KR101765971B1 - Photocrosslinkable polyrotaxane, composition comprising the photocrosslinkable polyrotaxane, crosslinked body derived from the composition, and methods for producing same - Google Patents

Abstract

The present invention provides a photo-crosslinkable polyrotaxane having scratch resistance, low hysteresis loss, etc., a composition having the photo-crosslinkable polyrotaxane and the like, and a crosslinked body from the composition, and a process for producing the same. The present invention is characterized in that the cyclic molecule of the polyrotaxane formed by arranging the blocking group such that the cyclic molecule is not separated from both ends of the similar polyrotaxane formed by covering the opening portion of the cyclic molecule with a straight chain molecule in skewer- Wherein X is a straight chain alkylene group having 1 to 8 carbon atoms, n is an average value of 1 to 10, and Y is a group having a photopolymerizable group), a photopolymerizable polyrotaxane having a group represented by the formula A composition having a photopolymerizable polyrotaxane, a crosslinked body derived from the composition, and a method for producing the same.

Description

FIELD OF THE INVENTION The present invention relates to a photopolymerizable polyrotaxane, a photopolymerizable polyrotaxane, a composition having the photopolymerizable polyrotaxane, a crosslinked structure derived from the composition, and a method for producing the same. BACKGROUND ART SAME}

The present invention relates to a photo-crosslinkable polyrotaxane, wherein the cyclic molecule constituting the polyrotaxane is a photo-crosslinkable polyrotaxane having a photo-crosslinkable group, a composition consisting essentially of the photo-crosslinkable polyrotaxane alone, a composition having the photo- And a process for producing the same.

Various applications have been considered for polyrotaxane depending on its viscoelastic properties, and various materials have been developed.

Patent Document 1 discloses a material in which at least a part of a polymer other than polyrotaxane and polyrotaxane, that is, another polymer, is bonded through cyclic molecules. Specifically, Patent Document 1 discloses an embodiment in which a polyrotaxane and another polymer are bonded by the addition of a crosslinking agent; And an example in which a photopolymerizable group is imparted to polyrotaxane and other polymers, and both are bonded by ultraviolet irradiation.

Patent Document 2 discloses a material in which polyrotaxane molecules or polyrotaxane molecules and other polymers bind to each other by photo-crosslinking reaction. Specifically, Patent Document 2 discloses a method in which polyrotaxane is made hydrophilic or water-soluble (hydroxypropylated polyrotaxane, methylated polyrotaxanic acid, etc.) and a photo-curing machine (photopolymerizable group) are introduced and an aqueous solution of these polyrotaxane Is irradiated with ultraviolet rays to start a gel or a crosslinked product having high transparency.

Patent Document 3 discloses a hydrophobic polyrotaxane obtained by modifying a hydroxyl group of a cyclodextrin of polyrotaxane with a hydrophobic group. Particularly, it is intended to modify cyclodextrin with? -Caprolactone and to improve the solubility of polyrotaxane in a solvent such as toluene, ethyl acetate or acetone. However, the hydrophobic polyrotaxane in the examples is low in the degree of modification by? -Caprolactone and is only about 0.02.

WO2005 / 095493 WO2006 / 088200 WO2007 / 026578

However, in Patent Documents 1 and 2, crosslinking of polyrotaxane with other polymer is initiated by photo-crosslinking, but the properties of the resulting crosslinked product are merely improved viscoelasticity and optical properties of the hydrogel, Is not disclosed at all.

Patent Document 3 discloses a hydrophobic polyrotaxane prepared by modifying a hydroxyl group of a cyclodextrin with a hydrophobic group and discloses improvement of solubility in a solvent. However, there is no suggestion of initiation of photocrosslinking at all.

In addition, in general polyacrylic resin, polyurethane resin, rubber and the like, particularly in the case of using in an environment in which strain is continuously repeated (for example, a printing plate, a paint, ), It is required to improve small residual strain after expansion and contraction, repetition resistance, deterioration of deterioration and the like by suppressing loss of a part of mechanical energy by heat (hysteresis loss), but it is still insufficient.

Accordingly, it is an object of the present invention to provide a photopolymerizable polyrotaxane having unexpected characteristics such as scratch resistance, low hysteresis loss and the like from the prior art, particularly Patent Documents 1 and 2 and Patent Document 3, A composition consisting essentially of distraction, a composition having the photo-crosslinkable polyrotaxane, and a crosslinked body from the composition.

It is another object of the present invention to provide a method for producing a photopolymerizable polyrotaxane having the above properties in addition to the above object or a method for producing a composition essentially consisting of the photopolymerizable polyrotaxane alone, A process for the preparation of a composition having a crosslinked polyrotaxane and a process for producing a crosslinked product from such a composition.

The present inventors have discovered the following inventions.

Further, by using the photo-crosslinkable polyrotaxane described later, the inventors of the present invention have found that by using a photo-crosslinkable polyrotaxane, which is inherently excellent in flexibility and / or stretchability, Sieve and a composition for the above-mentioned crosslinked body can be provided.

≪ 1 > A photochemically crosslinked composition essentially consisting of (A) a photopolymerizable polyrotaxane alone,

Wherein said photopolymerizable polyrotaxane has a cyclic molecule of polyrotaxane having a group represented by the following formula (I)

Wherein the polyrotaxane is formed by disposing a blocking group such that the cyclic molecule is not separated from both ends of the polyrotaxane, which is formed by covering the opening of the cyclic molecule with a straight-chain molecule in a skewer shape.

Wherein M is represented by the above formula (II)

X is a straight chain alkylene or alkenylene group having 1 to 8 carbon atoms; A branched alkylene group or an alkenylene group having 3 to 20 carbon atoms; An alkylene group or an alkenylene group in which a part of the alkylene group or the alkenylene group is substituted with an -O- bond or an -NH- bond; Or an alkylene group in which a part of the hydrogen atoms of the alkylene group is substituted with at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group and a halogen atom, and n has 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 photocrosslinking composition having (A) a photopolymerizable polyrotaxane,

The photopolymerizable polyrotaxane has a cyclic molecule of polyrotaxane having a group represented by the above formula (I) wherein M and Y have the same definitions as above,

Wherein the polyrotaxane is formed by arranging a blocker such that the cyclic molecule is not separated from both ends of the polyrotaxane, which is formed by covering the opening of the cyclic molecule with a linear molecule in the form of a skewer.

<3> The composition according to <2> above, wherein the composition further comprises (B) a photocrosslinking compound,

The photo-crosslinking compound (B) is preferably 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.

(Wherein R ₃₃ and R ₃₄ are each independently H or CH ₃ , m 2 is 0 or 1, and * represents a position directly bonding with the polymer of the compound or bonding to the polymer through the second spacer group )

<4> In any one of <1> to <3>, it is preferable that M is a polymer derived from a lactone monomer and / or a cyclic carbonate monomer.

<5> In any one of the above items <1> to <4>, it is preferable that Y has at least one group selected from the group consisting of the following formulas III-1 to III-4.

(Wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m 1 is 0 or 1, and * represents a position directly bonded to M in formula (I) or a position bonding with M via a first spacer group)

<6> It is preferable that in any one of <1> to <5>, M is a ring opening polymer from lactone, and Y is a group having the formula (III-1).

<7> In the above item <6>, it is preferable that the lactone of M is ε-caprolactone and Y has an acryloyl group and / or a methacryloyl group, and for example, Y represents an acryloyloxyethylcarbamoyl group And / or a methacryloyloxyethylcarbamoyl group.

<8> The polymer according to any one of <3> to <7>, wherein the polymer (B) has an average molecular weight of 300 to 10,000, preferably 350 to 8000, more preferably 400 to 5,000 .

<9> In any one of <3> to <8>, the photocrosslinkable compound (B) may be one selected from the group consisting of the following formulas IV-1 to IV-4.

