected to a tensile test, and a stress-strain curve is measured. The elongation at 20% of the effective length and the recovery (the first elongation-recovery cycle) is the hysteresis loss in the present application, and the hysteresis loss is calculated by measuring the area by the method shown in FIG. The

Hysteresis loss (%) =
Area (oabcd) in FIG. 1 / area (oabeo) in FIG. 1 × 100.

The photocrosslinkable polyrotaxane of the present invention, a composition consisting essentially of only a photocrosslinkable polyrotaxane or a composition having a photocrosslinkable polyrotaxane, and a crosslinked product derived from the composition are the viscoelasticity of the polyrotaxane and the flexibility that can be generated thereby. The present invention is not only applied to the field where properties and / or stretchability is required, but also various fields where scratch resistance is required and / or low hysteresis loss is required.
These fields include automobiles, electrical appliances, furniture and other paints and coating materials; automatic interior materials; adhesives and pressure sensitive adhesives; printing plate materials; dental hygiene materials, mechanical and automatic friction materials; Civil engineering and building materials such as materials and waterproof materials; Electronic and electrical materials such as clothing and sports equipment materials, insulating materials, sealing materials, heat transfer materials, conductive material binders; insulating actuator materials; optical materials, vibration and vibration control Examples include, but are not limited to, vibration-isolating materials, cosmetic materials, rheology control agents, fiber materials, medical biomaterials, and the like.

<Method for producing photocrosslinkable polyrotaxane>
The photocrosslinkable polyrotaxane of the present invention can be produced, for example, by the following production method:
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which the openings of the cyclic molecules are included in a skewered manner by linear molecules;
(2) a step of introducing -M- represented by the above formula II into a part or all of the polyrotaxane cyclic molecule; and (3) -M-Y by introducing a group Y having a photopolymerizable group into M. Forming a step;
Can be obtained.
In addition, you may have another process before and after the said process. For example, after step (1) and before step (2), after step (2) and before step (3), or after step (3), a group other than -MY is provided on the cyclic molecule. You may have a process.

  Step (1) is a step of preparing a polyrotaxane. Polyrotaxanes can be obtained by referring to documents published prior to the filing of the present application (eg, WO2005-080469, WO2005-108464, and WO2009-136618, all of which are incorporated herein by reference). Can get.

Step (2) is a step of introducing -M- represented by the above formula II into part or all of the cyclic molecule of polyrotaxane.
In this step, it is preferable to introduce -M- by ring-opening polymerization of a monomer having the structure of the following formula II '.

  Step (2) depends on the polyrotaxane to be used and -M- to be introduced, but the reaction temperature is 100 to 130 ° C., normal pressure, toluene, xylene, etc. are used as a solvent, and the reaction is performed in the presence of a tin catalyst. It is good to do below.

<Method for Producing Composition Consisting essentially of Photocrosslinkable Polyrotaxane>
The composition consisting essentially of the photocrosslinkable polyrotaxane can be obtained by mixing the above-mentioned photocrosslinkable polyrotaxane with a solvent and other additives.

<Method for Producing Composition Having Photocrosslinkable Polyrotaxane>
A composition having a photocrosslinkable polyrotaxane, in particular, a composition having (A) a photocrosslinkable polyrotaxane; and (B) a photocrosslinkable compound can be obtained, for example, by the following method.
(I) (A) a step of preparing a photocrosslinkable polyrotaxane;
(Ii) (B) preparing a photocrosslinkable compound; and (iii) (A) mixing a photocrosslinkable polyrotaxane and (B) a photocrosslinkable compound to obtain a composition having them;
Can be obtained.
In step i), the above-described method for producing a photocrosslinkable polyrotaxane is preferably performed.

<The manufacturing method of the crosslinked body derived from the said composition>
The crosslinked product of the present invention can be obtained, for example, by the following method.
For example, when using a composition consisting essentially only of a photocrosslinkable polyrotaxane,
(Iv ′) a step of adding a photopolymerization initiator to the composition; and (v ′) a step of irradiating the resulting composition with light to form a crosslinked product;
By having this, the crosslinked body of the present invention can be obtained.

When using a composition having a photocrosslinkable polyrotaxane as the composition, particularly a composition having (A) a photocrosslinkable polyrotaxane; and (B) a photocrosslinkable compound,
(I) (A) a step of preparing a photocrosslinkable polyrotaxane;
(Ii) (B) preparing a photocrosslinkable compound;
(Iii) mixing (A) a photocrosslinkable polyrotaxane and (B) a photocrosslinkable compound to obtain a composition having them;
(Iv) a step of adding a photopolymerization initiator to the composition; and (v) a step of irradiating the obtained composition with light to form a crosslinked product;
By having this, the crosslinked body of the present invention can be obtained.