Among the formulas (IV-1) to (IV-4)

R ₄₁ is H or CH ₃ ,

R ₄₂ is a linear alkyl or alkenyl group having 1 to 8 carbon atoms, a branched alkyl or alkenyl group having 3 to 20 carbon atoms, an alkyl or alkenyl group in which a part of the alkyl or alkenyl group is substituted with an -O- or -NH- An alkenyl group or an alkyl or alkenyl group in which a part of the hydrogen of the alkyl or alkenyl group is substituted with at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group and a halogen atom,

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 trimethylol propane, trimethylol ethane, glycerol, pentaerythritol, dipentaerythritol, isocyanuric acid, diisocyanuric acid, triazine, benzene or a derivative thereof,

M 'is a group having a polymer moiety,

Y 'represents at least one kind of group selected from the above-mentioned group Y'

m2 &quot; is 0 or 1,

Z each independently represent a simple bond or a divalent second spacer group,

r 'represents an integer of 3 to 6, preferably 3 to 4, more preferably 3,

The symbol () in parentheses indicates that it is a repeating unit.

<10> In any one of <1> to <9>, the cyclic molecule may be selected from the group consisting of? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin.

<11> The pharmaceutical composition according to any one of <1> to <10>, wherein the linear molecule is selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethylcellulose, hydroxyethylcellulose, Hydroxypropylcellulose and the like), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and the like and / Polyolefin-based resins such as polyethylene, polypropylene, and copolymer resins with other olefin-based monomers, polyester resins, polyvinyl chloride resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, (Meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer Acrylic resin such as a resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinylbutyral resin and the like; And derivatives or modified products thereof, polyamides such as polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin) and nylon, polyimides, polyisoprene, polybutadiene , Polysiloxanes such as polydimethylsiloxane and the like, polysulfones, polyimines, polyanhydrides, polyaromatics, polyarylates, polyphosphazenes, polyketones, polyphenols, For example, polyolefins such as polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, poly Propylene, polyvinyl alcohol, and polyvinyl methyl ether, and more specifically, Polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene. Particularly preferably, it is polyethylene glycol.

<12> In any one of <1> to <11>, it is preferable that 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.

<13> The method according to any one of <1> to <12> above, wherein the blocking group is selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluororesins, silsesquioxanes, Substituted benzenes (which may be substituted with one or more substituents, such as alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, A polynuclear aromatic group which may be substituted (the substituent may be the same as the above but is not limited thereto, one or plural substituents may be present), and steroids. Further, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluororesins, silsesquioxanes and pyrenes, more preferably adamantane groups Or a trityl stream.

<14> It is preferable that in any one of <1> to <13>, the cyclic molecule is derived from? -Cyclodextrin and the linear molecule is polyethylene glycol.

<15> In any one of the above items <1> to <14>, when the amount of encapsulating the cyclic molecule at the maximum when the cyclic molecule is enclosed in the skewer shape by the linear molecule is 1, , Preferably 0.01 to 0.5, more preferably 0.05 to 0.4.

<16> A crosslinked body derived from the composition according to any one of <1> and <10> to <15>.

<17> A crosslinked body derived from the composition according to any one of <2> and <10> to <15> above.

<18> A crosslinked body derived from the composition according to any one of <2> to <15> above.

<19> A crosslinked body derived from a composition according to any one of <3> to <15> above.

<20> In any one of <16> to <19>, the crosslinked body may be crosslinked through Y of a crosslinkable polyrotaxane (A) by light irradiation.

<21> In the above-mentioned <19>, it is preferable that Y in the crosslinkable polyrotaxane (A) and Y 'in the crosslinkable compound (B) are at least crosslinked by light irradiation.

<22> In any one of <16> to <21>, the cross-linked body preferably has a hysteresis loss of 25% or less, preferably 20% or less, more preferably 15% or less.

<23> A method for producing (A) a photopolymerizable polyrotaxane,

(1) a step of preparing a polyrotaxane in which a blocking group is arranged so that cyclic molecules are not separated from both ends of a similar polyrotaxane formed by covering the opening of the cyclic molecule with a linear molecule in the form of a skewer;

(2) introducing -M- represented by the following formula (II) to part or all of the cyclic molecule of the polyrotaxane;

(3) a step of introducing a group Y having a photopolymerizable group to M to form -M-Y

&Lt; / RTI &gt;

(Wherein X is a straight chain alkylene group or an alkenylene group having 1 to 8 carbon atoms, a branched chain alkylene group or an 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 an NH- bond, or an alkylene group in which part of the hydrogen atoms of the alkylene group is substituted with at least one member 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)

(A) a photopolymerizable polyrotaxane; And (B) a photocrosslinking compound,

(i) preparing (A) a photopolymerizable polyrotaxane;

(ii) preparing a photochemically crosslinkable compound (B); And

(iii) a step of mixing a photopolymerizable polyrotaxane (A) and a photopolymerizable compound (B) to obtain a composition having them

Lt; / RTI &

Step i)

(1) a step of preparing a polyrotaxane in which a blocking group is arranged so that cyclic molecules are not separated from both ends of a similar polyrotaxane formed by covering the opening of the cyclic molecule with a linear molecule in the form of a skewer;

(2) introducing -M- represented by the above formula (II) into part or all of the cyclic molecule of polyrotaxane; And

(3) a step of introducing a group Y having a photopolymerizable group to M to form -M-Y

&Lt; / RTI &gt;

(25) a photopolymerizable polyrotaxane; And (B) a photo-crosslinkable compound,

(i) preparing (A) a photopolymerizable polyrotaxane;

(ii) preparing a photochemically crosslinkable compound (B);

(iii) mixing the (A) photopolymerizable polyrotaxane and (B) the photocrosslinking compound to obtain a composition having them;

(iv) adding a photopolymerization initiator to the composition; And

(v) a step of irradiating the obtained composition with light to form a crosslinked body

Lt; / RTI &

Step i)

(1) a step of preparing a polyrotaxane in which a blocking group is arranged so that cyclic molecules are not separated from both ends of a similar polyrotaxane formed by covering the opening of the cyclic molecule with a linear molecule in the form of a skewer;

(2) introducing -M- represented by the above formula (II) into part or all of the cyclic molecule of polyrotaxane; And

(3) a step of introducing a group Y having a photopolymerizable group to M to form -M-Y

Lt; / RTI &gt;

<26> In any one of (23) to (25), the monomer having the structure represented by the following formula (II ') may be subjected to ring-opening polymerization to introduce -M-.

(Wherein X is a straight chain alkylene group or an alkenylene group having 1 to 8 carbon atoms, a branched chain alkylene group or an 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 an NH-bond, or an alkylene group in which a part of the hydrogen atoms of the alkylene group is substituted with at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group and a halogen atom)

According to the present invention there is provided a photopolymerizable composition comprising a photopolymerizable polyrotaxane, each having an unexpected characteristic from the prior art, such as scratch resistance, low hysteresis loss, etc., a composition essentially consisting of said photopolymerizable polyrotaxane alone, And a cross-linked form from these compositions.

In addition to or in addition to the above effects, the present invention also provides a method for producing a photopolymerizable polyrotaxane having the above characteristics, a method for producing a composition essentially consisting of the photopolymerizable polyrotaxane alone, A process for preparing a composition having a crosslinked polyrotaxane, and a process for producing a crosslinked product from the composition.

1 is a view for explaining how a hysteresis loss value is obtained from a stress-strain curve of a tensile test.
Fig. 2 is a diagram showing a history of tension and recovery five times in the tensile test for measuring the hysteresis loss value, wherein (a) shows Comparative Example 1, (e) shows the result of Example 9, (c) and (d) are the results of Example 11, and the arrows in the drawing show the first stretching curve.

Hereinafter, the present invention will be described in detail.

The present invention relates to a photo-crosslinkable polyrotaxane, wherein the cyclic molecule constituting the polyrotaxane is a photo-crosslinkable polyrotaxane having a photo-crosslinkable group, a composition consisting essentially of the photo-crosslinkable polyrotaxane alone, a composition having the photo- And a process for producing the same. The following description will be given in the order mentioned above.

&Lt; Photo-crosslinkable polyroctic acid having cyclic molecule constituting polyrotaxane is a photocrosslinkable group >

The photopolymerizable polyrotaxane of the present invention has a group in which the cyclic molecule of polyrotaxane is represented by the following formula (I).

Further, polyrotaxane refers to a block copolymer which is formed by arranging a blocker so that the cyclic molecule is not separated from both ends of the polyrotaxane, which is formed by covering the opening of the cyclic molecule with a straight-chain molecule in a skewer shape.

In the formula (I), M is represented by the following formula (II), and Y represents a group having a photopolymerizable group.

In Formula (II), X is a straight chain alkylene group or alkenylene group having 1 to 8 carbon atoms; A branched alkylene group or an alkenylene group having 3 to 20 carbon atoms; An alkylene group or an alkenylene group in which a part of the alkylene group or the alkenylene group is substituted with an -O- bond or an -NH- bond; Or an alkylene group in which a part of hydrogen of the alkylene group is substituted with at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group and a halogen atom. Preferably, X is a straight chain 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 a straight-chain 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. Although n is a structural integer, n is not limited to an integer because it has dispersibility depending on the conditions of introduction of M and the like.

As an example, n can be calculated as follows. That is, polyrotaxane (straight chain molecule: polyethylene glycol having an average molecular weight of 35,000, cyclic molecule:? -Cyclodextrin (? -Cyclodextrin (?)) Produced by the method described in WO2005 / 080469 (the contents of which are incorporated herein by reference in its entirety) 4 to 6 ppm (derived from H of the hydroxyl group of the? -CD and H of the C1) in the ¹ H-NMR (DMSO-d6) analysis chart in the polyrotaxane including the blocking agent: adamantanamine group) From the integral ratio of 3 to 4 ppm (H of PEG), it was found that the porosity of alpha -CD was 0.25. ¹ H-NMR analysis was performed with 400 MHz JEOL JNM-AL400 (manufactured by Nihon Denshi Kabushiki Kaisha). However, it is assumed that 2 units of the -CH ₂ -CH ₂ -O- repeating unit of PEG corresponds to the thickness of? -CD, and the case of the closest coverage is 1.0. Thereby, it was calculated that the theoretical hydroxyl value of the polyrotaxane was 13.6 mmol / g (average molecular weight: 35000+ (35000/88 * 0.25 * 972) 88 * 0.25 * 18) mmol / g). Further, in the case of adding a mercapto group to a part of? -CD, for example, in the case of a hydroxypropyl group (-CH ₂ CH (CH ₃ ) OH), ¹ H-NMR (DMSO- Based on the integral value of the methyl group in the hydroxypropyl group as the signal). For example, 50%. The theoretical hydroxyl value is calculated by the same method and it is 9.7 mmol / g. Further, ring-opening polymerization is carried out at a hydroxyl group using? -Caprolactone monomer. Consumption of the monomers used in the reaction is confirmed by gas chromatography (GC) (GC-2014 manufactured by Shimadzu Corporation, use column CBP1-W12-100). The consumption of monomers almost matched the feed (almost all). Therefore, the value of [monomer] / [OH] in the polyrotaxane grafted with the target compound, polycaprolactone, can be calculated and the value is taken as the average n. In the above example, n = (4.5 / 114.1 * 1000) /9.7=4.1 when all is consumed by using 4.5 g of epsilon -caprolactone using 1 g of hydroxypropyl-modified polyrotaxane.

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

4-membered ring lactones such as? -Propiolactone,? -Methylpropiolactone and L-serine-? -Lactone derivatives as lactone monomers; ? -hexanolactone,? -hexanolactone,? -decanolactone,? -dodecanolactone,? -hexyl-? -butyrolactone,? -heptanolactone,? -heptanolactone, ? -butyrolactone,? -butyrolactone,? -butyrolactone,? -hydroxy-? -butyrolactone,? -methyl-? -decanolactone,? -methylene- ? -Undecanolactone,? -Valerolactone,? -Butyrolactone,? -Butyrolactone,? -Butyrolactone,? -Butyrolactone, , 2-pentamethylene-1,3-dioxolan-4-one,? -Bromo-? -Butyrolactone,? -Crotonolactone,? -Methylene-? -Butyrolactone,? -Methacryloyloxy 5-membered ring lactone such as cy-y-butyrolactone, and beta -methacryloyloxy- gamma -butyrolactone; ? -decenoolactone,? -treecanolactone,? -trecanolactone,? -decanolactone,? -decanolactone,? -decanolactone,? -decanolactone,? -valerolactone,? -valerolactone,? -hexanolactone, 6-membered cyclic lactones such as tetradecanolactone, DL-mevalonolactone and 4-hydroxy-1-cyclohexanecarboxylic acid? -Lactone; 7-membered ring lactone such as epsilon -caprolactone; Lactide, and 1,5-dioxepan-2-one. It is preferable that the lactone monomer is? -Caprolactone,? -Butyrolactone,? -Methyl-? -Butyrolactone,? -Valerolactone and lactide, more preferably? -Caprolactone.

As the cyclic carbonate, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, glycerol 1,2-carbonate, 4- (methoxymethyl) -1,3-dioxolan- 4-chloromethyl-5-methyl-1,3-dioxol-2-one, 4 Dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolane-2 5-membered cyclic carbonates such as &lt; RTI ID = 0.0 &gt; Dioxolan-2-one, 5-methyl-5-propyl-1,3-dioxolan- And the like, but is not limited thereto.

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). Wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m 1 is 0 or 1, and * represents a position directly bonded to M in formula (I) or a position bonding with M through a first spacer group.

Also, the first spacer group is a group which bonds with a divalent group, that is, Y and M. The -CH ₂ -CH ₂ a first spacer group -, -C (= O) -NH -CH 2 -CH 2 -, -C (CH 3) 2 NH-C (= O) -, -CH (OH) _{CH 2 -, -CH 2 -CH 2} -O-CH 2 -CH 2 -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 -CH ₂ -, but, and the like, and the like.

Specifically, Y can be introduced, for example, by reacting with the terminal hydroxyl group of M using the following compounds.

(Meth) acryloyl chloride, (meth) acrylic acid anhydride, 2- (meth) acryloyloxyethyl isocyanate, 2- (2- methacryloyloxyethyl) ethyl isocyanate, 2- (Meth) acrylate, glycidyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) succinate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl Methacryloyloxy-γ-butyrolactone, p-vinylbenzoic acid, pt-butylstyrene, isocyanic acid 3- Maleimidopropionic acid N-succinimidyl, 4-maleimidobutyric acid N-succinimidyl, 6-maleimidohexanoic acid N - Succin Imilil and so on.

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

Hereinafter, the elements constituting the polyrotaxane will be described.

<< illusion molecule >>

The cyclic molecule is not particularly limited as long as it is a molecule in which linear molecules are encapsulated in a skewer shape in the opening portion.

The cyclic molecule is preferably a cyclic molecule having a hydroxyl group, and is preferably selected from the group consisting of? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin. When the cyclic molecule has a hydroxyl group, a part of the hydroxyl group may be substituted by another group. Examples of the other group include, but are not limited to, a hydrophilic group that hydrophilizes the polyrotaxane of the present invention, a hydrophobic group that hydrophobizes the polyrotaxane of the present invention, and a photoreactive group.

<< Straight Molecules >>

The straight chain molecule of the polyrotaxane of the present invention is not particularly limited as long as it can be embedded in the opening of the cyclic molecule in a skewer shape.