As the photopolymerization initiator of (iv) or (iv ′) above, quinones, aromatic ketones, benzoin, benzoin ethers, biimidazole compounds and derivatives thereof, N-phenylglycines, thioxanthones and alkylaminobenzoic acid And at least one selected from the group consisting of a combination of a biimidazole compound and a derivative thereof and Michler's ketone, an acridine, and an oxime ester. Specifically, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone , 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, quinones such as 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4'-bis (Dimethylamino) benzophenone], aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin; Biimidazole compounds such as rudimethyl ketal, benzyl diethyl ketal, triarylimidazolyl dimer and derivatives thereof, N-phenyl such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine Glycines, combinations of thioxanthones and alkylaminobenzoic acids, such as ethylthioxanthone and ethyl dimethylaminobenzoate, combinations of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, isopropylthioxanthone and ethyl dimethylaminobenzoate, and triaryls Combinations of biimidazole compounds such as imidazolyl dimer and derivatives thereof and Michler's ketone, acridines such as 9-phenylacridine, 1-phenyl-1,2-propanedione-2-o- Oxime esters such as benzoin oxime and 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime are preferred. Preferably, thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoates such as ethyl dimethylaminobenzoate, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) Biimidazole compounds such as benzophenone and triarylimidazolyl dimers and derivatives thereof, 9-phenylacridine, N-phenylglycines, and combinations thereof may be used. Examples of biimidazole compounds such as triarylimidazolyl dimers and derivatives thereof include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ′, 5-tris- (o -Chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl)- Diphenylimidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl Dimer, 2,2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, , 2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2, 4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3 -Methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer 2-mer, 2,2′-bis- (2,3,5-trifluorofe ) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4' , 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis -(3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -Imidazolyl dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′ 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5 Examples include, but are not limited to, '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer.
In addition, when including a photoinitiator in a composition, process (iv) or (iv ') does not need to have.

Step (v) is a step of irradiating the composition with light to form a crosslinked product.
Light irradiation depends on conditions such as the photopolymerization initiator, sensitizer, sample thickness, and shape to be used, but basically contains light in the wavelength region (200 nm to 450 nm) from ultraviolet to visible light. Any device that can be used. For example, a device using a mercury lamp, a metal halide lamp, or a mercury xenon lamp as a light source may be used. For example, it may be performed under conditions such as wavelength: 365 nm; light intensity: 30 to 150 mW / cm ² ; irradiation time: 10 seconds to 5 minutes;
In addition, you may have the process of apply | coating a composition to a various base material by a conventionally well-known method before a process (v). Thereby, a desired crosslinked body can be formed on the base material, and the crosslinked body has not only the effects of the present invention, for example, the inherently inherent viscoelasticity of the polyrotaxane and the flexibility and / or stretchability that can be generated thereby, It can have scratch resistance, low hysteresis loss, and the like.

(Example)
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

  Linear molecule: polyethylene glycol (average molecular weight 35,000), cyclic molecule: α-cyclodextrin (hereinafter, “dextrin” is simply abbreviated as “CD”), blocking group: polyrotaxane composed of adamantaneamine group, A hydroxypropylated compound (hereinafter, hydroxypropylated polyrotaxane is abbreviated as “HAPR35”) is similar to the method described in WO2005-080469 (the contents of this document are all incorporated herein by reference). (Α-CD inclusion rate: 25%; hydroxypropyl group modification rate: 50%; theoretical hydroxyl group content: 9.7 mmol / g; average weight molecular weight Mw: 150,000 by gel permeation chromatography (GPC)) . The molecular weight and molecular weight distribution were measured with a TOSOH HLC-8220 GPC apparatus. Column: TSK guard column Super AW-H and TSKgel Super AWM-H (two linked), eluent: dimethyl sulfoxide / 0.01 M LiBr, column oven: 50 ° C., flow rate: 0.5 ml / min, sample concentration about Measurement was performed under the conditions of 0.2 wt / vol%, injection amount: 20 μl, pretreatment: filtration through a 0.2 μm filter, and standard molecular weight: PEO.