Examples of the linear molecule include polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like), polyacrylamide, Polypropylene, and other olefin-based monomers such as polyethylene, polypropylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and the like and / A polystyrene resin such as a polystyrene or an acrylonitrile-styrene copolymer resin, a polymethyl methacrylate or a (meth) acrylic acid ester copolymer, an acrylonitrile- Nitrile-methyl acrylate copolymer resin, and the like, Polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resin, polyvinylbutyral resin and the like; And derivatives or modified products thereof, polyamides such as polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin) and nylon, polyimides, polyisoprene, polybutadiene , Polysiloxanes such as polydimethylsiloxane and the like, polysulfones, polyimines, polyanhydrides, polyaromatics, polyarylates, polyphosphazenes, polyketones, polyphenols, And olefins, and derivatives thereof. For example, a polymer selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether good. More specifically, it is preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene, particularly preferably polyethylene glycol.

The straight-chain molecule preferably has 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, it is preferable that the cyclic molecule is derived from? -Cyclodextrin and the linear molecule is polyethylene glycol.

When the amount of the cyclic molecule is maximally encapsulated when the cyclic molecule is enclosed in a skewer shape by the straight chain molecule, the cyclic molecule preferably has a cyclic molecule in an amount of 0.001 to 0.6, preferably 0.01 to 0.5, more preferably 0.05 to 0.4 It is preferable to enclose the linear molecule in a skewer shape in an amount.

Further, 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 alpha -cyclodextrin molecule, the maximum inclusion amount is experimentally determined (see Macromolecules 1993, 26, 5698-5703) All incorporated herein by reference).

<< Sealer >>

The blocking group of the polyrotaxane of the present invention is not particularly limited as long as it is a group disposed at both ends of a similar polyrotaxane and acting to prevent the cyclic molecule from leaving.

For example, as the blocking agent, there can be used at least one compound selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluororesins, silsesquioxanes, pyrenes, (Which may be substituted with one or more substituents), a polynuclear aromatic group which may be substituted (a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms as a substituent, The substituents may be the same or a plurality of substituents may be present), and steroids. Further, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluororesins, silsesquioxanes and pyrenes, more preferably adamantane groups Or a trityl stream.

&Lt; Composition consisting essentially of photopolymerizable polyrotaxane only >

The present invention provides a composition consisting essentially of the above-described photo-crosslinkable polyrotaxane alone.

The phrase &quot; essentially consisting of only &quot; means that the photocrosslinkable material of the composition is composed only of a photopolymerizable polyrotaxane and does not contain other photocrosslinkable substances, and various other additives, for example, A photopolymerization initiator; Sensitizer; Silane coupling agents; Surfactants; Plasticizers; Thickener; Silica fine particles; Alumina fine particles; Pigments; Antioxidants; Antistatic agents; Antimicrobial agents; Light stabilizer; Natural oil; A solvent for dissolving the photopolymerizable polyrotaxane, and the like.

In other words, when the photo-crosslinking is carried out by using the &quot; composition consisting essentially of the photo-crosslinkable polyrotaxane alone &quot;, the resulting crosslinked product is derived exclusively from the photo-crosslinkable polyrotaxane. However, the above-mentioned additives may be included in the composition.

The solvent for dissolving the photopolymerizable polyrotaxane depends on the kind of M, the kind of Y described above, the linear molecule used, the cyclic molecule used, the blocking group used, and the like. Examples of the solvent include, but are not limited to, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methylene chloride, N, N'-dimethylformamide, dimethylacetamide .

&Lt; Composition having photopolymerizable polyrotaxane >

The present invention also provides a composition having the above-mentioned photo-crosslinkable polyrotaxane.

The term &quot; having photopolymerizable polyrotaxane &quot;, particularly &quot; having photopolymerizable &quot; means that the photopolymerizable compound in the composition includes not only photopolymerizable polyrotaxane but also other photocrosslinkable. The composition may, of course, also contain various other additives, such as those mentioned above; A solvent for dissolving the photopolymerizable polyrotaxane, and the like.

<< (B) Photocrosslinkable compound >>

Other photo-crosslinkable compounds in the composition of the present invention include photo-crosslinkable compounds. That is, the composition of the present invention preferably has (B) a photo-crosslinkable compound in addition to (A) the photo-crosslinkable polyrotaxane.

The photo-crosslinking compound is preferably a polymer having at least one group selected from the group Y 'consisting of the following formulas (III'-1 to III'-4) in the molecule of the compound. Wherein R ₃₃ and R ₃₄ are each independently H or CH ₃ , m 2 is 0 or 1, and * represents a position directly bonding with the polymer of the compound or bonding to the polymer via the second spacer group. Further, the second spacer group has the same definition as the first spacer described above, and the same one can be used independently of the first spacer.

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

In particular, the photocrosslinkable compound is preferably one selected from the group consisting of the following formulas (IV-1) to (IV-4).

Among the formulas (IV-1) to (IV-4)

R ₄₁ is H or CH ₃ ,

R ₄₂ is a linear alkyl or alkenyl group having 1 to 8 carbon atoms, a branched alkyl or alkenyl group having 3 to 20 carbon atoms, an alkyl or alkenyl group in which a part of the alkyl or alkenyl group is substituted with an -O- or -NH- An alkenyl group or an alkyl or alkenyl group in which a part of the hydrogen of the alkyl or alkenyl group is substituted with at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group and a halogen atom,

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 trimethylol propane, trimethylol ethane, glycerol, pentaerythritol, dipentaerythritol, isocyanuric acid, diisocyanuric acid, triazine, benzene or a derivative thereof,

M 'is a group having a polymer moiety,

Y 'represents at least one kind of group selected from the above-mentioned group Y'

m2 &quot; is 0 or 1,

Z each independently represent a simple bond or a divalent second spacer group,

r 'represents an integer of 3 to 6, preferably 3 to 4, more preferably 3,

In the formulas (IV-1) to (IV-4), parentheses () indicate that they are repeating units.

The second spacer group can be specifically the same as the first spacer group described above.

&Lt; Crosslinked body derived from the composition &

The present invention provides a crosslinked body derived from the above composition.

That is, the present invention relates to a crosslinked product derived from a composition consisting essentially of two kinds of photopolymerizable polyrotaxane only; And b) a crosslinked body derived from a composition having a photopolymerizable polyrotaxane.

Further, the crosslinked product derived from the composition consisting essentially of (a) the photo-crosslinking polyrotaxane alone is derived from the photo-crosslinkable polyroctic acid only as described above. On the other hand, when a) a bridged product derived from a composition having a) a photopolymerizable polyrotaxane is derived only from a photopolymerizable polyrotaxane, a photopolymerizable polyrotaxane and a photopolymerizable compound other than the photopolymerizable polyrotaxane, May be derived from a photo-crosslinking compound.

It is preferable that the crosslinked product of (a) and / or (b) is crosslinked through Y of the crosslinkable polyrotaxane (A) described above by light irradiation.

Particularly, a crosslinked form of a) essentially consisting of a crosslinked form of a), that is, a composition consisting essentially of a photopolymerizable polyrotaxane only, is preferably crosslinked through at least two molecules of (A) the crosslinkable polyrotaxane.

(B), that is, a crosslinked product derived from a composition having a photopolymerizable polyrotaxane, is a crosslinked product which is crosslinked through Y-links of at least two molecules of (A) a crosslinkable polyrotaxane; (A) Crosslinkable polyrotaxane Y and other photo-crosslinkable ones, for example, a cross-linked product which is crosslinked through Y 'of the above-mentioned (B) photo-crosslinkable compound; (A) Y of the crosslinkable polyrotaxane and (Y) of the crosslinkable compound (B) are preferably at least crosslinked.

The crosslinked product of the present invention preferably has an initial modulus of elasticity in the 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 preferably has a hysteresis loss of 25% or less, preferably 20% or less, more preferably 15% or less.

Here, the hysteresis loss refers to a mechanical energy loss rate (hysteresis loss) in one cycle of deformation and recovery in accordance with JIS K6400, in which a deformation by a tensile test of a material is used instead of a deformation of a material.

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 to measure a stress-strain curve. The hysteresis loss at this time is calculated by measuring the area by the method shown in Fig. 1, where the elongation is 20% of the effective length and the recovery is at rest (first elongation-recovery cycle).

Hysteresis loss (%) = area (oabcd) of Figure 1 / area (oabeo) of Figure 1 × 100

Compositions consisting essentially of the photo-crosslinkable polyrotaxane, the photo-crosslinkable polyrotaxane alone or the photo-crosslinkable polyrotaxane of the present invention, the crosslinked body derived from the above-mentioned composition is a mixture of the viscoelasticity of polyrotaxane and the Flexibility, and / or stretchability, as well as applications in which scratch resistance is required and / or low hysteresis loss is required.

These fields include paints and coating materials for automobiles, electric appliances, furniture and the like; Interior materials of automobiles; Adhesive or pressure sensitive adhesive; Material of printing plate; Rubbing members of dental hygiene materials, machines, automobiles, etc .; Sealing materials, and waterproofing materials; Electronic and electrical materials such as materials for medical and sports goods, insulating materials, sealing materials, heat transfer materials, and binders for conductive materials; Insulated actuator material; But are not limited to, optical materials, vibration-proof / vibration-damping / anti-seismic materials, cosmetic materials, rheology control agents, fiber materials, and medical biomaterials.

&Lt; Preparation of photo-crosslinkable polyrotaxane >

The photo-crosslinkable polyrotaxane of the present invention can be produced, for example, by the following production method.

(1) a step of preparing a polyrotaxane in which a blocking group is arranged so that cyclic molecules are not separated from both ends of a similar polyrotaxane formed by covering the opening of the cyclic molecule with a linear molecule in the form of a skewer;

(2) introducing -M- represented by the above formula (II) into part or all of the cyclic molecule of polyrotaxane; And

(3) a step of introducing a group Y having a photopolymerizable group to M to form -M-Y

. &Lt; / RTI &gt;

Further, other steps may be carried out before or after the above-mentioned steps. For example, after the step (1), before the step (2), after the step (2), before the step (3), or after the step (3) .

Step (1) is a step of preparing polyrotaxane. The polyrotaxane can be obtained by reference to documents published prior to the present application (for example, WO2005 / 080469, WO2005 / 108464 and WO2009 / 136618, the entire contents of which are incorporated herein by reference).

Step (2) is a step of introducing -M- represented by the above formula (II) into part or all of the cyclic molecules of the polyrotaxane.

In this step, a monomer having a structure represented by the following formula (II ') is subjected to ring-opening polymerization to introduce -M-.

The step (2) depends on the polyrotaxane to be used and -M- to be introduced. The reaction is carried out under the conditions of 100 ° C to 130 ° C, normal pressure, toluene, xylene or the like in the presence of a tin catalyst It is good to do.

&Lt; Process for producing composition essentially consisting of photopolymerizable polyrotaxane only >

The composition consisting essentially of the photopolymerizable polyrotaxane alone can be obtained by mixing the above-mentioned photopolymerizable polyrotaxane with a solvent and other additives.

&Lt; Process for producing a composition having photopolymerizable polyrotaxane >

Compositions having photopolymerizable polyrotaxane, in particular (A) a photopolymerizable polyrotaxane; And (B) a photo-crosslinkable compound can be obtained, for example, by the following method.

(i) preparing (A) a photopolymerizable polyrotaxane;

(ii) preparing a photochemically crosslinkable compound (B); And

(iii) a step of mixing a photopolymerizable polyrotaxane (A) and a photopolymerizable compound (B) to obtain a composition having them

. &Lt; / RTI &gt;

Further, the step i) is preferably carried out by the above-described method for producing a photopolymerizable polyrotaxane.

&Lt; Process for producing a crosslinked product derived from the composition &

The crosslinked product of the present invention can be obtained, for example, by the following method.

For example, when a composition consisting essentially of a photopolymerizable polyrotaxane alone is used as the composition,

(iv ') adding a photopolymerization initiator to the composition; And

(v ') Step of forming a crosslinked body by irradiating the obtained composition with light

The crosslinked product of the present invention can be obtained.

Also disclosed is a composition having a photopolymerizable polyrotaxane, particularly (A) a photopolymerizable polyrotaxane; And (B) a photo-crosslinkable compound is used,

(i) preparing (A) a photopolymerizable polyrotaxane;

(ii) preparing a photochemically crosslinkable compound (B);

(iii) mixing the (A) photopolymerizable polyrotaxane and (B) the photocrosslinking compound to obtain a composition having them;

(iv) adding a photopolymerization initiator to the composition; And

(v) a step of irradiating the obtained composition with light to form a crosslinked body

The crosslinked product of the present invention can be obtained.

Examples of the photopolymerization initiator of the above (iv) or (iv ') include quinones, aromatic ketones, benzoin, benzoin ethers, biimidazole compounds and derivatives thereof, N-phenylglycines, A combination thereof, a combination of a nonimidazole compound and its derivative and a Michler's ketone, at least one selected from the group consisting of acridines and oxime esters. Specific examples thereof include 2-ethyl anthraquinone, octaethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, , Quinones such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone and 3- , Aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone] and 4,4'-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, Benzoin ethers such as phenyl ether, methyl benzoin and ethyl benzoin, nonimidazole compounds and derivatives thereof such as benzyldimethyl ketal, benzyldiethyl ketal and triarylimidazolyl dimer, N-phenylglycine, N- N-phenylglycine such as methyl-N-phenylglycine and N-ethyl-N-phenylglycine, a combination of thioxanthones and alkylaminobenzoic acid such as ethylthioxanthone and dimethylamino A combination of ethyl benzoate, 2-chlorothioxanthone and ethyl dimethylaminobenzoate, a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate, and a triarylimidazolyl dimer and other nonimidazole compounds and derivatives thereof, and Michler's ketone , Acridines such as 9-phenyl acridine, 1-phenyl-1,2-propanedione-2-o-benzoin oxime, 1-phenyl- Oxycarbonyl) oxime, and the like. Preferably, dialkylaminobenzoic acid esters such as diethylthioxanthone, chlorothioxanthone and the like and ethyl dimethylaminobenzoate, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4 , 4'-bis (diethylamino) benzophenone, triarylimidazolyl dimer and the like, 9-phenylacridine, N-phenylglycine, and combinations thereof. Examples of nonimidazole compounds and derivatives thereof such as triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ', 5 (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- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis (triphenylphosphine) - (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetrakis- (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 2,2 ' (2,6-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- , 3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- 5,4'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-tri Fluorophenyl) -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 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) 4 ', 5 , 5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and the like, but are not limited thereto.

Further, when the photopolymerization initiator is contained in the composition, the step (iv) or (iv ') may not be present.

Step (v) is a step of irradiating the composition with light to form a crosslinked body.

The light irradiation depends on the conditions such as the photopolymerization initiator, the sensitizer, the thickness and the shape of the sample to be used, and basically, it can be used as long as it is a device mainly composed of light rays from the ultraviolet ray to the wavelength region of visible light (200 to 450 nm). For example, a mercury lamp, a metal halide lamp, or a mercury xenon lamp may be used as a light source. For example, the wavelength: 365 nm; Light intensity: 30 to 150 mW / cm ² ; And irradiation time: 10 seconds to 5 minutes.

Further, before the step (v), the composition may be applied to various substrates by a conventionally known method. As a result, it is possible to form a desired crosslinked body on a substrate, and the crosslinked body can be used not only for the effects of the present invention, for example, the viscoelasticity inherent to polyrotaxane and the flexibility and / Low hysteresis loss, and the like.

(Example)

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1

Straight chain molecule: polyethylene glycol (average molecular weight: 3.5 million), polyrotaxane containing cyclic molecule:? -Cyclodextrin (hereinafter simply referred to as "dextrin" (Hereinafter, referred to as &quot; HAPR35 &quot;) is described in WO2005 / 080469 (the contents of which are incorporated herein by reference in their entirety) (Average molecular weight Mw: 150,000 by gel permeation chromatography (GPC)) was prepared in the same manner as in Example 1 (? -CD porosity: 25%; hydroxypropyl group modification ratio: ). The measurement of the molecular weight and the molecular weight distribution was carried out using a Tosoh HLC-8220 GPC apparatus. Column: TSK guard column Super AW-H and TSKgel Super AWM-H (two connections) Eluent: dimethyl sulfoxide / 0.01M LiBr Column oven 50 ° C Flow rate 0.5 ml / / vol%, injection amount: 20 쨉 l, pre-treatment: filtration with a 0.2 탆 filter, and measurement under a standard molecular weight: PEO.