<1-1. Hydroxypropylated polyrotaxane modified with polycaprolactone>
A mixed solution in which 5 g of the hydroxypropylated polyrotaxane (HAPR35) obtained above was dissolved in 22.5 g of ε-caprolactone at a temperature of 80 ° C. was obtained. The mixture was stirred at 110 ° C. for 1 hour while blowing dry nitrogen, 0.16 g of a 50 wt% xylene solution of tin (II) 2-ethylhexanoate was added, and the mixture was stirred at 130 ° C. for 6 hours. Thereafter, xylene was added to obtain a xylene solution of polycaprolactone-modified hydroxypropylated polyrotaxane (HAPR35) X-1 having a nonvolatile concentration of about 35 wt%.
The obtained modified polyrotaxane X-1 was examined for the degree of polymerization of polycaprolactone by the theoretical hydroxyl group content of raw material HAPR35 and the monomer consumption (approximately 100%) of gas chromatography (GC). As a result, the polymerization degree was 4.1. I found out.

<1-2. Introduction of acryloyl group into polycaprolactone-modified hydroxypropylated polyrotaxane>
After adding 0.01 g of dibutylhydroxytoluene (polymerization inhibitor) to a xylene solution of polycaprolactone-modified hydroxypropylated polyrotaxane X-1 cooled to room temperature, 7.1 g of 2-acryloyloxyethyl isocyanate was added dropwise. The mixture was stirred at 40 ° C. for 16 hours to obtain a xylene solution of acryloylated polyrotaxane A-1 in which acryloyloxyethylcarbamoyl group was introduced into polycaprolactone-modified hydroxypropylated polyrotaxane. The weight average molecular weight Mw of the obtained polyrotaxane was 550,000 by GPC measurement. In the obtained polyrotaxane A-1, Y is an acryloyl group (—OC (═O) —CH═CH ₂ ), and the first spacer group is —C (═O) —NH—CH ₂ —CH _2. Met.

Modification was performed in the same manner as in Example 1 except that 21.5 g of ε-caprolactone and 1.0 g of α-methyl-γ-butyrolactone were used instead of 22.5 g of ε-caprolactone in <1-1> of Example 1. Polyrotaxane A-2 was produced. The average weight molecular weight Mw of the obtained polyrotaxane was 580,000 by GPC measurement.
About the obtained modified polyrotaxane A-2, the copolymer of ε-caprolactone and α-methyl-γ-butyrolactone was determined by the theoretical hydroxyl group content of the raw material HAPR35 and the monomer consumption (approximately 100%) of gas chromatography (GC). As a result of examining the degree of polymerization, it was found that the degree of polymerization was 4.1.

A modified polyrotaxane A-3 was prepared in the same manner as in Example 1 except that 43.0 g of ε-caprolactone and 2.0 g of propylene carbonate were used instead of 22.5 g of ε-caprolactone in <1-1> of Example 1. Produced. The average weight molecular weight Mw of the obtained polyrotaxane was 560,000 by GPC measurement.
The obtained modified polyrotaxane A-3 was examined for the degree of polymerization of a copolymer of ε-caprolactone and propylene carbonate based on the theoretical hydroxyl group content of the raw material HAPR35 and the GC monomer consumption (almost 100%). It was found to be 9.0.

A modified polyrotaxane A-4 was produced in the same manner as in Example 1, except that acetylated polyrotaxane was used instead of the hydroxypropylated polyrotaxane of Example 1. The average weight molecular weight Mw of the obtained polyrotaxane was 480,000 by GPC measurement.
In addition, acetylated polyrotaxane (α-CD packing rate: 27% by ¹ H-NMR analysis, modification rate of acetyl group: 50%, theoretical hydroxyl value: 5.4 mmol / g; average weight molecular weight Mw by GPC: 100,000 ) Was prepared similarly to the method described in WO-2005-080469, the contents of which are all incorporated herein by reference.
In addition, the polymerization degree of polycaprolactone of the obtained modified polyrotaxane A-4 was 7.3 as in Example 1.

<Introduction of methacryloyl group into polycaprolactone-modified hydroxypropylated polyrotaxane>
A modified polyrotaxane A-5 was produced in the same manner as in Example 1, except that 7.8 g of 2-methacryloyloxyethyl isocyanate was used instead of 7.1 g of 2-acryloyloxyethyl isocyanate of Example 1. The average weight molecular weight Mw of the obtained polyrotaxane was 560,000 by GPC measurement. In the obtained A-5, Y is a methacryloyl group (—OC (═O) —CH (CH ₃ ) —CH ₂ ), and the first spacer group is —C (═O) —NH—CH _2. It was -CH _2.