<1-1. Polycaprolactone Modification of Hydroxypropylated Polyroctic Acid>

5 g of the hydroxypropylated polyrotaxane (HAPR35) obtained above was dissolved in 22.5 g of? -Caprolactone at a temperature of 80 占 폚 to obtain a mixed solution. This mixed solution was stirred at 110 ° C for 1 hour while blowing dry nitrogen, and then 0.16 g of a 50 wt% xylene solution of tin (II) 2-ethylhexanoate was added and 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 non-volatile concentration of about 35% by weight.

Polymerization degree of polycaprolactone was examined based on the amount of theoretical hydroxyl group of the raw material HAPR35 and the amount of monomer consumption (approximately 100%) of gas chromatography (GC) with respect to the obtained polyrotaxane X-1. As a result, there was.

<1-2. Introduction of Acrylyl Group into Polycaprolactone Modified Hydroxypropylated Polyroctanic Acid>

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

Example 2

Except that 21.5 g of? -Caprolactone and 1.0 g of? -Methyl-? -Butyrolactone were used instead of 22.5 g of? -Caprolactone of Example 1-1, To prepare taxane A-2. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 580,000.

The copolymer of ε-caprolactone and α-methyl-γ-butyrolactone was obtained from the obtained polyrotaxane A-2 by the theoretical hydroxyl group content of the raw material HAPR35 and the monomer consumption (approximately 100%) by gas chromatography (GC) As a result of investigation of the polymerization degree of the coalescence, it was found that the degree of polymerization was 4.1.

Example 3

A modified polyrotaxane A-3 was prepared in the same manner as in Example 1, except that 43.0 g of? -Caprolactone and 2.0 g of propylene carbonate were used instead of 22.5 g of? -Caprolactone of Example 1-1 Respectively. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 560,000.

The degree of polymerization of the copolymer of? -Caprolactone and propylene carbonate was examined with respect to the obtained polyrotaxane A-3 by the theoretical hydroxyl group content of the raw material HAPR35 and the monomer consumption amount (approximately 100%) of GC, Could know.

Example 4

A modified polyrotaxane A-4 was prepared in the same manner as in Example 1 except that acetylated polyrotaxanic acid was used instead of the hydroxypropylated polyrotaxane of Example 1. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 480,000.

Further, the acetylated polyrotaxane (? -CD packing ratio: 27%, acetyl group modifying rate: 50%, theoretical hydroxyl value: 5.4 mmol / g by ¹ H-NMR analysis, average weight molecular weight Mw: 100,000 ) Was prepared in the same manner as described in WO2005 / 080469 (the contents of which are all incorporated herein by reference).

The degree of polymerization of the polycaprolactone of the obtained polyrotaxane A-4 was 7.3 as in Example 1.

Example 5

&Lt; Introduction of methacryloyl group to hydroxpropylated polyroctic acid with polycaprolactone >

A modified polyrotaxane A-5 was prepared 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 in Example 1. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 560,000. Y is a methacryloyl group (-OC (═O) -CH (CH ₃ ) -CH ₂ ), and the first spacer group is -C (═O) -NH-CH ₂ -CH ₂ .

Example 6

<Introduction of Acrylyl Group and Butyl Carbamoyl Group to Hydroxypropylated Polyrotaxane Represented by Polycaprolactone>

Acryloyloxyethyl isocyanate and 2.5 g of butyl isocyanate were used instead of 7.1 g of 2-acryloyloxyethyl isocyanate in Example 1, the modified polyrotaxane A-6 Respectively. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 590,000. In the obtained A-6, Y is an acryloyl group (-OC (= O) -CH = CH ₂ ), the first spacer group is -C (= O) -NH-CH ₂ -CH ₂ , Some were modified with butyl carbamoyl groups.

Example 7

&Lt; Introduction of methacryloyl group and butyl carbamoyl group to hydroxpropylated polyrotaxane represented by polycaprolactone >

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, and the modified polyrotaxane A- 7 was prepared. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 600,000. Y is a methacryloyl group (-OC (= O) -CH = CH ₂ ), the first spacer group is -C (= O) -NH-CH ₂ -CH ₂ , and M Was modified with a butylcarbamoyl group.

Example 8

<Introduction of? -Methylstyryl group into polycaprolactone-modified hydroxypropylated polyrotaxane>

Except that 9.0 g of 3-isopropenyl-?,? -Dimethylbenzyl isocyanate was used instead of 7.1 g of 2-acryloyloxyethyl isocyanate in Example 1 to obtain a modified polyrotaxane A -8. By GPC measurement, the average weight-average molecular weight Mw of the obtained polyroctic acid was 470,000. 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- O) -.

&Lt; Production example of photo-crosslinkable oligomer &

[Synthesis Example 1]

&Lt; Synthesis of methacryloyl group-modified polycarbonate >

(Polycarbonate diol having a polyalkylene carbonate diol content of 96% by weight or more, 1,5-pentanediol 2% by weight or less and 1,6-hexanediol 2% by weight or less, Asahi Kasei 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko K.K.) was added to 30 g of a commercially available polyvinyl alcohol (trade name: DYRANOL (registered trademark) T-5650J, manufactured by Chemicals, (MOI), 0.01 g of dibutylhydroxytoluene (polymerization inhibitor) and 0.06 g of dibutyltin dilaurate were slowly added dropwise, and the mixture was allowed to react at 40 DEG C for 5 hours to obtain a 71% non-volatile fraction containing both methacryloyl groups Thereby obtaining a polycarbonate oligomer B-1.

The average molecular weight Mw of the obtained oligomer B-1 was measured by GPC and found to be 1270.

[Synthesis Example 2]

<Synthesis of acryloyl group-modified polycaprolactone oligomer>

5 g of polycaprolactone-modified hydroxyethyl acrylate (Flaxel (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 was added 8.3 g of isocyanurate type hexamethylene diisocyanate (DURANATE (registered trademark) TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd.), and the reaction was carried out. Thus, three acrylic To obtain a modified polycaprolactone oligomer B-2 having a diarrhea.

The average molecular weight Mw of the obtained oligomer B-2 was measured by GPC and found to be 1540.

[Synthesis Example 3]

&Lt; Synthesis of Methacryloyl Group-Modified Acrylic Copolymer >

9 ml of butyl acetate was placed in a reactor equipped with a stirrer, a reflux condenser and a thermometer, and while refluxing at 120 DEG C, 14 g of butyl acrylate, 4 g of methyl methacrylate, 2 g of hydroxyethyl methacrylate, And 1.2 g of bisisobutyronitrile (AIBN) was added dropwise to the reactor over 2 hours. Thereafter, 0.2 g of AIBN was further added, and the reaction was continued for 3 hours. The reaction solution cooled to room temperature was poured into hexane, and the precipitated liquid product was recovered. To the recovered product, 20 ml of butyl acetate, 1 ml of dibutylhydroxytoluene (polymerization inhibitor) and 0.02 g of dibutyltin dilaurate were added, 2-methacryloyloxyisocyanate was added dropwise at 40 ° C with stirring, To obtain an acrylic oligomer (copolymer of butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate) B-3 having a large number of methacryloyl groups having a nonvolatile content of about 52% ( ¹ H-NMR analysis due to). As a result of GPC analysis, the weight average molecular weight Mw was 7,500 and the dispersion Mw / Mn was 1.8. Further, it was confirmed that a methacryloyl group was introduced from H signals of CH ₂ = C- in the vicinity of 5.7 and 6.1 ppm of ¹ H-NMR.

[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 was added 1.0 g of isocyanurate-type hexamethylene diisocyanate (DURANATE (registered trademark) TPA-100) and reacted to obtain a modified polyethylene glycol having three methacryloyl groups in a molecule having a nonvolatile content of 50% To obtain oligomer B-4.

The average molecular weight Mw of the obtained oligomer B-4 was found to be 1740 by GPC.

[Synthesis Example 5]

<Synthesis of acryloyl group-modified dimethylsiloxane-caprolactone block copolymer>

4 g of carbinol (hydroxyl) -terminal polydimethylsiloxane caprolactone block polymer (manufactured by Asmax, Mw 5700 to 6900) was dissolved in toluene, and a tin catalyst was added. To this solution was added 0.22 g of 2-acryloyloxyethyl isocyanate (Car lens AOI (registered trademark) manufactured by Showa Denko K.K.), and the reaction was carried out to obtain a two-terminal acryloyl group-modified dimethylsiloxane-caprolactone block copolymer B -5.

The average molecular weight Mw of the obtained oligomer B-5 was found to be 7100 by GPC.

Example 9

&Lt; Preparation of crosslinked body derived from composition comprising photopolymerizable polyrotaxane only >

To a xylene solution of acryloylated polyrotaxane A-1 obtained in Example 1 was added Irgacure 500 (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone, Ciba Specialty Chemicals Inc., Ltd.) was added in an amount of 5% by weight based on the solid content. This mixture was coated on a glass substrate treated with a release agent using a bar coater and 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 (30 mm in length and 4 mm in width) to prepare test pieces.

The mixture was coated on a black acrylic plate to 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 scratch resistance test.

Example 10

A test piece of a crosslinked product was prepared in the same manner as in Example 9 except that the acryloylated polyrotaxane A-6 obtained in Example 6 was used in place of the acryloylated polyrotaxane A-1 used in Example 9.

Example 11

&Lt; Preparation of crosslinked body derived from composition having photopolymerizable polyrotaxane >

The acryloylated polyrotaxane A-1 obtained in Example 1 and the polycarbonate oligomer B-1 prepared in Synthesis Example 1 were blended at a solid weight ratio of 2: 8, 5: 5, 7: 3, IRGACURE 500 as an initiator was added in an amount of 5% by weight based on the solid content.

The obtained composition was coated on a glass substrate treated with a stripping agent by a bar coater and irradiated with ultraviolet rays at 30 mW / cm ² for 90 seconds, and then the cured film was dried at 110 캜 for 1 hour. The dried film (thickness: 0.2 mm) was peeled off and cut to prepare a test piece.

The obtained composition was coated on a black acrylic plate to 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 scratch resistance test.

Example 12

A crosslinked test piece was prepared 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.

Example 13

A crosslinked test piece was prepared 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.

Example 14

A crosslinked test piece was prepared 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.

Example 15

A test piece of a crosslinked product was prepared in the same manner as in Example 11 except that polypropylene glycol diacrylate B-6 (manufactured by Aldrich, Mn900) was used instead of polycarbonate oligomer B-1.

Example 16

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

Example 17

The acryloylated polyrotaxane A-1 obtained in Example 1 and the polycarbonate oligomer B-1 prepared in Synthesis Example 1 were blended at a solid weight ratio of 7: 3, and the dimethylsiloxane -Caprolactone block copolymer B-5 was added in an amount of 1%. As the photopolymerization initiator, Irgacure 500 was used in an amount of 5% by weight based on the solid content.

The resulting composition was cured in the same manner as in Example 11 to obtain a test piece of a crosslinked body.

Example 18

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. As the photopolymerization initiator, Irgacure 500 was used in an amount of 5% by weight based on the solid content.

The resulting composition was cured in the same manner as in Example 11 to obtain a test piece of a crosslinked body.

(Comparative Examples 1 to 6)

Examples 11 to 15 and 17 were subjected to ultraviolet curing with oligomers alone without addition of polyrotaxane, and Test Specimens C-1 to C-6 of crosslinked oligomers were obtained by the same method.

&Lt; Properties of crosslinked body &

The test pieces prepared in Examples 9 to 18 and Comparative Examples 1 to 6 were evaluated by the following methods.

<< End curl >>

The peeled sheet-like film was repeatedly bent 180 degrees to check for bending streaks and breakage. As a result, the test was carried out five times, and "no change" &Quot; DELTA &quot; indicates that there are slight bending streaks in five tests; &Quot; x &quot; The results are shown in Table 1.

<< Scratch resistance >>

In the tests described above, the surface of the test piece was scratched with a brush made of brass (three rows of bristles, line diameter: 0.15 mm), and the degree of scratching was visually observed Lt; / RTI &gt; As a result, "○" indicates that no scratches were found; &Quot; DELTA &quot; indicates slight scratches but acceptable level; &Quot; x &quot; The results are shown in Table 1.

<< Hysteresis loss >>

The hysteresis loss was measured by the above-described test method.

An example of measurement is shown in Fig. In Fig. 2, (a) shows the results of Comparative Example 1, and (e) shows the results of Example 9. Fig. (B), (c) and (d) show the results of Example 11, wherein the weight ratio of the modified polyrotaxane A-1: oligomer B-1 was 2: 8, 5: 5, and 7: 3 . The arrow in the figure shows the first stretching curve.

In addition, the tensile test of FIG. 2 is performed five times of tension and recovery, and their history is shown.

In FIG. 2 (e), that is, in Example 9, it can be seen that the history is almost straight, and almost the same history is obtained even when the number of times of tension and recovery is five times. When this is regarded as a hysteresis loss value, it is 6%, and it can be seen that the value is close to 0 and the hysteresis loss is low.

On the other hand, in FIG. 2 (a), that is, in Comparative Example 1, it can be seen that the history of five times is different. When this is regarded as the hysteresis loss value, it is 53%, which means that the hysteresis loss value is not satisfactory.

2 (b), 2 (c) and 2 (d) show a history 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 is a table summarizing the above-mentioned characteristics. In the table, "A" indicates the type of polyrotaxane used, "B" indicates the type of the crosslinkable compound used, and "A: B" indicates the weight ratio of the solid content of the crosslinkable compound used with the polyrotaxane used.

From Table 1, it was found that the crosslinked films obtained by using Comparative Examples 1 to 6, that is, the photocrosslinkable compounds alone, did not satisfy both the bending resistance, the scratch resistance and the hysteresis loss.

On the other hand, it can be seen that the crosslinked bodies of the present invention, that is, Examples 9 to 18, satisfy both the bending resistance, the scratch resistance and the hysteresis loss.

From these, the photopolymerizable polyrotaxane of the present invention, the composition having the same, and the crosslinked material derived from the composition have significant effects as compared with those of the conventional ones (Comparative Examples 1 to 6), namely, the bending resistance, scratch resistance and hysteresis loss It was possible to obtain a satisfactory value for all.