<Introduction of acryloyl group and butylcarbamoyl group into polycaprolactone-modified hydroxypropylated polyrotaxane>
A modified polyrotaxane A-6 was prepared in the same manner as in Example 1 except that 3.5 g of 2-acryloyloxyethyl isocyanate and 2.5 g of butyl isocyanate were used instead of 7.1 g of 2-acryloyloxyethyl isocyanate of Example 1. Produced. The average weight molecular weight Mw of the obtained polyrotaxane was 590,000 by GPC measurement. In the obtained A-6, Y is an acryloyl group (—OC (═O) —CH═CH ₂ ), and the first spacer group is —C (═O) —NH—CH ₂ —CH ₂ . Furthermore, a part of M was modified with a butylcarbamoyl group.

<Introduction of methacryloyl and butylcarbamoyl groups into polycaprolactone-modified hydroxypropylated polyrotaxane>
The modified polyrotaxane A-7 was prepared in the same manner as in Example 1 except that 3.9 g of 2-methacryloyloxyethyl isocyanate and 2.5 g of butyl isocyanate were used instead of 7.1 g of 2-acryloyloxyethyl isocyanate of Example 1. Produced. The average weight molecular weight Mw of the obtained polyrotaxane was 600,000 by GPC measurement. In the obtained A-7, Y is a methacryloyl group (—OC (═O) —CH═CH ₂ ), and the first spacer group is —C (═O) —NH—CH ₂ —CH ₂ . Furthermore, a part of M was modified with a butylcarbamoyl group.

<Introduction of α-methylstyryl group into polycaprolactone-modified hydroxypropylated polyrotaxane>
A modified polyrotaxane A-8 was prepared in the same manner as in Example 1 except that 9.0 g of 3-isopropenyl-α-isocyanate and α-dimethylbenzyl were used in place of 7.1 g of 2-acryloyloxyethyl isocyanate of Example 1. Was made. The average weight molecular weight Mw of the obtained polyrotaxane was 470,000 by GPC measurement. In the obtained A-8, Y is a 3-isopropenylbenzyl group (—C ₆ H ₄ —C (CH ₃ ) ═CH ₂ ), and the first spacer group is —C (CH ₃ ) ₂ NH -C (= O)-.

<Preparation example of photocrosslinkable oligomer>
[Synthesis Example 1]
<Synthesis of methacryloyl group-modified polycarbonate>
Polycarbonate diol (polyalkylene carbonate diol 96 wt% or more, 1,5-pentanediol 2 wt% or less, polycarbonate having a composition of 1,6-hexanediol 2 wt% or less, DURANOL (registered trademark) T-5650J manufactured by Asahi Kasei Chemicals Corporation, 30 g of Mn: 800) 13.3 g of 2-methacryloyloxyethyl isocyanate (Karenz (registered trademark) MOI manufactured by Showa Denko KK) dissolved in 18 g of xylene, 0.01 g of dibutylhydroxytoluene (polymerization inhibitor), dibutyl dilaurate 0.06 g of tin was slowly added dropwise and reacted at 40 ° C. for 5 hours to obtain a methacryloyl group both-end modified polycarbonate oligomer B-1 having a nonvolatile content of 71%.
As a result of examining the average weight molecular weight Mw of the obtained oligomer B-1 by GPC, it was found to be 1270.

[Synthesis Example 2]
<Synthesis of acryloyl group-modified polycaprolactone oligomer>
5 g of polycaprolactone-modified hydroxyethyl acrylate (Placcel (registered trademark) FA2D manufactured by Daicel Chemical Industries, Ltd.) was dissolved in 13.3 g of xylene, and 0.02 g of dibutyltin dilaurate was added. To this solution, 8.3 g of isocyanurate type hexamethylene diisocyanate (Duranate (registered trademark) TPA-100 manufactured by Asahi Kasei Chemicals Corporation) was added and reacted, and the modification having three acryloyl groups in the molecule having a nonvolatile content of 50%. Polycaprolactone oligomer B-2 was obtained.
As a result of examining the average weight molecular weight Mw of the obtained oligomer B-2 by GPC, it was found to be 1540.

[Synthesis Example 3]
<Synthesis of methacryloyl group-modified acrylic copolymer>
A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 9 ml of butyl acetate, and 14 g of butyl acrylate, 4 g of methyl methacrylate, 2 g of hydroxyethyl methacrylate and 2,2′-azobisiso prepared in advance while refluxing at 120 ° C. A mixed solution of 1.2 g of butyronitrile (AIBN) was dropped into the reactor over 2 hours. Thereafter, 0.2 g of AIBN was further added, and the reaction was continued for 3 hours. The reaction liquid cooled to room temperature was poured into hexane, and the precipitated liquid was recovered. Add 20 ml of butyl acetate, 1 mg of dibutylhydroxytoluene (polymerization inhibitor) and 0.02 g of dibutyltin dilaurate to the recovered product, add 2-methacryloyloxyisocyanate dropwise with stirring at 40 ° C., and react for 3 hours. As a result, an acrylic oligomer (copolymer of butyl acrylate, methyl methacrylate, and hydroxyethyl methacrylate) B-3 having a large number of methacryloyl groups of about 52% was obtained (by ¹ H-NMR analysis). As a result of analysis by GPC, the average weight molecular weight Mw was 7,500, and the dispersion Mw / Mn was 1.8. Also ^{the 1} H-NMR 5.7 and _CH 2 = C-methacryloyl group than H signals around 6.1ppm of was introduced was observed.

[Synthesis Example 4]
<Synthesis of methacryloyl group-modified polyethylene glycol oligomer>
2 g of polyethylene glycol methacrylate (manufactured by Aldrich, Mn: 360) was dissolved in 3 g of xylene, and 0.01 g of dibutyltin dilaurate was added. To this solution, 1.0 g of isocyanurate type hexamethylene diisocyanate (Duranate (registered trademark) TPA-100) was added and reacted, and a modified polyethylene glycol oligomer B- having 3 methacryloyl groups in the molecule having a nonvolatile content of 50%. 4 was obtained.
As a result of examining the average weight molecular weight Mw of the obtained oligomer B-4 by GPC, it was found to be 1740.

[Synthesis Example 5]
<Synthesis of acryloyl group-modified dimethylsiloxane-caprolactone block copolymer>
4 g of Carbinol (hydroxyl) terminated polydimethylsiloxane caprolactone block polymer) (Azmax, Mw 5700-6900) was dissolved in toluene, and a tin catalyst was added. To this solution, 0.22 g of 2-acryloyloxyethyl isocyanate (Karenz AOI (registered trademark) manufactured by Showa Denko KK) was added and reacted to obtain acryloyl group-modified dimethylsiloxane-caprolactone block copolymer B-5 at both ends.
As a result of examining the average weight molecular weight Mw of the obtained oligomer B-5 by GPC, it was found to be 7100.

<Preparation of a crosslinked product derived from a composition comprising only photocrosslinkable polyrotaxane>
To the xylene solution of acryloylated polyrotaxane A-1 obtained in Example 1, Irgacure 500 (mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator. 5 wt% was added with respect to solid content. This mixture was applied to a glass substrate treated with a release agent with a bar coater, irradiated with ultraviolet rays at 30 mW / cm ² for 90 seconds, and then the cured film was dried at 110 ° C. for 1 hour. The dried film (thickness 0.2 mm) was peeled off and cut out (length 30 mm, width 4 mm) to prepare a test piece.
Further, this mixture was applied to a black acrylic plate with a thickness of 0.1 mm, irradiated with ultraviolet rays at 30 mW / cm ² for 90 seconds, and then dried to prepare a coating film for a scratch resistance test.

  A cross-linked test piece was prepared in the same manner as in Example 9 except that the acryloylated polyrotaxane A-6 obtained in Example 6 was used instead of the acryloylated polyrotaxane A-1 used in Example 9.

<Preparation of a crosslinked product derived from a composition having a photocrosslinkable polyrotaxane>
Photopolymerization was started by blending the acryloylated polyrotaxane A-1 obtained in Example 1 and the polycarbonate oligomer B-1 prepared in Synthesis Example 1 at a solid weight ratio of 2: 8, 5: 5, 7: 3. As an agent, 5 wt% of Irgacure 500 was added to the solid content.
The obtained composition was applied to a glass substrate treated with a release agent with a bar coater, irradiated with ultraviolet rays at 30 mW / cm ² for 90 seconds, and the cured film was dried at 110 ° C. for 1 hour. The dried film (thickness 0.2 mm) was peeled off and cut out to prepare a test piece.
Further, the obtained composition was applied on a black acrylic plate in a thickness of 0.1 mm, irradiated with ultraviolet rays at 30 mW / cm ² for 90 seconds and dried to prepare a coating film for a scratch resistance test.

  A test piece of a crosslinked product was produced in the same manner as in Example 11 except that the oligomer B-2 obtained in Synthesis Example 2 was used instead of the polycarbonate oligomer B-1.