Claims (19)

Wherein the cyclic molecule of the polyrotaxane having a blockade group in which the cyclic molecule is not separated from the both ends of a polyrotaxane formed by covering the opening of the cyclic molecule with a skeleton by linear molecules has a hydroxyl group, Some or all of which are substituted with a group represented by the following formula (I)

(Wherein M is represented by the above formula (II)

,
X is a straight chain alkylene or alkenylene group having 1 to 8 carbon atoms; A branched alkylene group or an alkenylene group having 3 to 20 carbon atoms; An alkylene group or an alkenylene group in which a part of the alkylene group or the alkenylene group is substituted with an -O- bond or an -NH- bond; Or an alkylene group in which part of the hydrogen atoms of the alkylene group is substituted with at least one member 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 4.1 to 10,
Y is a group having a photopolymerizable group),
Wherein the cyclic molecule is selected from the group consisting of? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin,
Wherein M is a polymer derived from a lactone monomer, a polymer derived from a cyclic carbonate monomer, or a polymer derived from a lactone monomer and a cyclic carbonate monomer,
Wherein Y has at least one group selected from the group consisting of the following formulas (III-1) to (III-4)

(Wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m 1 is 0 or 1, and * represents a position directly bonded to M in formula (I) or a position bonding with M via a first spacer group) ,
Photopolymerizable polyrotaxane. The photo-crosslinkable polyrose of claim 1, wherein M is a ring-opening polymer from lactone and Y is a group having formula (III-1). The photo-crosslinkable polyroctic acid according to claim 2, wherein the lactone of M is? -Caprolactone, and Y has an acryloyl group, a methacryloyl group, or an acryloyl group and a methacryloyl group. A composition comprising the photo-crosslinkable polyrotaxane according to claim 1 and the photo-crosslinkable compound (B)
The photo-crosslinkable compound (B) is a polymer having at least one group selected from the group Y 'consisting of the following formulas (III'-1 to III'-4)

(Wherein R ₃₃ and R ₃₄ are each independently H or CH ₃ , m 2 is 0 or 1, and * represents a position directly bonding with the polymer of the compound or bonding to the polymer through the second spacer group ). The composition according to claim 4, wherein the polymer of the photo-crosslinking compound (B) has an average weight-average molecular weight of 300 to 10,000. The composition according to claim 4, wherein the photo-crosslinking compound (B) is one selected from the group consisting of the following formulas (IV-1) to (IV-4)

(In the formula,
R ₄₁ is H or CH ₃ ,
R ₄₂ is a linear alkyl or alkenyl group having 1 to 8 carbon atoms, a branched alkyl or alkenyl group having 3 to 20 carbon atoms, an alkyl or alkenyl group in which a part of the alkyl or alkenyl group is substituted with an -O- or -NH- An alkenyl group or an alkyl or alkenyl group in which a part of the hydrogen of the alkyl or alkenyl group is substituted with at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an acyl group, a phenyl group and a halogen atom,
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 trimethylol propane, trimethylol ethane, glycerol, pentaerythritol, dipentaerythritol, isocyanuric acid, diisocyanuric acid, triazine, benzene or a derivative thereof,
M 'is a group having a polymer moiety,
Y 'represents at least one kind of group selected from the group Y'
m2 &quot; is 0 or 1,
Z each independently represent a simple bond or a divalent second spacer group,
r 'represents an integer of 3 to 6,
And the symbol () in parentheses indicates that it is a repeating unit). A crosslinked product derived from the photo-crosslinkable polyrolactone as described in claim 1. A crosslinked body derived from the composition according to claim 4. The crosslinked product according to claim 7 or 8, wherein the photo-crosslinkable polyrotaxane is crosslinked through the Y by light irradiation. The crosslinked product according to claim 8, wherein the Y of the photo-crosslinkable polyrotaxane and the Y 'of the photo-crosslinkable compound (B) are at least crosslinked by light irradiation. The crosslinked product according to claim 7 or 8, wherein the crosslinked product has a hysteresis loss of 25% or less. (1) a step of preparing a polyrotaxane having a blockade group disposed on both ends of a polyrotaxane-like polyanthenic acid in which openings of the cyclic molecule are entangled in a skewer shape by linear molecules so that the cyclic molecules are not separated;
(2) a step of introducing -M- represented by the following formula (II) into a part or all of the cyclic molecule of the polyrotaxane

(Wherein X is a straight chain alkylene group or an alkenylene group having 1 to 8 carbon atoms, a branched chain alkylene group or an 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 an NH- bond, or an alkylene group in which part of the hydrogen atoms of the alkylene group is substituted with at least one member 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 of 4.1 to 10;
(3) a step of introducing a group Y having a photopolymerizable group to the M to form -MY
Lt; / RTI &
Wherein the cyclic molecule is selected from the group consisting of? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin,
Wherein M is a polymer derived from a lactone monomer, a polymer derived from a cyclic carbonate monomer, or a polymer derived from a lactone monomer and a cyclic carbonate monomer,
Wherein Y has at least one group selected from the group consisting of the following formulas (III-1) to (III-4)

(Wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m 1 is 0 or 1, and * represents a position directly bonded to M in formula (I) or a position bonding with M via a first spacer group) ,
(A) A process for producing a photopolymerizable polyrotaxane. The method according to claim 12, wherein in (2), the monomer having the structure of the following formula (II ') is subjected to ring-opening polymerization to introduce the -M-.

(In the formula, X is as defined in claim 12) (A) a photopolymerizable polyrotaxane; And (B) a photocrosslinking compound,
(i) preparing the photopolymerizable polyrotaxane (A);
(ii) preparing the photo-crosslinking compound (B); And
(iii) a step of mixing the photopolymerizable polyrotaxane (A) and the photopolymerizable compound (B) to obtain a composition having them
Lt; / RTI &
The step i)
(1) a step of preparing a polyrotaxane having a blockade group disposed on both ends of a polyrotaxane-like polyanthenic acid in which openings of the cyclic molecule are entangled in a skewer shape by linear molecules so that the cyclic molecules are not separated;
(2) a step of introducing -M- represented by the following formula (II) into a part or all of the cyclic molecule of the polyrotaxane

(Wherein X is a straight chain alkylene group or an alkenylene group having 1 to 8 carbon atoms, a branched chain alkylene group or an 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 an NH- bond, or an alkylene group in which part of the hydrogen atoms of the alkylene group is substituted with at least one member 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 of 4.1 to 10; And
(3) a step of introducing a group Y having a photopolymerizable group to the M to form -MY
Lt; / RTI &
Wherein the cyclic molecule is selected from the group consisting of? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin,
Wherein M is a polymer derived from a lactone monomer, a polymer derived from a cyclic carbonate monomer, or a polymer derived from a lactone monomer and a cyclic carbonate monomer,
Wherein Y has at least one group selected from the group consisting of the following formulas (III-1) to (III-4)

(Wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m 1 is 0 or 1, and * represents a position directly bonded to M in formula (I) or a position bonding with M via a first spacer group) ,
(A) a photopolymerizable polyrotaxane; And (B) a photocrosslinkable compound. (A) a photopolymerizable polyrotaxane; And (B) a photo-crosslinkable compound,
(i) preparing the photopolymerizable polyrotaxane (A);
(ii) preparing the photo-crosslinking compound (B);
(iii) mixing the photopolymerizable polyrotaxane (A) and the photopolymerizable compound (B) to obtain a composition having them;
(iv) adding a photopolymerization initiator to the composition; And
(v) a step of irradiating the obtained composition with light to form a crosslinked body
Lt; / RTI &
The step i)
(1) a step of preparing a polyrotaxane having a blockade group disposed on both ends of a polyrotaxane-like polyanthenic acid in which openings of the cyclic molecule are entangled in a skewer shape by linear molecules so that the cyclic molecules are not separated;
(2) a step of introducing -M- represented by the following formula (II) into a part or all of the cyclic molecule of the polyrotaxane

(Wherein X is a straight chain alkylene group or an alkenylene group having 1 to 8 carbon atoms, a branched chain alkylene group or an 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 an NH- bond, or an alkylene group in which part of the hydrogen atoms of the alkylene group is substituted with at least one member 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 of 4.1 to 10; And
(3) a step of introducing a group Y having a photopolymerizable group to the M to form -MY
Lt; / RTI &
Wherein the cyclic molecule is selected from the group consisting of? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin,
Wherein M is a polymer derived from a lactone monomer, a polymer derived from a cyclic carbonate monomer, or a polymer derived from a lactone monomer and a cyclic carbonate monomer,
Wherein Y has at least one group selected from the group consisting of the following formulas (III-1) to (III-4)

(Wherein R ₃₁ and R ₃₂ are each independently H or CH ₃ , m 1 is 0 or 1, and * represents a position directly bonded to M in formula (I) or a position bonding with M via a first spacer group) ,
(A) a photopolymerizable polyrotaxane; And (B) a photocrosslinking compound. delete delete delete delete

Images