  A test piece of a crosslinked product was produced in the same manner as in Example 11 except that the oligomer B-3 obtained in Synthesis Example 3 was used instead of the polycarbonate oligomer B-1.

  A test piece of a crosslinked product was produced in the same manner as in Example 11 except that the oligomer B-4 obtained in Synthesis Example 4 was used instead of the polycarbonate oligomer B-1.

  A test piece of a crosslinked product was produced in the same manner as in Example 11 except that polypropylene glycol diacrylate B-6 (manufactured by Aldrich, Mn 900) was used instead of the polycarbonate oligomer B-1.

  A test piece of a crosslinked product was produced in the same manner as in Example 11 except that the modified polyrotaxane A-6 obtained in Example 6 was used instead of the acryloylated polyrotaxane A-1 obtained in Example 1.

Dimethylsiloxane-caprolactone prepared by blending the acryloylated polyrotaxane A-1 obtained in Example 1 and the polycarbonate oligomer B-1 prepared in Synthesis Example 1 at a solid content weight ratio of 7: 3 and further adjusting in Synthesis Example 5 1% of block copolymer B-5 was added. Irgacure 500 was used as a photopolymerization initiator at 5 wt% based on the solid content.
The obtained composition was cured in the same manner as in Example 11 to obtain a test piece of a crosslinked product.

The acryloylated polyrotaxane A-3 obtained in Example 3 and the oligomer B-2 prepared in Synthesis Example 2 were blended at a solid content weight ratio of 7: 3. Irgacure 500 was used as a photopolymerization initiator at 5 wt% based on the solid content.
The obtained composition was cured in the same manner as in Example 11 to obtain a test piece of a crosslinked product.

(Comparative Examples 1-6)
About Examples 11-15, 17, the polyrotaxane was not added but the ultraviolet-ray hardening | curing was carried out by the oligomer alone, and the test piece C-1 to C-6 of the crosslinked body of oligomers was obtained with the same method.

<Characteristics of crosslinked body>
The test pieces prepared in Examples 9 to 18 and Comparative Examples 1 to 6 were evaluated by the following methods.
<< Folding resistance >>
The peeled sheet-like film was repeatedly bent by 180 ° to confirm bending streaks and breakage. As a result, the test was performed five times, and “◯” indicates that there was no change; “Δ” indicates that there is a slight bending streak in five tests; and “×” indicates that the sample was broken in one test. The results are shown in Table 1.

<< Scratch resistance >>
In the above-mentioned, about the test piece produced on the black acrylic board, the coating-film surface of the test piece was scratched with the brass brush (3 rows of bristle material, wire diameter 0.15mm), and the damage degree was observed visually. As a result, “◯” indicates that the scratch was found, “△” indicates that the scratch was slightly but acceptable, and “X” indicates that the scratch was immediately damaged. The results are shown in Table 1.

<< Hysteresis loss >>
Hysteresis loss was measured by the test method described above.
A measurement example is shown in FIG. In FIG. 2, (a) shows the result of Comparative Example 1, and (e) shows the result of Example 9. Further, (b), (c) and (d) show the results of Example 11, and the weight ratios of modified polyrotaxane A-1: oligomer B-1 are 2: 8, 5: 5 and 7: 3, respectively. Indicates. In addition, the arrow in a figure shows the 1st extending | stretching curve.

Further, the tensile test of FIG. 2 is performed by performing the number of times of tension and recovery five times, and their history is shown.
In FIG. 2 (e), that is, Example 9, the history is almost a straight line, and it can be seen that the same history is shown even if the number of times of tension and recovery is 5 times. When this is set as the hysteresis loss value, it is 6%, and the value is almost as close to 0, indicating that the hysteresis loss is low.
On the other hand, (a) of FIG. 2, ie, the comparative example 1, shows that the history of 5 times is mixed. When this is the hysteresis loss value, it is 53%, and it can be seen that the hysteresis loss value is not satisfactory.
Note that (b), (c), and (d) in FIG. 2 show histories close to (e), and the hysteresis loss values are 23%, 21%, and 14%, respectively.

  The hysteresis loss value was obtained from the history of the tensile test as shown in FIG. The results are shown in Table 1.

  Table 1 summarizes the above characteristics. In the table, “A” indicates the type of polyrotaxane used, “B” indicates the type of crosslinkable compound used, and “A: B” indicates the solid weight ratio of the polyrotaxane used and the crosslinkable compound used.

From Table 1, Comparative Examples 1 to 6, that is, a crosslinked film obtained using only the photocrosslinkable compound, did not satisfy all of folding resistance, scratch resistance and hysteresis loss.
On the other hand, it can be seen that the crosslinked product of the present invention, that is, Examples 9 to 18, satisfied all of folding resistance, scratch resistance and hysteresis loss.
From these facts, the photocrosslinkable polyrotaxane of the present invention, the composition having the same, and the crosslinked product derived from the composition have a significant effect compared to the conventional ones (Comparative Examples 1 to 6), that is, folding resistance. Satisfactory values can be achieved in all of properties, scratch resistance and hysteresis loss.

Claims (19)

(A) a photocrosslinkable polyrotaxane; a photocrosslinking composition consisting essentially of:
The photocrosslinkable polyrotaxane has a polyrotaxane cyclic molecule represented by the following formula I:
(In the formula, M is represented by the following formula II,
X represents a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; a branched alkylene group or alkenylene group having 3 to 20 carbon atoms; a part of the alkylene group or alkenylene group is an —O— bond or —NH -An alkylene group or alkenylene group substituted with a bond; or a part of hydrogen of the alkylene group is substituted with at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom. And n is an average value of 1 to 10,
Y is a group having a photopolymerizable group)
Having a group represented by
The said polyrotaxane is the said composition formed by arrange | positioning the blocking group so that the said cyclic molecule may not detach | desorb at the both ends of the pseudo polyrotaxane in which the opening part of a cyclic molecule is skewered by the linear molecule.

(A) a photocrosslinkable polyrotaxane;
The photocrosslinkable polyrotaxane has a polyrotaxane cyclic molecule represented by the following formula I:
(In the formula, M is represented by the following formula II,
X represents a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; a branched alkylene group or alkenylene group having 3 to 20 carbon atoms; a part of the alkylene group or alkenylene group is an —O— bond or —NH -An alkylene group or alkenylene group substituted with a bond; or a part of hydrogen of the alkylene group is substituted with at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom. And n is an average value of 1 to 10,
Y is a group having a photopolymerizable group)
Having a group represented by
The said polyrotaxane is the said composition formed by arrange | positioning the blocking group so that the said cyclic molecule may not detach | desorb at the both ends of the pseudo polyrotaxane in which the opening part of a cyclic molecule is skewered by the linear molecule.

The composition according to claim 2, further comprising (B) a photocrosslinkable compound,
The photocrosslinkable compound (B) is represented by the following formulas III′-1 to III′-4 (wherein R ₃₃ and R ₃₄ are each independently H or CH ₃ , m2 is 0 or 1, * Represents at least one group selected from the group Y ′ consisting of the compound directly bonded to the polymer of the compound or bonded to the polymer via a second spacer group). The above composition, which is a polymer having at least two molecules in the molecule.

  The composition according to any one of claims 1 to 3, wherein M is a polymer derived from a lactone monomer and / or a cyclic carbonate monomer. Y is represented by the following formulas III-1 to III-4 (wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m1 is 0 or 1, and * is directly related to M in formula I). The composition according to any one of claims 1 to 4, wherein the composition has at least one group selected from the group consisting of a bond or a bond with M via a first spacer group.

  The composition according to any one of claims 1 to 5, wherein M is a ring-opening polymer from lactone, and Y is a group having the formula III-1.   The composition according to claim 6, wherein the M lactone is ε-caprolactone and the Y has an acryloyl group and / or a methacryloyl group.   The composition according to any one of claims 3 to 7, wherein the polymer of the (B) photocrosslinkable compound has an average weight molecular weight of 300 to 10,000. The (B) photocrosslinkable compound has the following formulas IV-1 to IV-4 (wherein
R ₄₁ is H or CH ₃ ;
R ₄₂ represents a linear alkyl group or alkenyl group having 1 to 8 carbon atoms, a branched alkyl group or alkenyl group having 3 to 20 carbon atoms, a part of the alkyl group or alkenyl group being —O— bond or — An alkyl group or an alkenyl group substituted with an NH-bond, or at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, and a halogen atom, in which a part of hydrogen of the alkyl group or alkenyl group is An alkyl group or an alkenyl group substituted with
R ₄₃ is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms, a branched alkylene group or alkenylene group having 3 to 20 carbon atoms, or a —Si (CH ₃ ) ₂ — group.
R ₄₄ is a group having trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, dipentaerythritol, isocyanuric acid, diisocyanuric acid, triazine, benzene, or a derivative thereof;
M ′ is a group having a polymer part,
Y ′ represents at least one group selected from the Y ′ group,
m2 ′ is 0 or 1,
Each Z independently represents a simple bond or a divalent second spacer group;
r ′ represents an integer of 3 to 6,
The composition according to any one of claims 3 to 8, which is one selected from the group consisting of a parenthesis symbol () indicating a repeating unit).

  A crosslinked product derived from the composition according to claim 1.   The crosslinked body derived from the composition of any one of Claims 2-9.   The crosslinked body derived from the composition of any one of Claims 3-9.   The crosslinked body according to any one of claims 10 to 12, wherein the crosslinked body is crosslinked through the Y of the (A) crosslinkable polyrotaxane by light irradiation.   The cross-linked product according to claim 12, wherein the cross-linked product is at least cross-linked (Y) of the cross-linkable polyrotaxane (A) and Y 'of the cross-linkable compound (B) by light irradiation.   The crosslinked body according to any one of claims 10 to 14, wherein the crosslinked body has a hysteresis loss of 25% or less. (A) A method for producing a photocrosslinkable polyrotaxane,
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which openings of the cyclic molecules are skewered by linear molecules;
(2) A part or all of the cyclic molecule of the polyrotaxane is represented by the following formula II (wherein X is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; branched alkylene having 3 to 20 carbon atoms) A group or alkenylene group; an alkylene group or alkenylene group in which a part of the alkylene group or alkenylene group is substituted with an —O— bond or —NH— bond; or a part of hydrogen of the alkylene group is a hydroxyl group or a carboxyl group An alkylene group substituted with at least one selected from the group consisting of an acyl group, a phenyl group, and a halogen atom; and n is an average value of 1 to 10)
A step of introducing -M- represented by formula:
(3) A step of introducing a group Y having a photopolymerizable group into M to form -MY.
The above method.

The method according to claim 16, wherein in (2), the monomer having the following structure II 'is subjected to ring-opening polymerization to introduce the -M-.

(A) a photocrosslinkable polyrotaxane; and (B) a photocrosslinkable compound;
(I) preparing the (A) photocrosslinkable polyrotaxane;
(Ii) preparing the (B) photocrosslinkable compound; and (iii) mixing the (A) photocrosslinkable polyrotaxane and the (B) photocrosslinkable compound to obtain a composition having them. ;
Have
Said step i)
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which openings of the cyclic molecules are skewered by linear molecules;
(2) A part or all of the cyclic molecule of the polyrotaxane is represented by the following formula II (wherein X is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; branched alkylene having 3 to 20 carbon atoms) A group or alkenylene group; an alkylene group or alkenylene group in which a part of the alkylene group or alkenylene group is substituted with an —O— bond or —NH— bond; or a part of hydrogen of the alkylene group is a hydroxyl group or a carboxyl group An alkylene group substituted with at least one selected from the group consisting of an acyl group, a phenyl group, and a halogen atom; and n is an average value of 1 to 10)
A step of introducing -M- represented by: and (3) a step of introducing a group Y having a photopolymerizable group into M to form -MY.
The above method.

(A) a photocrosslinkable polyrotaxane; and (B) a photocrosslinkable compound;
(I) preparing the (A) photocrosslinkable polyrotaxane;
(Ii) preparing the (B) photocrosslinkable compound;
(Iii) mixing the (A) photocrosslinkable polyrotaxane and the (B) photocrosslinkable compound to obtain a composition having them;
(Iv) a step of adding a photopolymerization initiator to the composition; and (v) a step of irradiating the obtained composition with light to form a crosslinked product;
Have
Said step i)
(1) A step of preparing a polyrotaxane in which blocking groups are arranged so that the cyclic molecules are not detached at both ends of a pseudopolyrotaxane in which openings of the cyclic molecules are skewered by linear molecules;
(2) A part or all of the cyclic molecule of the polyrotaxane is represented by the following formula II (wherein X is a linear alkylene group or alkenylene group having 1 to 8 carbon atoms; branched alkylene having 3 to 20 carbon atoms) A group or alkenylene group; an alkylene group or alkenylene group in which a part of the alkylene group or alkenylene group is substituted with an —O— bond or —NH— bond; or a part of hydrogen of the alkylene group is a hydroxyl group or a carboxyl group An alkylene group substituted with at least one selected from the group consisting of an acyl group, a phenyl group, and a halogen atom; and n is an average value of 1 to 10)
A step of introducing -M- represented by: and (3) a step of introducing a group Y having a photopolymerizable group into M to form -MY.
The above method.

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